Structure and dynamics of confined flexible and unentangled polymer melts in highly adsorbing cylindrical pores

Carrillo, Jan-Michael Y.; Sumpter, Bobby G.

doi:10.1063/1.4893055

Title: Structure and dynamics of confined flexible and unentangled polymer melts in highly adsorbing cylindrical pores

Journal Article · Fri Aug 01 00:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4893055· OSTI ID:1159493

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ORNL

Coarse-grained molecular dynamics simulations are used to probe the dynamic phenomena of polymer melts confined in nanopores. The simulation results show excellent agreement in the values obtained for the normalized coherent single chain dynamic structure factor, S(Q,t) S(Q,0) . In the bulk configuration, both simulations and experiments confirm that the polymer chains follow Rouse dynamics. However, under confinement, the Rouse modes are suppressed. The mean-square radius of gyration R2 g and the average relative shape anisotropy κ2 of the conformation of the polymer chains indicate a pancake-like conformation near the surface and a bulk-like conformation near the center of the confining cylinder. This was confirmed by direct visualization of the polymer chains. Despite the presence of these different conformations, the average form factor of the confined chains still follows the Debye function which describes linear ideal chains, which is in agreement with small angle neutron scattering experiments (SANS). The experimentally inaccessible mean-square displacement (MSD) of the confined monomers, calculated as a function of radial distance from the pore surface, was obtained in the simulations. The simulations show a gradual increase of the MSD from the adsorbed, but mobile layer, to that similar to the bulk far away from the surface.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1159493

Journal Information:: Journal of Chemical Physics, Vol. 141, Issue 7; ISSN 0021-9606

Country of Publication:: United States

Language:: English

References (37)

