Polymer dynamics under cylindrical confinement featuring a locally repulsive surface: A quasielastic neutron scattering study

Krutyeva, M.; Pasini, S.; Monkenbusch, M.; Allgaier, J.; Maiz, J.; Mijangos, C.; Hartmann-Azanza, B.; Steinhart, M.; Jalarvo, N.; Richter, D.

doi:10.1063/1.4974836

Polymer dynamics under cylindrical confinement featuring a locally repulsive surface: A quasielastic neutron scattering study

Journal Article · Wed Feb 01 23:00:00 EST 2017 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4974836· OSTI ID:1399384

^[1]; Pasini, S. ^[1]; Monkenbusch, M. ^[1]; Allgaier, J. ^[1]; Maiz, J. ^[2]; Mijangos, C. ^[2]; Hartmann-Azanza, B. ^[3]; Steinhart, M. ^[3]; ^[4]; Richter, D. ^[1]

Julich Research Centre (Germany). Inst. for Complex Systems
Spanish National Research Council (CSIC), Madrid (Spain). Inst. of Science and Polymer Technology
Univ. of Osnabruck (Germany). Inst. of Chemistry for New Materials
Julich Research Centre (Germany). Inst. for Complex Systems; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division

We investigated the effect of intermediate cylindrical confinement with locally repulsive walls on the segmental and entanglement dynamics of a polymer melt by quasielastic neutron scattering. As a reference, we measured the corresponding polymer melt under identical conditions. The locally repulsive confinement was realized by hydrophilic anodic alumina nanopores with a diameter of 20 nm. The end-to-end distance of the hydrophobic infiltrated polyethylene-alt-propylene was close to this diameter. In the case of hard wall repulsion with negligible local attraction, several simulations predicted an acceleration of segmental dynamics close to the wall. Other than in attractive or neutral systems, where the segmental dynamics is slowed down, we found that the segmental dynamics in the nanopores is identical to the local mobility in the bulk. Even under very careful scrutiny, we could not find any acceleration of the surface-near segmental motion. On the larger time scale, the neutron spin-echo experiment showed that the Rouse relaxation was not altered by confinement effects. Moreover, the entanglement dynamics was not affected. Thus at moderate confinement conditions, facilitated by locally repulsive walls, the dynamics remains as in the bulk melt, a result that is not so clear from simulations.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1399384

