Multiscale Dynamics of Polymers in Particle-Rich Nanocomposites
Abstract
In this paper we report on the dynamics of entangled polymers in polymer–nanoparticle composites (PNCs) with moderate and high particle loadings. Using composites comprised of poly(ethylene glycol) (PEG)-tethered silica (SiO2) nanoparticles and poly(methyl methacrylate) (PMMA), we show by means of small-angle X-ray scattering (SAXS) analysis that the nanoparticles are uniformly dispersed over a range of particle concentrations. From oscillatory shear rheology measurements, we find that the time–temperature superposition (TTS) principle holds for these SiO2-PEG/PMMA PNCs up to a particle concentration ΦG ≈ 11% where the materials begin to exhibit soft glassy rheological properties. At particle concentrations below ΦG, we take advantage of TTS to create dynamic maps for PNCs that span time scales ranging from fast segmental motions to slow terminal relaxation of polymer chains. These maps reveal that at low Φ and depending on the host polymer (PMMA) molecular weight (Mw), hairy nanoparticles may either speed up or slow down terminal relaxation of the host. In contrast, at high Φ, nanoparticles slow down polymer dynamics on intermediate and long time scales, irrespective of the host polymer Mw. The slowdown coincides with particle concentrations at which the mean interparticle spacing lies below the equilibrium tube diameter of the entangled PMMAmore »
- Authors:
-
- Cornell Univ., Ithaca, NY (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Science Foundation (NSF)
- OSTI Identifier:
- 1327063
- Grant/Contract Number:
- CBET-1512297; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 49; Journal Issue: 14; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Polymer particles; Nanoparticles; Nanocomposites; Organic compounds; Polymers
Citation Formats
Mangal, Rahul, Wen, Yu Ho, Choudhury, Snehashis, and Archer, Lynden A. Multiscale Dynamics of Polymers in Particle-Rich Nanocomposites. United States: N. p., 2016.
Web. doi:10.1021/acs.macromol.6b00496.
Mangal, Rahul, Wen, Yu Ho, Choudhury, Snehashis, & Archer, Lynden A. Multiscale Dynamics of Polymers in Particle-Rich Nanocomposites. United States. https://doi.org/10.1021/acs.macromol.6b00496
Mangal, Rahul, Wen, Yu Ho, Choudhury, Snehashis, and Archer, Lynden A. Thu .
"Multiscale Dynamics of Polymers in Particle-Rich Nanocomposites". United States. https://doi.org/10.1021/acs.macromol.6b00496. https://www.osti.gov/servlets/purl/1327063.
@article{osti_1327063,
title = {Multiscale Dynamics of Polymers in Particle-Rich Nanocomposites},
author = {Mangal, Rahul and Wen, Yu Ho and Choudhury, Snehashis and Archer, Lynden A.},
abstractNote = {In this paper we report on the dynamics of entangled polymers in polymer–nanoparticle composites (PNCs) with moderate and high particle loadings. Using composites comprised of poly(ethylene glycol) (PEG)-tethered silica (SiO2) nanoparticles and poly(methyl methacrylate) (PMMA), we show by means of small-angle X-ray scattering (SAXS) analysis that the nanoparticles are uniformly dispersed over a range of particle concentrations. From oscillatory shear rheology measurements, we find that the time–temperature superposition (TTS) principle holds for these SiO2-PEG/PMMA PNCs up to a particle concentration ΦG ≈ 11% where the materials begin to exhibit soft glassy rheological properties. At particle concentrations below ΦG, we take advantage of TTS to create dynamic maps for PNCs that span time scales ranging from fast segmental motions to slow terminal relaxation of polymer chains. These maps reveal that at low Φ and depending on the host polymer (PMMA) molecular weight (Mw), hairy nanoparticles may either speed up or slow down terminal relaxation of the host. In contrast, at high Φ, nanoparticles slow down polymer dynamics on intermediate and long time scales, irrespective of the host polymer Mw. The slowdown coincides with particle concentrations at which the mean interparticle spacing lies below the equilibrium tube diameter of the entangled PMMA host and is thought to reflect the onset of confinement dynamics of polymer chains in PNCs. Studies of PNCs in the confinement regime reveal important analogies between glassy attributes of 3D-confined polymer chains in nanocomposites with those of polymer thin films supported on attractive substrates.},
doi = {10.1021/acs.macromol.6b00496},
journal = {Macromolecules},
number = 14,
volume = 49,
place = {United States},
year = {Thu Jul 14 00:00:00 EDT 2016},
month = {Thu Jul 14 00:00:00 EDT 2016}
}
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Works referenced in this record:
Processing and properties of polymeric nano-composites
journal, November 2001
- Wang, Hua; Zeng, Changchun; Elkovitch, Mark
- Polymer Engineering & Science, Vol. 41, Issue 11
Polymer Layered Silicate Nanocomposites
journal, January 1996
- Giannelis, Emmanuel P.