Strain localization in glassy polymers under cylindrical confinement Shavit, Amit; Riggleman, Robert A. Physical Chemistry Chemical Physics, Vol. 16, Issue 22 https://doi.org/10.1039/c3cp55330b	journal	January 2014
Polymer Dynamics of Polybutadiene in Nanoscopic Confinement As Revealed by Field Cycling ¹ H NMR Hofmann, M.; Herrmann, A.; Ok, S. Macromolecules, Vol. 44, Issue 11 https://doi.org/10.1021/ma2002504	journal	June 2011
Implementing molecular dynamics on hybrid high performance computers – short range forces Brown, W. Michael; Wang, Peng; Plimpton, Steven J. Computer Physics Communications, Vol. 182, Issue 4 https://doi.org/10.1016/j.cpc.2010.12.021	journal	April 2011
One Dimensional PMMA Nanofibers from AAO Templates. Evidence of Confinement Effects by Dielectric and Raman Analysis Blaszczyk-Lezak, Iwona; Hernández, Marianella; Mijangos, Carmen Macromolecules, Vol. 46, Issue 12 https://doi.org/10.1021/ma400173q	journal	June 2013
Coherent Dynamic Structure Factor of a Polymer Chain Confined Into a Harmonic Radial Potential Dolgushev, Maxim; Krutyeva, Margarita Macromolecular Theory and Simulations, Vol. 21, Issue 8 https://doi.org/10.1002/mats.201200045	journal	August 2012
Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids Weeks, John D.; Chandler, David; Andersen, Hans C. The Journal of Chemical Physics, Vol. 54, Issue 12 https://doi.org/10.1063/1.1674820	journal	June 1971
Interface and Interphase Dynamics of Polystyrene Chains near Grafted and Ungrafted Silica Nanoparticles Ndoro, Tinashe V. M.; Böhm, Michael C.; Müller-Plathe, Florian Macromolecules, Vol. 45, Issue 1 https://doi.org/10.1021/ma2020613	journal	December 2011
Polymers under Confinement Rice, Stuart A.; Dinner, Aaron R. Advances in Chemical Physics, Vol. 149 https://doi.org/10.1002/9781118180396.ch4	book	January 2012
What Happens to Polymer Chains Confined in Rigid Cylindrical Inorganic (AAO) Nanopores Noirez, L.; Stillings, C.; Bardeau, J. -F. Macromolecules, Vol. 46, Issue 12 https://doi.org/10.1021/ma4005605	journal	June 2013
Enhanced mobility of confined polymers Shin, Kyusoon; Obukhov, Sergei; Chen, Jiun-Tai Nature Materials, Vol. 6, Issue 12 https://doi.org/10.1038/nmat2031	journal	October 2007
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Monte Carlo Studies of Lattice‐Model Polymer Chains. I. Correlation Functions in the Statistical‐Bead Model Verdier, Peter H. The Journal of Chemical Physics, Vol. 45, Issue 6 https://doi.org/10.1063/1.1727896	journal	September 1966
Shape of unperturbed linear polymers: polypropylene Theodorou, Doros N.; Suter, Ulrich W. Macromolecules, Vol. 18, Issue 6 https://doi.org/10.1021/ma00148a028	journal	November 1985
Nanoporous anodic aluminium oxide: Advances in surface engineering and emerging applications Md Jani, Abdul Mutalib; Losic, Dusan; Voelcker, Nicolas H. Progress in Materials Science, Vol. 58, Issue 5 https://doi.org/10.1016/j.pmatsci.2013.01.002	journal	June 2013
Effect of Nanoconfinement on Polymer Dynamics: Surface Layers and Interphases Krutyeva, M.; Wischnewski, A.; Monkenbusch, M. Physical Review Letters, Vol. 110, Issue 10 https://doi.org/10.1103/PhysRevLett.110.108303	journal	March 2013
Single-polymer dynamics under constraints: scaling theory and computer experiment Milchev, Andrey Journal of Physics: Condensed Matter, Vol. 23, Issue 10 https://doi.org/10.1088/0953-8984/23/10/103101	journal	February 2011
Characterization of Polymer Nanocomposite Interphase and Its Impact on Mechanical Properties Ciprari, Dan; Jacob, Karl; Tannenbaum, Rina Macromolecules, Vol. 39, Issue 19 https://doi.org/10.1021/ma0602270	journal	September 2006
A Theory of the Linear Viscoelastic Properties of Dilute Solutions of Coiling Polymers Rouse, Prince E. The Journal of Chemical Physics, Vol. 21, Issue 7 https://doi.org/10.1063/1.1699180	journal	July 1953
Microscopic Dynamics of Polyethylene Glycol Chains Interacting with Silica Nanoparticles Glomann, T.; Schneider, G. J.; Allgaier, J. Physical Review Letters, Vol. 110, Issue 17 https://doi.org/10.1103/PhysRevLett.110.178001	journal	April 2013
Statics and dynamics of a single polymer chain confined in a tube Sheng, Yu-Jane; Wang, Meng-Chieh The Journal of Chemical Physics, Vol. 114, Issue 10 https://doi.org/10.1063/1.1345879	journal	January 2001
Glass-Transition Temperature Gradient in Nanocomposites: Evidence from Nuclear Magnetic Resonance and Differential Scanning Calorimetry Papon, Aurélie; Montes, Hélène; Hanafi, Mohamed Physical Review Letters, Vol. 108, Issue 6 https://doi.org/10.1103/PhysRevLett.108.065702	journal	February 2012
Segmental dynamics of polymers during capillary flow into nanopores Serghei, A.; Chen, D.; Lee, D. H. Soft Matter, Vol. 6, Issue 6 https://doi.org/10.1039/b921757f	journal	January 2010
Rouse Dynamics of Polyelectrolyte Solutions: Molecular Dynamics Study Liao, Qi; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V. Macromolecules, Vol. 40, Issue 21 https://doi.org/10.1021/ma070666e	journal	October 2007
Combined FTIR and Dielectric Investigation of Poly(vinyl acetate) Adsorbed on Silica Particles Füllbrandt, Marieke; Purohit, Purv J.; Schönhals, Andreas Macromolecules, Vol. 46, Issue 11 https://doi.org/10.1021/ma400461p	journal	May 2013
Closed-Form Expressions for the Form Factor of a Polymer under Strong Confinement: Form Factor of a Polymer under Strong Confinement Zorn, Reiner Macromolecular Theory and Simulations, Vol. 23, Issue 2 https://doi.org/10.1002/mats.201300135	journal	November 2013
Segment diffusion in polymers confined in nanopores: A fringe-field NMR diffusometry study Fischer, Elmar; Kimmich, Rainer; Beginn, Uwe Physical Review E, Vol. 59, Issue 4 https://doi.org/10.1103/PhysRevE.59.4079	journal	April 1999
The structure of a hard-sphere fluid in contact with a soft repulsive wall Abraham, Farid F.; Singh, Y. The Journal of Chemical Physics, Vol. 67, Issue 5 https://doi.org/10.1063/1.435080	journal	January 1977
Unexpected relaxation dynamics of a self-avoiding polymer in cylindrical confinement Arnold, Axel; Bozorgui, Behnaz; Frenkel, Daan The Journal of Chemical Physics, Vol. 127, Issue 16 https://doi.org/10.1063/1.2799513	journal	October 2007
Compression and Stretching of a Self-Avoiding Chain in Cylindrical Nanopores Jun, Suckjoon; Thirumalai, D.; Ha, Bae-Yeun Physical Review Letters, Vol. 101, Issue 13 https://doi.org/10.1103/PhysRevLett.101.138101	journal	September 2008
Study of the dynamics of poly(ethylene oxide) by combining molecular dynamic simulations and neutron scattering experiments Brodeck, M.; Alvarez, F.; Arbe, A. The Journal of Chemical Physics, Vol. 130, Issue 9 https://doi.org/10.1063/1.3077858	journal	March 2009
Immobilized Polymer Layers on Spherical Nanoparticles Harton, Shane E.; Kumar, Sanat K.; Yang, Hoichang Macromolecules, Vol. 43, Issue 7 https://doi.org/10.1021/ma902484d	journal	April 2010
Elasticity of flexible polymers under cylindrical confinement: appreciating the blob scaling regime in computer simulations Kim, Juin; Jeon, Chanil; Jeong, Hawoong Soft Matter, Vol. 9, Issue 26 https://doi.org/10.1039/c3sm50742d	journal	January 2013
Influence of Surface Grafted Polymers on the Polymer Dynamics in a Silica–Polystyrene Nanocomposite: A Coarse-Grained Molecular Dynamics Investigation Ghanbari, Azadeh; Rahimi, Mohammad; Dehghany, Jaber The Journal of Physical Chemistry C, Vol. 117, Issue 47 https://doi.org/10.1021/jp407109r	journal	November 2013
Non-ideality of polymer melts confined to nanotubes Lee, N. -K.; Farago, J.; Meyer, H. EPL (Europhysics Letters), Vol. 93, Issue 4 https://doi.org/10.1209/0295-5075/93/48002	journal	February 2011
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
Neutron scattering study of the dynamics of a polymer melt under nanoscopic confinement Krutyeva, Margarita; Martin, Jaime; Arbe, Arantxa The Journal of Chemical Physics, Vol. 131, Issue 17 https://doi.org/10.1063/1.3258329	journal	November 2009
Dynamics at the Polymer/Nanoparticle Interface in Poly(2-vinylpyridine)/Silica Nanocomposites Holt, Adam P.; Griffin, Philip J.; Bocharova, Vera Macromolecules, Vol. 47, Issue 5 https://doi.org/10.1021/ma5000317	journal	February 2014

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