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 146; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Simulated glass transition in free-standing thin polystyrene films Baljon, A. R. C.; Williams, S.; Balabaev, N. K. Journal of Polymer Science Part B: Polymer Physics, Vol. 48, Issue 11 https://doi.org/10.1002/polb.22005	journal	June 2010
Neutron Spin Echo in Polymer Systems Richter, Dieter; Monkenbusch, Michael; Arbe, Arantxa https://doi.org/10.1007/b106578	book	January 2005
Structure and dynamics of polymer nanocomposites studied by X-ray and neutron scattering techniques Genix, Anne-Caroline; Oberdisse, Julian Current Opinion in Colloid & Interface Science, Vol. 20, Issue 4 https://doi.org/10.1016/j.cocis.2015.10.002	journal	August 2015
Local Polymer Dynamics and Diffusion in Cylindrical Nanoconfinement Tung, Wei-Shao; Composto, Russell J.; Riggleman, Robert A. Macromolecules, Vol. 48, Issue 7 https://doi.org/10.1021/acs.macromol.5b00085	journal	March 2015
Untangling the Effects of Chain Rigidity on the Structure and Dynamics of Strongly Adsorbed Polymer Melts Carrillo, Jan-Michael Y.; Cheng, Shiwang; Kumar, Rajeev Macromolecules, Vol. 48, Issue 12 https://doi.org/10.1021/acs.macromol.5b00624	journal	June 2015
Dynamics of Hyperbranched Polymers under Confinement: A Dielectric Relaxation Study Androulaki, Krystalenia; Chrissopoulou, Kiriaki; Prevosto, Daniele ACS Applied Materials & Interfaces, Vol. 7, Issue 23 https://doi.org/10.1021/am507571y	journal	January 2015
Temperature dependence of the unperturbed dimensions of alternating poly(ethylene-propylene) Zirkel, A.; Richter, D.; Pyckhout-Hintzen, W. Macromolecules, Vol. 25, Issue 2 https://doi.org/10.1021/ma00028a069	journal	March 1992
On the origins of entanglement constraints Richter, D.; Farago, B.; Butera, R. Macromolecules, Vol. 26, Issue 4 https://doi.org/10.1021/ma00056a034	journal	July 1993
The dynamic structure factor of a star polymer in a concentrated solution Clarke, N.; Mcleish, T. C. B. Macromolecules, Vol. 26, Issue 19 https://doi.org/10.1021/ma00071a046	journal	September 1993
Quasielastic Neutron Scattering Study on the Effect of Blending on the Dynamics of Head-to-Head Poly(propylene) and Poly(ethylene−propylene) Pérez Aparicio, R.; Arbe, A.; Colmenero, J. Macromolecules, Vol. 39, Issue 3 https://doi.org/10.1021/ma052006k	journal	February 2006
Dynamic Confinement Effects in Polymer Blends. A Quasielastic Neutron Scattering Study of the Slow Component in the Blend Poly(vinyl acetate)/Poly(ethylene oxide) Tyagi, M.; Arbe, A.; Alegría, A. Macromolecules, Vol. 40, Issue 13 https://doi.org/10.1021/ma070539i	journal	June 2007
Dynamics of Entangled Chains in Polymer Nanocomposites Schneider, G. J.; Nusser, K.; Willner, L. Macromolecules, Vol. 44, Issue 15 https://doi.org/10.1021/ma200899y	journal	August 2011
Do Attractive Polymer–Nanoparticle Interactions Retard Polymer Diffusion in Nanocomposites? Lin, Chia-Chun; Gam, Sangah; Meth, Jeffrey S. Macromolecules, Vol. 46, Issue 11 https://doi.org/10.1021/ma4000557	journal	May 2013
Dynamics of Unentangled cis -1,4-Polyisoprene Confined to Nanoporous Alumina Alexandris, Stelios; Sakellariou, Georgios; Steinhart, Martin Macromolecules, Vol. 47, Issue 12 https://doi.org/10.1021/ma5006638	journal	June 2014
Modeling Dielectric Relaxation in Polymer Glass Simulations: Dynamics in the Bulk and in Supported Polymer Films Peter, S.; Napolitano, S.; Meyer, H. Macromolecules, Vol. 41, Issue 20 https://doi.org/10.1021/ma800694v	journal	October 2008
Synthesis and Characterization of Poly[1,4-isoprene- b -(ethylene oxide)] and Poly[ethylene- co -propylene- b -(ethylene oxide)] Block Copolymers Allgaier, Jürgen; Poppe, Andreas; Willner, Lutz Macromolecules, Vol. 30, Issue 6 https://doi.org/10.1021/ma961311q	journal	March 1997
Segmental Dynamics in Poly(vinylethylene)/Polyisoprene Miscible Blends Revisited. A Neutron Scattering and Broad-Band Dielectric Spectroscopy Investigation Arbe, A.; Alegría, A.; Colmenero, J. Macromolecules, Vol. 32, Issue 22 https://doi.org/10.1021/ma990402v	journal	November 1999
Molecular dynamics of pyrene based discotic liquid crystals confined in nanopores probed by incoherent quasielastic neutron scattering Ndao, Makha; Lefort, Ronan; Cerclier, Carole V. RSC Adv., Vol. 4, Issue 103 https://doi.org/10.1039/C4RA13032D	journal	January 2014
Effects of nanoscopic-confinement on polymer dynamics Chrissopoulou, Kiriaki; Anastasiadis, Spiros H. Soft Matter, Vol. 11, Issue 19 https://doi.org/10.1039/C5SM00554J	journal	January 2015
Rouse mode analysis of chain relaxation in polymer nanocomposites Kalathi, Jagannathan T.; Kumar, Sanat K.; Rubinstein, Michael Soft Matter, Vol. 11, Issue 20 https://doi.org/10.1039/C5SM00754B	journal	January 2015
Microscopic origin of the terminal relaxation time in polymer nanocomposites: an experimental precedent Nusser, Klaus; Schneider, Gerald J.; Richter, Dieter Soft Matter, Vol. 7, Issue 18 https://doi.org/10.1039/c1sm05555k	journal	January 2011
Dynamic structure of unentangled polymer chains in the vicinity of non-attractive nanoparticles Li, Ying; Kröger, Martin; Liu, Wing Kam Soft Matter, Vol. 10, Issue 11 https://doi.org/10.1039/c3sm51564h	journal	January 2014