- Advanced Materials, Vol. 8, Issue 1
Flammability and thermal stability studies of polymer layered-silicate (clay) nanocomposites
journal, September 1999
- Gilman, J.
- Applied Clay Science, Vol. 15, Issue 1-2
A review on polymer–layered silicate nanocomposites
journal, December 2008
- Pavlidou, S.; Papaspyrides, C. D.
- Progress in Polymer Science, Vol. 33, Issue 12
Polymer/clay nanocomposites and their gas barrier properties
journal, June 2013
- Kalendova, Alena; Merinska, Dagmar; Gerard, Jean Francois
- Polymer Composites, Vol. 34, Issue 9
Microstructure and tribological behavior of polymeric nanocomposites
journal, April 2001
- Zhi Rong, Min; Qiu Zhang, Ming; Liu, Hong
- Industrial Lubrication and Tribology, Vol. 53, Issue 2
A highly reversible room-temperature lithium metal battery based on crosslinked hairy nanoparticles
journal, December 2015
- Choudhury, Snehashis; Mangal, Rahul; Agrawal, Akanksha
- Nature Communications, Vol. 6, Issue 1
Stress Relaxation of Star/Linear Polymer Blends
journal, August 2002
- Lee, Jung Hun; Archer, Lynden A.
- Macromolecules, Vol. 35, Issue 17
Entanglement friction and dynamics in blends of starlike and linear polymer molecules
journal, January 2001
- Lee, Jung Hun; Archer, Lynden A.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 39, Issue 20
Enthalpic Stabilization of Brush-Coated Particles in a Polymer Melt
journal, June 2002
- Borukhov, Itamar; Leibler, Ludwik
- Macromolecules, Vol. 35, Issue 13
Nanorod Self-Assembly for Tuning Optical Absorption
journal, October 2010
- Hore, Michael J. A.; Composto, Russell J.
- ACS Nano, Vol. 4, Issue 11
Phase stability and dynamics of entangled polymer–nanoparticle composites
journal, June 2015
- Mangal, Rahul; Srivastava, Samanvaya; Archer, Lynden A.
- Nature Communications, Vol. 6, Issue 1
Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites
journal, January 2016
- Mangal, Rahul; Srivastava, Samanvaya; Narayanan, Suresh
- Langmuir, Vol. 32, Issue 2
Mobility of Nonsticky Nanoparticles in Polymer Liquids
journal, October 2011
- Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
- Macromolecules, Vol. 44, Issue 19
Hopping Diffusion of Nanoparticles in Polymer Matrices
journal, January 2015
- Cai, Li-Heng; Panyukov, Sergey; Rubinstein, Michael
- Macromolecules, Vol. 48, Issue 3
Microscopic Theory of the Long-Time Diffusivity and Intermediate-Time Anomalous Transport of a Nanoparticle in Polymer Melts
journal, December 2014
- Yamamoto, Umi; Schweizer, Kenneth S.
- Macromolecules, Vol. 48, Issue 1
Monolithic Composite Electrodes Comprising Silicon Nanoparticles Embedded in Lignin-derived Carbon Fibers for Lithium-Ion Batteries
journal, August 2014
- Rios, Orlando; Martha, Surendra K.; McGuire, Michael A.
