Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation

Xu, Wen -Sheng; Carrillo, Jan-Michael Y.; Lam, Christopher N.; Sumpter, Bobby G.; Wang, Yangyang

doi:10.1021/acsmacrolett.7b00900

Title: Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation

Journal Article · 24 January 2018 · ACS Macro Letters

DOI: https://doi.org/10.1021/acsmacrolett.7b00900 · OSTI ID:1479793

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

The chain retraction hypothesis of the tube model for nonlinear polymer rheology has been challenged by the recent small-angle neutron scattering (SANS) experiment. In this study, we further examine the microscopic relaxation mechanism of entangled polymer melts after a large step uniaxial extension by using large-scale molecular dynamics simulation. We show that the unique structural features associated with the chain retraction mechanism of the tube model are absent in our simulations, in agreement with the previous experimental results. In contrast to SANS experiments, molecular dynamics simulations allow us to accurately and unambiguously determine the evolution of the radius of gyration tensor of a long polymer chain after a large step deformation. Contrary to the prediction of the tube model, our simulations reveal that the radius of gyration in the perpendicular direction to stretching increases monotonically toward its equilibrium value throughout the stress relaxation. These results provide a critical step in improving our understanding of nonlinear rheology of entangled polymers.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: DOE Office of Science; USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1479793

Journal Information:: ACS Macro Letters, Journal Name: ACS Macro Letters Journal Issue: 2 Vol. 7; ISSN 2161-1653