Coherent scattering by one reptating chain De Gennes, P. G. Journal de Physique, Vol. 42, Issue 5 https://doi.org/10.1051/jphys:01981004205073500	journal	January 1981
Self-organized formation of hexagonal pore arrays in anodic alumina Jessensky, O.; Müller, F.; Gösele, U. Applied Physics Letters, Vol. 72, Issue 10 https://doi.org/10.1063/1.121004	journal	March 1998
A molecular dynamics simulation study of the viscoelastic properties of polymer nanocomposites Smith, Grant D.; Bedrov, Dmitry; Li, Liwei The Journal of Chemical Physics, Vol. 117, Issue 20 https://doi.org/10.1063/1.1516589	journal	November 2002
Dynamics of free chains in polymer nanocomposites Picu, R. C.; Rakshit, A. The Journal of Chemical Physics, Vol. 126, Issue 14 https://doi.org/10.1063/1.2719196	journal	April 2007
Dynamics of polymer melts confined by smooth walls: Crossover from nonentangled region to entangled region Li, Yijie; Wei, Dongshan; Han, Charles C. The Journal of Chemical Physics, Vol. 126, Issue 20 https://doi.org/10.1063/1.2737044	journal	May 2007
Quasielastic neutron scattering of poly(methyl phenyl siloxane) in the bulk and under severe confinement Chrissopoulou, K.; Anastasiadis, S. H.; Giannelis, E. P. The Journal of Chemical Physics, Vol. 127, Issue 14 https://doi.org/10.1063/1.2775449	journal	October 2007
A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS Mamontov, E.; Herwig, K. W. Review of Scientific Instruments, Vol. 82, Issue 8 https://doi.org/10.1063/1.3626214	journal	August 2011
Fast internal dynamics in alcohol dehydrogenase Monkenbusch, M.; Stadler, A.; Biehl, R. The Journal of Chemical Physics, Vol. 143, Issue 7 https://doi.org/10.1063/1.4928512	journal	August 2015
Tube theory of entangled polymer dynamics McLeish, T. C. B. Advances in Physics, Vol. 51, Issue 6 https://doi.org/10.1080/00018730210153216	journal	September 2002
Polymer Dynamics in a Polymer-Solid Interphase: Molecular Dynamics Simulations of 1,4-Polybutadiene At a Graphite Surface Solar, Mathieu; Yelash, Leonid; Virnau, Peter Soft Materials, Vol. 12, Issue sup1 https://doi.org/10.1080/1539445X.2014.937495	journal	November 2014
Reduction of the glass transition temperature in polymer films: A molecular-dynamics study Varnik, F.; Baschnagel, J.; Binder, K. Physical Review E, Vol. 65, Issue 2 https://doi.org/10.1103/PhysRevE.65.021507	journal	January 2002
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
Sensing Polymer Chain Dynamics through Ring Topology: A Neutron Spin Echo Study Gooßen, Sebastian; Krutyeva, Margarita; Sharp, Melissa Physical Review Letters, Vol. 115, Issue 14 https://doi.org/10.1103/PhysRevLett.115.148302	journal	September 2015
Direct Observation of the Transition from Free to Constrained Single-Segment Motion in Entangled Polymer Melts Wischnewski, A.; Monkenbusch, M.; Willner, L. Physical Review Letters, Vol. 90, Issue 5 https://doi.org/10.1103/PhysRevLett.90.058302	journal	February 2003
Direct Observation of Confined Single Chain Dynamics by Neutron Scattering Martín, J.; Krutyeva, M.; Monkenbusch, M. Physical Review Letters, Vol. 104, Issue 19 https://doi.org/10.1103/physrevlett.104.197801	journal	May 2010
Publisher’s Note: Effect of Nanoconfinement on Polymer Dynamics: Surface Layers and Interphases [Phys. Rev. Lett. 110 , 108303 (2013)] Krutyeva, M.; Wischnewski, A.; Monkenbusch, M. Physical Review Letters, Vol. 110, Issue 11 https://doi.org/10.1103/physrevlett.110.119901	journal	March 2013
Ordered Metal Nanohole Arrays Made by a Two-Step Replication of Honeycomb Structures of Anodic Alumina Masuda, H.; Fukuda, K. Science, Vol. 268, Issue 5216 https://doi.org/10.1126/science.268.5216.1466	journal	June 1995
On the dynamics and disentanglement in thin and two-dimensional polymer films Meyer, H.; Kreer, T.; Cavallo, A. The European Physical Journal Special Topics, Vol. 141, Issue 1 https://doi.org/10.1140/epjst/e2007-00035-9	journal	February 2007
Ten (or more) years of dynamics in confinement: Perspectives for 2010 McKenna, G. B. The European Physical Journal Special Topics, Vol. 189, Issue 1 https://doi.org/10.1140/epjst/e2010-01334-8	journal	October 2010
The dielectric α -relaxation in polymer films: A comparison between experiments and atomistic simulations Solar, M.; Mapesa, E. U.; Kremer, F. EPL (Europhysics Letters), Vol. 104, Issue 6 https://doi.org/10.1209/0295-5075/104/66004	journal	December 2013
Rouse mode analysis of chain relaxation in polymer nanocomposites K., Kumar, Sanat; T., Kalathi, Jagannathan; S., Grest, Gary The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/nxdc-7116	text	January 2015
Reduction of the Glass Transition Temperature in Polymer Films: A Molecular-Dynamics Study Varnik, F.; Baschnagel, J.; Binder, K. arXiv https://doi.org/10.48550/arxiv.cond-mat/0106305	text	January 2001
On the Dynamics and Disentanglement in Thin and Two-Dimensional Polymer Films Meyer, H.; Kreer, T.; Cavallo, A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0609127	preprint	January 2006
Neutron Spin-Echo and TOF Reveals Protein Dynamics in Solution Stadler, Andreas; Monkenbusch, Michael; Biehl, Ralf Journal of the Physical Society of Japan, Vol. 82, Issue Suppl.A https://doi.org/10.7566/jpsjs.82sa.sa016	journal	January 2013

