Heterogeneous Directional Mobility in the Early Stages of Polymer Crystallization
Abstract
Recently we demonstrated via large large-scale molecular dynamics simulations a 'coexistence period' in polymer melt ordering before crystallization, where nucleation and growth mechanisms coexist with a phase phase-separation mechanism. Here we present an extension of this work, where we analyze the directional displacements as a measure of the mobility of monomers as they order during crystallization over more than 100 ns of simulation time. It is found that the polymer melt, after quenching, rapidly separates into many ordered hexagonal domains separated by amorphous regions, where surprisingly, the magnitude of the monomer's displacement in the ordered state, parallel to the domain axial direction, is similar to its magnitude in the melt. T. The monomer he displacements in the domain's lateral direction are found to decrease during the time of the simulation. The ordered hexagonal domains do not align into uniform lamellar structures during the timescales of our simulations.
- Authors:
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 947247
- Report Number(s):
- LLNL-JRNL-408396
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US200909%%134
- DOE Contract Number:
- W-7405-ENG-48
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 128; Journal Issue: 1; Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUMM MECHANICS, GENERAL PHYSICS; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTALLIZATION; MONOMERS; NUCLEATION; POLYMERS; QUENCHING; SIMULATION
Citation Formats
Lacevic, N, Fried, L E, and Gee, R H. Heterogeneous Directional Mobility in the Early Stages of Polymer Crystallization. United States: N. p., 2008.
Web. doi:10.1063/1.2813896.
Lacevic, N, Fried, L E, & Gee, R H. Heterogeneous Directional Mobility in the Early Stages of Polymer Crystallization. United States. https://doi.org/10.1063/1.2813896
Lacevic, N, Fried, L E, and Gee, R H. 2008.
"Heterogeneous Directional Mobility in the Early Stages of Polymer Crystallization". United States. https://doi.org/10.1063/1.2813896. https://www.osti.gov/servlets/purl/947247.
@article{osti_947247,
title = {Heterogeneous Directional Mobility in the Early Stages of Polymer Crystallization},
author = {Lacevic, N and Fried, L E and Gee, R H},
abstractNote = {Recently we demonstrated via large large-scale molecular dynamics simulations a 'coexistence period' in polymer melt ordering before crystallization, where nucleation and growth mechanisms coexist with a phase phase-separation mechanism. Here we present an extension of this work, where we analyze the directional displacements as a measure of the mobility of monomers as they order during crystallization over more than 100 ns of simulation time. It is found that the polymer melt, after quenching, rapidly separates into many ordered hexagonal domains separated by amorphous regions, where surprisingly, the magnitude of the monomer's displacement in the ordered state, parallel to the domain axial direction, is similar to its magnitude in the melt. T. The monomer he displacements in the domain's lateral direction are found to decrease during the time of the simulation. The ordered hexagonal domains do not align into uniform lamellar structures during the timescales of our simulations.},
doi = {10.1063/1.2813896},
url = {https://www.osti.gov/biblio/947247},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 1,
volume = 128,
place = {United States},
year = {Sat Nov 01 00:00:00 EDT 2008},
month = {Sat Nov 01 00:00:00 EDT 2008}
}
Works referenced in this record:
An approach to the formation and growth of new phases with application to polymer crystallization: effect of finite size, metastability, and Ostwald's rule of stages
journal, May 1994
- Keller, A.; Hikosaka, M.; Rastogi, S.
- Journal of Materials Science, Vol. 29, Issue 10
Computer "Experiments" on Classical Fluids. I. Thermodynamical Properties of Lennard-Jones Molecules
journal, July 1967
- Verlet, Loup
- Physical Review, Vol. 159, Issue 1
Relaxation processes in crystalline polymers: experimental behaviour — a review
journal, March 1985
- Boyd, Richard H.
- Polymer, Vol. 26, Issue 3
Ultrafast crystallization of polar polymer melts
journal, February 2003
- Gee, Richard H.; Fried, Laurence E.
- The Journal of Chemical Physics, Vol. 118, Issue 8
Small-angle neutron scattering from star-branched polymers in the molten state
journal, March 1989
- Horton, J. C.; Squires, G. L.; Boothroyd, A. T.
- Macromolecules, Vol. 22, Issue 2
Conformational Characteristics of Poly(tetrafluoroethylene) Chains Based upon ab Initio Electronic Structure Calculations on Model Molecules
journal, June 1994
- Smith, Grant D.; Jaffe, Richard L.; Yoon, Do Y.