- Energy Technology, Vol. 2, Issue 9-10
Cooperation between Active Material, Polymeric Binder and Conductive Carbon Additive in Lithium Ion Battery Cathode
journal, February 2012
- Zheng, Honghe; Yang, Ruizhi; Liu, Gao
- The Journal of Physical Chemistry C, Vol. 116, Issue 7
Highly Stretchable and Conductive Silver Nanoparticle Embedded Graphene Flake Electrode Prepared by In situ Dual Reduction Reaction
journal, September 2015
- Yoon, Yeoheung; Samanta, Khokan; Lee, Hanleem
- Scientific Reports, Vol. 5, Issue 1
A Solution Processed Flexible Nanocomposite Electrode with Efficient Light Extraction for Organic Light Emitting Diodes
journal, March 2014
- Li, Lu; Liang, Jiajie; Chou, Shu-Yu
- Scientific Reports, Vol. 4, Issue 1
Materials for suspension (semi-solid) electrodes for energy and water technologies
journal, January 2015
- Hatzell, Kelsey B.; Boota, Muhammad; Gogotsi, Yury
- Chemical Society Reviews, Vol. 44, Issue 23
Nanoscale Ionic Materials
journal, November 2008
- Rodriguez, Robert; Herrera, Rafael; Archer, Lynden A.
- Advanced Materials, Vol. 20, Issue 22
Tethered Nanoparticle–Polymer Composites: Phase Stability and Curvature
journal, April 2012
- Srivastava, Samanvaya; Agarwal, Praveen; Archer, Lynden A.
- Langmuir, Vol. 28, Issue 15
Glass-transition temperatures of compatible polymer mixtures
journal, February 1979
- Couchman, P. R.
- Physics Letters A, Vol. 70, Issue 2
Dependence of the Fictive Temperature of Glass on Cooling Rate
journal, January 1976
- Moynihan, Cornelius T.; Easteal, Allan J.; Bolt, Mary Ann
- Journal of the American Ceramic Society, Vol. 59, Issue 1-2
Ideal copolymers and the second-order transitions of synthetic rubbers. i. non-crystalline copolymers
journal, September 1952
- Gordon, Manfred; Taylor, James S.
- Journal of Applied Chemistry, Vol. 2, Issue 9
Compositional Variation of Glass-Transition Temperatures. 2. Application of the Thermodynamic Theory to Compatible Polymer Blends
journal, November 1978
- Couchman, P. R.
- Macromolecules, Vol. 11, Issue 6
Relationship between the glass transition temperature and the interaction parameter of miscible binary polymer blends
journal, June 1992
- Lu, Xinya; Weiss, R. A.
- Macromolecules, Vol. 25, Issue 12
Influence of composition and molecular mass on the morphology, crystallization and melting behaviour of poly(ethylene oxide)/poly(methyl methacrylate) blends
journal, August 1984
- Martuscelli, E.; Pracella, M.; Wang, Ping Yue
- Polymer, Vol. 25, Issue 8
Melting point depression in poly (ethylene oxide)-poly (methyl methacrylate) blends
journal, January 1982
- Cortazar, M. M.; Calahorra, M. E.; Guzmán, G. M.
- European Polymer Journal, Vol. 18, Issue 2
Miscibility prediction based on the corresponding states theory: poly(ethylene oxide)/atactic poly(methyl methacrylate) system
journal, March 1989
- Cimmino, S.; Martuscelli, E.; Silvestre, C.
- Polymer, Vol. 30, Issue 3
Thermodynamics of blends of poly(ethylene oxide) with poly(methyl methacrylate) and poly(vinyl acetate): Prediction of miscibility based on Flory solution theory modified by Hamada
journal, September 1998
- Chen, Xue; Yin, Jinghua; Alfonso, G. C.
- Polymer, Vol. 39, Issue 20
Interactions in mixtures of poly(ethylene oxide) and poly(methyl methacrylate)
journal, September 1987
- Ito, H.; Russell, T. P.; Wignall, G. D.