Cited By (3)

High-resolution neutron spectroscopy using backscattering and neutron spin-echo spectrometers in soft and hard condensed matter Gardner, Jason S.; Ehlers, Georg; Faraone, Antonio Nature Reviews Physics, Vol. 2, Issue 2 https://doi.org/10.1038/s42254-019-0128-1	journal	January 2020
Neutron spin echo monitoring of segmental-like diffusion of water confined in the cores of carbon nanotubes Parmentier, Alexandra; Maccarini, Marco; De Francesco, Alessio Physical Chemistry Chemical Physics, Vol. 21, Issue 38 https://doi.org/10.1039/c9cp04248b	journal	January 2019
Polymer dynamics under confinement Richter, Dieter; Kruteva, Margarita Soft Matter, Vol. 15, Issue 37 https://doi.org/10.1039/c9sm01141b	journal	January 2019

Similar Records

Chain dynamics and nanoparticle motion in attractive polymer nanocomposites subjected to large deformations

Journal Article · Thu Sep 28 00:00:00 EDT 2017 · Soft Matter · OSTI ID:1427470

Two-population Rouse models for polymer segmental dynamics in nanocomposites

Journal Article · Wed Dec 31 19:00:00 EST 2025 · Physical Review E · OSTI ID:3013446

Communication: Polymer entanglement dynamics: Role of attractive interactions

Journal Article · Mon Oct 10 00:00:00 EDT 2016 · Journal of Chemical Physics · OSTI ID:1343059

Related Subjects

36 MATERIALS SCIENCE

Polymer dynamics under cylindrical confinement featuring a locally repulsive surface: A quasielastic neutron scattering study

Citation Formats

References (46)

Cited By (3)

Similar Records

Related Subjects