- Macromolecules, Vol. 27, Issue 12
Molecular dynamics modeling of polymer crystallization from the melt
journal, February 2004
- Yamamoto, Takashi
- Polymer, Vol. 45, Issue 4
Hoover NPT dynamics for systems varying in shape and size
journal, February 1993
- Melchionna, Simone; Ciccotti, Giovanni; Lee Holian, Brad
- Molecular Physics, Vol. 78, Issue 3
Role of mobile phases in the crystallization of polyethylene. Part 1. Metastability and lateral growth
journal, November 1991
- Rastogi, S.; Hikosaka, M.; Kawabata, H.
- Macromolecules, Vol. 24, Issue 24
Formation of Chain-Folded Structures in Supercooled Polymer Melts Examined by MD Simulations
journal, February 2002
- Meyer, Hendrik; Müller-Plathe, Florian
- Macromolecules, Vol. 35, Issue 4
DREIDING: a generic force field for molecular simulations
journal, December 1990
- Mayo, Stephen L.; Olafson, Barry D.; Goddard, William A.
- The Journal of Physical Chemistry, Vol. 94, Issue 26, p. 8897-8909
Formation of Polymer Crystals with Folded Chains from Dilute Solution
journal, December 1959
- Lauritzen, John I.; Hoffman, John D.
- The Journal of Chemical Physics, Vol. 31, Issue 6
Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995
- Plimpton, Steve
- Journal of Computational Physics, Vol. 117, Issue 1
Statistical mechanics of chain molecules
journal, November 1969
- Flory, Paul. J.; Volkenstein, M.
- Biopolymers, Vol. 8, Issue 5
Evidence of Early Stage Precursors of Polymer Crystals by Dielectric Spectroscopy
journal, January 2007
- Soccio, M.; Nogales, A.; Lotti, N.
- Physical Review Letters, Vol. 98, Issue 3
Polymer crystallization from the metastable melt: The formation mechanism of spherulites
journal, July 2006
- Imai, Masayuki; Kaji, Keisuke
- Polymer, Vol. 47, Issue 15
Chain conformation in the induction period of crystallization of poly(ethylene terephthalate)
journal, August 1995
- Imai, M.; Kaji, K.; Kanaya, T.
- Physica B: Condensed Matter, Vol. 213-214
From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major route followed in polymer crystallization?
journal, October 2000
- Strobl, G.
- The European Physical Journal E, Vol. 3, Issue 2
The role of the torsional potential in relaxation dynamics: a molecular dynamics study of polyethylene
journal, January 1998
- Gee, Richard H.; Boyd, Richard H.
- Computational and Theoretical Polymer Science, Vol. 8, Issue 1-2
Chain diffusion between crystalline and amorphous regions in polyethylene detected by 2D exchange carbon-13 NMR
journal, September 1991
- Schmidt-Rohr, K.; Spiess, H. W.
- Macromolecules, Vol. 24, Issue 19
Topological Mechanism of Polymer Nucleation and Growth – The Role of Chain Sliding Diffusion and Entanglement
book, October 2005
- Hikosaka, Masamichi; Watanabe, Kaori; Okada, Kiyoka
- Interphases and Mesophases in Polymer Crystallization III
Atomistic simulations of spinodal phase separation preceding polymer crystallization
journal, December 2005
- Gee, Richard H.; Lacevic, Naida; Fried, Laurence E.
- Nature Materials, Vol. 5, Issue 1
Unified theory of nucleation of folded-chain crystals and extended-chain crystals of linear-chain polymers
journal, July 1987
- Hikosaka, Masamichi
- Polymer, Vol. 28, Issue 8
Liquid crystalline phase transition of a semiflexible polymer: acetoxypropyl cellulose
journal, September 1985
- Laivins, Gunar V.; Gray, Derek G.
- Macromolecules, Vol. 18, Issue 9
An optimized united atom model for simulations of polymethylene melts
journal, July 1995
- Paul, Wolfgang; Yoon, Do Y.; Smith, Grant D.
- The Journal of Chemical Physics, Vol. 103, Issue 4
A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984
- Nosé, Shuichi
- The Journal of Chemical Physics, Vol. 81, Issue 1
Molecular Dynamics Simulation of Polymer Crystallization from the Melt
journal, January 2003
- Yamamoto, Takashi
- Journal of Macromolecular Science, Part B, Vol. 42, Issue 3-4
Modeling Polymer Crystallization
book, October 2005
- Muthukumar, M.
- Interphases and Mesophases in Polymer Crystallization III
Spinodal-Assisted Crystallization in Polymer Melts
journal, July 1998
- Olmsted, P. D.; Poon, W. C. K.; McLeish, T. C. B.
- Physical Review Letters, Vol. 81, Issue 2
Molecular Mechanisms of Polymer Crystallization from Solution
journal, November 2001
- Welch, P.; Muthukumar, M.
- Physical Review Letters, Vol. 87, Issue 21