- Macromolecules, Vol. 20, Issue 9
Thermodynamics of poly(ethylene oxide)-poly(methyl methacrylate) blends: prediction of miscibility based on the corresponding-states theory
journal, July 1994
- Pedemonte, E.; Polleri, V.; Turturro, A.
- Polymer, Vol. 35, Issue 15
Quantitative equivalence between polymer nanocomposites and thin polymer films
journal, August 2005
- Bansal, Amitabh; Yang, Hoichang; Li, Chunzhao
- Nature Materials, Vol. 4, Issue 9
Interface and surface effects on the glass-transition temperature in thin polymer films
journal, January 1994
- Keddie, Joseph L.; Jones, Richard A. L.; Cory, Rachel A.
- Faraday Discussions, Vol. 98
Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites
journal, March 2007
- Rittigstein, Perla; Priestley, Rodney D.; Broadbelt, Linda J.
- Nature Materials, Vol. 6, Issue 4
Effect of strongly favorable substrate interactions on the thermal properties of ultrathin polymer films
journal, March 1996
- van Zanten, John H.; Wallace, William E.; Wu, Wen-li
- Physical Review E, Vol. 53, Issue 3
Experimental Evidence for a New Parameter to Control the Glass Transition of Confined Polymers
journal, April 2007
- Srivastava, S.; Basu, J. K.
- Physical Review Letters, Vol. 98, Issue 16
Effects of confinement on material behaviour at the nanometre size scale
journal, April 2005
- Alcoutlabi, Mataz; McKenna, Gregory B.
- Journal of Physics: Condensed Matter, Vol. 17, Issue 15
Relation between Glass Transition Temperatures in Polymer Nanocomposites and Polymer Thin Films
journal, August 2008
- Kropka, Jamie M.; Pryamitsyn, Victor; Ganesan, Venkat
- Physical Review Letters, Vol. 101, Issue 7
Molecular mass dependence of point-to-set correlation length scale in polymers
journal, August 2012
- Hanson, Ben; Pryamitsyn, Victor; Ganesan, Venkat
- The Journal of Chemical Physics, Vol. 137, Issue 8
Size-Dependent Depression of the Glass Transition Temperature in Polymer Films
journal, July 1994
- Keddie, J. L.; Jones, R. A. L.; Cory, R. A.
- Europhysics Letters (EPL), Vol. 27, Issue 1
Dynamics and Rheology of Soft Colloidal Glasses
journal, January 2015
- Wen, Yu Ho; Schaefer, Jennifer L.; Archer, Lynden A.
- ACS Macro Letters, Vol. 4, Issue 1
Dynamics of Entangled Chains in Polymer Nanocomposites
journal, August 2011
- Schneider, G. J.; Nusser, K.; Willner, L.
- Macromolecules, Vol. 44, Issue 15
Nanoparticle Effect on the Dynamics of Polymer Chains and Their Entanglement Network
journal, September 2012
- Li, Ying; Kröger, Martin; Liu, Wing Kam
- Physical Review Letters, Vol. 109, Issue 11
Theory of Entanglements and Tube Confinement in Rod–Sphere Nanocomposites
journal, October 2013
- Yamamoto, Umi; Schweizer, Kenneth S.
- ACS Macro Letters, Vol. 2, Issue 11
Relaxation in glassforming liquids and amorphous solids
journal, September 2000
- Angell, C. A.; Ngai, K. L.; McKenna, G. B.
- Journal of Applied Physics, Vol. 88, Issue 6
Probing Slow Dynamics in Supported Thin Polymer Films
journal, July 2005
- Fakhraai, Zahra; Forrest, James A.
- Physical Review Letters, Vol. 95, Issue 2
Glass Transition Dynamics and Surface Layer Mobility in Unentangled Polystyrene Films
journal, June 2010
- Yang, Z.; Fujii, Y.; Lee, F. K.
- Science, Vol. 328, Issue 5986
On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids
journal, July 1965
- Adam, Gerold; Gibbs, Julian H.