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Dynamics of entangled linear, branched, and cyclic polymers Klein, Jacob Macromolecules, Vol. 19, Issue 1 https://doi.org/10.1021/ma00155a018	journal	January 1986
Spatial distribution of entanglements in thin free-standing films Sussman, Daniel M. Physical Review E, Vol. 94, Issue 1 https://doi.org/10.1103/PhysRevE.94.012503	journal	July 2016
Small-angle neutron scattering from a polymer coil undergoing stress relaxation Maconnachie, Ann; Allen, Geoffrey; Richards, Randal W. Polymer, Vol. 22, Issue 9 https://doi.org/10.1016/0032-3861(81)90126-9	journal	September 1981
Molecular dynamics simulations of deformation mechanisms of amorphous polyethylene Hossain, D.; Tschopp, M. A.; Ward, D. K. Polymer, Vol. 51, Issue 25 https://doi.org/10.1016/j.polymer.2010.10.009	journal	November 2010
Plastic Deformation Mechanisms of Semicrystalline and Amorphous Polymers Jabbari-Farouji, Sara; Rottler, Joerg; Lame, Olivier ACS Macro Letters, Vol. 4, Issue 2 https://doi.org/10.1021/mz500754b	journal	January 2015
Segment connectivity, chain-length breathing, segmental stretch, and constraint release in reptation models. I. Theory and single-step strain predictions Hua, Chi C.; Schieber, Jay D. The Journal of Chemical Physics, Vol. 109, Issue 22 https://doi.org/10.1063/1.477670	journal	December 1998
Communication: Polymer entanglement dynamics: Role of attractive interactions Grest, Gary S. The Journal of Chemical Physics, Vol. 145, Issue 14 https://doi.org/10.1063/1.4964617	journal	October 2016
Molecular Mechanisms of Plastic Deformation in Sphere-Forming Thermoplastic Elastomers Parker, Amanda J.; Rottler, Jörg Macromolecules, Vol. 48, Issue 22 https://doi.org/10.1021/acs.macromol.5b01339	journal	October 2015
Dynamics of concentrated polymer systems. Part 3.—The constitutive equation Doi, Masao; Edwards, S. F. J. Chem. Soc., Faraday Trans. 2, Vol. 74, Issue 0 https://doi.org/10.1039/F29787401818	journal	January 1978
Effect of Chain Orientation and Stretch on the Stress Overshoot of Entangled Polymeric Materials under Start-Up Shear Jeong, Sohdam; Kim, Jun Mo; Baig, Chunggi Macromolecules, Vol. 50, Issue 8 https://doi.org/10.1021/acs.macromol.7b00288	journal	April 2017
Microscopic theory of linear, entangled polymer chains under rapid deformation including chain stretch and convective constraint release Graham, Richard S.; Likhtman, Alexei E.; McLeish, Tom C. B. Journal of Rheology, Vol. 47, Issue 5 https://doi.org/10.1122/1.1595099	journal	September 2003
Fingerprinting Molecular Relaxation in Deformed Polymers Wang, Zhe; Lam, Christopher N.; Chen, Wei-Ren Physical Review X, Vol. 7, Issue 3 https://doi.org/10.1103/PhysRevX.7.031003	journal	July 2017
Entangled Polymer Dynamics in Equilibrium and Flow Modeled Through Slip Links Schieber, Jay D.; Andreev, Marat Annual Review of Chemical and Biomolecular Engineering, Vol. 5, Issue 1 https://doi.org/10.1146/annurev-chembioeng-060713-040252	journal	June 2014
Polymer Melts under Uniaxial Elongational Flow: Stress−Optical Behavior from Experiments and Nonequilibrium Molecular Dynamics Computer Simulations Kröger, M.; Luap, C.; Muller, R. Macromolecules, Vol. 30, Issue 3 https://doi.org/10.1021/ma960317c	journal	February 1997
Molecular modelling of entanglement Doi, Masao; Takimoto, Jun-ichi Philosophical Transactions of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, Vol. 361, Issue 1805 https://doi.org/10.1098/rsta.2002.1168	journal	February 2003
Deviations from Dynamic Dilution in the Terminal Relaxation of Star Polymers Shanbhag, S.; Larson, R. G.; Takimoto, J. Physical Review Letters, Vol. 87, Issue 19 https://doi.org/10.1103/PhysRevLett.87.195502	journal	October 2001
Reptation of a Polymer Chain in the Presence of Fixed Obstacles de Gennes, P. G. The Journal of Chemical Physics, Vol. 55, Issue 2 https://doi.org/10.1063/1.1675789	journal	July 1971
The entanglement concept in polymer rheology Graessley, William W. The Entanglement Concept in Polymer Rheology https://doi.org/10.1007/BFb0031037	book	January 2005
Dynamics of concentrated polymer systems. Part 4.—Rheological properties Doi, Masao; Edwards, S. F. J. Chem. Soc., Faraday Trans. 2, Vol. 75, Issue 0 https://doi.org/10.1039/F29797500038	journal	January 1979
Simple models for complex nonequilibrium fluids Kroger, M. Physics Reports, Vol. 390, Issue 6 https://doi.org/10.1016/j.physrep.2003.10.014	journal	February 2004
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
Polymer coil relaxation in uniaxially strained polystyrene observed by small angle neutron scattering Boué, F.; Nierlich, M.; Jannink, G. Journal de Physique, Vol. 43, Issue 1 https://doi.org/10.1051/jphys:01982004301013700	journal	January 1982
Equilibration of long chain polymer melts in computer simulations Auhl, Rolf; Everaers, Ralf; Grest, Gary S. The Journal of Chemical Physics, Vol. 119, Issue 24 https://doi.org/10.1063/1.1628670	journal	December 2003
Static and dynamic properties of large polymer melts in equilibrium Hsu, Hsiao-Ping; Kremer, Kurt The Journal of Chemical Physics, Vol. 144, Issue 15 https://doi.org/10.1063/1.4946033	journal	April 2016
Bond Orientation Decay and Stress Relaxation in a Model Polymer Melt Gao, Jianping; Weiner, Jerome H. Macromolecules, Vol. 29, Issue 18 https://doi.org/10.1021/ma9602177	journal	January 1996
Microscopic theory of convective constraint release Milner, S. T.; McLeish, T. C. B.; Likhtman, A. E. Journal of Rheology, Vol. 45, Issue 2 https://doi.org/10.1122/1.1349122	journal	March 2001
Dynamics of concentrated polymer systems. Part 2.—Molecular motion under flow Doi, Masao; Edwards, S. F. J. Chem. Soc., Faraday Trans. 2, Vol. 74, Issue 0 https://doi.org/10.1039/F29787401802	journal	January 1978
Dynamics of concentrated polymer systems. Part 1.—Brownian motion in the equilibrium state Doi, Masao; Edwards, S. F. J. Chem. Soc., Faraday Trans. 2, Vol. 74, Issue 0 https://doi.org/10.1039/F29787401789	journal	January 1978
Nonlinear Polymer Rheology Wang, Shi-Qing https://doi.org/10.1002/9781119029038	book	January 2018
Molten Polymers in Strong Flows: A Nonclassical Proposal de Gennes, P. G. MRS Bulletin, Vol. 16, Issue 1 https://doi.org/10.1557/S0883769400057857	journal	January 1991
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
Tube Model Under Tension Read, Daniel J. Physics, Vol. 10 https://doi.org/10.1103/Physics.10.77	journal	July 2017
Viscoelasticity and Molecular Rheology Likhtman, A. E. Polymer Science: A Comprehensive Reference https://doi.org/10.1016/B978-0-444-53349-4.00008-X	book	January 2012
Dynamics of entanglements: A nonlinear model consistent with the Cox-Merz rule Marrucci, G. Journal of Non-Newtonian Fluid Mechanics, Vol. 62, Issue 2-3 https://doi.org/10.1016/0377-0257(95)01407-1	journal	February 1996
Transient behavior of entangled polymers at high shear rates Pearson, D.; Herbolzheimer, E.; Grizzuti, N. Journal of Polymer Science Part B: Polymer Physics, Vol. 29, Issue 13 https://doi.org/10.1002/polb.1991.090291304	journal	December 1991
Rheological Evidence for a Dynamical Crossover in Polymer Melts via Nonequilibrium Molecular Dynamics Kröger, Martin; Hess, Siegfried Physical Review Letters, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevLett.85.1128	journal	July 2000
Simulating Startup Shear of Entangled Polymer Melts Cao, Jing; Likhtman, Alexei E. ACS Macro Letters, Vol. 4, Issue 12 https://doi.org/10.1021/acsmacrolett.5b00708	journal	November 2015
Simulating the Flow of Entangled Polymers Masubuchi, Yuichi Annual Review of Chemical and Biomolecular Engineering, Vol. 5, Issue 1 https://doi.org/10.1146/annurev-chembioeng-060713-040401	journal	June 2014
Topological analysis of polymeric melts: Chain-length effects and fast-converging estimators for entanglement length Hoy, Robert S.; Foteinopoulou, Katerina; Kröger, Martin Physical Review E, Vol. 80, Issue 3 https://doi.org/10.1103/PhysRevE.80.031803	journal	September 2009
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
Small Angle Neutron Scattering Observation of Chain Retraction after a Large Step Deformation Blanchard, A.; Graham, R. S.; Heinrich, M. Physical Review Letters, Vol. 95, Issue 16 https://doi.org/10.1103/PhysRevLett.95.166001	journal	October 2005
Reconstruction of three-dimensional anisotropic structure from small-angle scattering experiments Huang, Guan-Rong; Wang, Yangyang; Wu, Bin Physical Review E, Vol. 96, Issue 2 https://doi.org/10.1103/PhysRevE.96.022612	journal	August 2017