- The Journal of Chemical Physics, Vol. 43, Issue 1
Glass transition behavior and dynamic fragility in polylactides containing mobile and rigid amorphous fractions
journal, September 2008
- Zuza, Ester; Ugartemendia, Jone M.; Lopez, Alberto
- Polymer, Vol. 49, Issue 20
Dielectric Spectroscopy Investigation of Relaxation in C 60 −Polyisoprene Nanocomposites
journal, April 2009
- Ding, Yifu; Pawlus, Sebastian; Sokolov, Alexei P.
- Macromolecules, Vol. 42, Issue 8
Glass formation and stability of polystyrene–fullerene nanocomposites
journal, April 2010
- Wong, Him C.; Sanz, Alejandro; Douglas, Jack F.
- Journal of Molecular Liquids, Vol. 153, Issue 1
Slow dynamics near glass transitions in thin polymer films
journal, June 2001
- Fukao, Koji; Miyamoto, Yoshihisa
- Physical Review E, Vol. 64, Issue 1
Influence of Confinement on the Fragility of Antiplasticized and Pure Polymer Films
journal, July 2006
- Riggleman, Robert A.; Yoshimoto, Kenji; Douglas, Jack F.
- Physical Review Letters, Vol. 97, Issue 4
Molecular Mobility and Glass Transition of Thin Films of Poly(bisphenol A carbonate)
journal, January 2012
- Yin, Huajie; Napolitano, Simone; Schönhals, Andreas
- Macromolecules, Vol. 45, Issue 3
A unifying framework to quantify the effects of substrate interactions, stiffness, and roughness on the dynamics of thin supported polymer films
journal, June 2015
- Hanakata, Paul Z.; Pazmiño Betancourt, Beatriz A.; Douglas, Jack F.
- The Journal of Chemical Physics, Vol. 142, Issue 23
Local variation of fragility and glass transition temperature of ultra-thin supported polymer films
journal, December 2012
- Hanakata, Paul Z.; Douglas, Jack F.; Starr, Francis W.
- The Journal of Chemical Physics, Vol. 137, Issue 24
Nanoconfinement effects on the fragility of glass formation of a model freestanding polymer film
journal, January 2014
- Marvin, M. D.; Lang, R. J.; Simmons, D. S.
- Soft Matter, Vol. 10, Issue 18
Works referencing / citing this record:
Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations
journal, January 2017
- Senses, Erkan; Tyagi, Madhusudan; Natarajan, Bharath
- Soft Matter, Vol. 13, Issue 43
Dynamics heterogeneity in silica-filled nitrile butadiene rubber
journal, February 2018
- Xu, Huilong; Song, Yihu; Jia, Erwen
- Journal of Applied Polymer Science, Vol. 135, Issue 22
Glass transition of polymers in bulk, confined geometries, and near interfaces
journal, January 2017
- Napolitano, Simone; Glynos, Emmanouil; Tito, Nicholas B.
- Reports on Progress in Physics, Vol. 80, Issue 3
Translational and rotational dynamics of an ultra-thin nanorod probe particle in linear polymer melts
journal, January 2018
- Li, Shu-Jia; Qian, Hu-Jun; Lu, Zhong-Yuan
- Physical Chemistry Chemical Physics, Vol. 20, Issue 32
Strain rate and temperature dependence of the mechanical properties of polymers: A universal time-temperature superposition principle
journal, July 2018
- Tao, Wei; Shen, Jianxiang; Chen, Yulong
- The Journal of Chemical Physics, Vol. 149, Issue 4
Influence of molecular weight on molecular dynamics and dynamic rheology of polypropylene glycol filled with silica
journal, January 2018
- Ma, Furui; Xu, Bei; Song, Yihu
- RSC Advances, Vol. 8, Issue 56
Miscibility and Nanoparticle Diffusion in Ionic Nanocomposites
text, January 2018
- V., Karatrantos, Argyrios,; Yao, Koutsawa,; Philippe, Dubois,
- ETH Zurich