Cited By (10)

Recovery rheology via rheo‐SANS: Application to step strains under out‐of‐equilibrium conditions Lee, Johnny C. ‐W.; Porcar, Lionel; Rogers, Simon A. AIChE Journal, Vol. 65, Issue 12 https://doi.org/10.1002/aic.16797	journal	October 2019
Dynamical structure of entangled polymers simulated under shear flow Korolkovas, Airidas; Gutfreund, Philipp; Wolff, Max The Journal of Chemical Physics, Vol. 149, Issue 7 https://doi.org/10.1063/1.5035170	journal	August 2018
Simulation of semidilute polymer solutions in planar extensional flow via conformationally averaged Brownian noise Young, Charles D.; Sing, Charles E. The Journal of Chemical Physics, Vol. 151, Issue 12 https://doi.org/10.1063/1.5122811	journal	September 2019
Contraction of Entangled Polymers After Large Step Shear Deformations in Slip-Link Simulations Masubuchi, Yuichi Polymers, Vol. 11, Issue 2 https://doi.org/10.3390/polym11020370	journal	February 2019
Slip-Spring and Kink Dynamics Models for Fast Extensional Flow of Entangled Polymeric Fluids Moghadam, Soroush; Saha Dalal, Indranil; Larson, Ronald Polymers, Vol. 11, Issue 3 https://doi.org/10.3390/polym11030465	journal	March 2019
Simulation of semidilute polymer solutions in planar extensional via conformationally averaged Brownian noise Young, Charles D.; Sing, Charles E. arXiv https://doi.org/10.48550/arxiv.1907.10817	text	January 2019
Dynamical structure of entangled polymers simulated under shear flow Korolkovas, Airidas; Gutfreund, Philipp; Wolff, Max arXiv https://doi.org/10.48550/arxiv.1703.10946	text	January 2017
Entangled chain polymer liquids under continuous shear deformation: consequences of a microscopically anharmonic confining tube Xie, Shi-Jie; Schweizer, Kenneth S. Soft Matter, Vol. 14, Issue 34 https://doi.org/10.1039/c8sm01182f	journal	January 2018
Nonlinear shear of entangled polymers from nonequilibrium molecular dynamics Anwar, Muhammad; Graham, Richard S. Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 24 https://doi.org/10.1002/polb.24904	journal	November 2019
Clustering of entanglement points in highly strained polymer melts Hsu, Hsiao-Ping; Kremer, Kurt arXiv https://doi.org/10.48550/arxiv.1906.00109	text	January 2019

Similar Records

Composite entanglement topology and extensional rheology of symmetric ring-linear polymer blends

Journal Article · 2021 · Journal of Rheology · OSTI ID:1832940

O’Connor, Thomas C.; Ge, Ting; Grest, Gary S.

Small Angle Neutron Scattering Observation of Chain Retraction after a Large Step Deformation

Journal Article · 2005 · Physical Review Letters · OSTI ID:20696576

Blanchard, A; Heinrich, M; Pyckhout-Hintzen, W; +7 more

Modeling orthogonal superposition rheometry to probe nonequilibrium dynamics of entangled polymers

Journal Article · 2021 · Journal of Rheology · OSTI ID:1808220

Zhang, Jiamin; Jurzyk, Andres; Helgeson, Matthew E.; +1 more

Related Subjects

36 MATERIALS SCIENCE

Title: Molecular Dynamics Investigation of the Relaxation Mechanism of Entangled Polymers after a Large Step Deformation

Citation Formats

References (42)

Cited By (10)

Similar Records

Related Subjects