Molecular dynamics modeling of PPTA crystallite mechanical properties in the presence of defects

Mercer, Brian; Zywicz, Edward; Papadopoulos, Panayiotis

doi:10.1016/j.polymer.2017.03.012

Title: Molecular dynamics modeling of PPTA crystallite mechanical properties in the presence of defects

Journal Article · 11 March 2017 · Polymer

DOI: https://doi.org/10.1016/j.polymer.2017.03.012 · OSTI ID:1351138

^[1]; Zywicz, Edward ^[2]; Papadopoulos, Panayiotis ^[3]

Univ. of California, Berkeley, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of California, Berkeley, CA (United States)

Here, the mechanical properties of PPTA crystallites, the fundamental building blocks of aramid polymer fibers such as Kevlar® and Twaron®, are studied here using molecular dynamics simulations. The ReaxFF interatomic potential is employed to study crystallite failure via covalent and hydrogen bond rupture in constant strain-rate tensile loading simulations. Emphasis is placed on analyzing how chain-end defects in the crystallite influence its mechanical response and fracture strength. Chain-end defects are found to affect the behavior of nearby chains in a region of the PPTA crystallite that is small relative to the typical crystallite size in manufactured aramid fibers. The central Csingle bondN bond along the backbone chain is identified as the weakest in the PPTA polymer chain backbone in dynamic strain-to-failure simulations of the crystallite. It is found that clustering of chain-ends leads to reduced crystallite strength and crystallite failure via hydrogen bond rupture and chain sliding, whereas randomly scattered defects impact the strength less and failure is by covalent bond rupture and chain scission. The axial crystallite modulus increases with increasing chain length and is independent of chain-end defect locations. On the basis of these findings, a theoretical model is proposed to predict the axial modulus as a function of chain length.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1351138

Alternate ID(s):: OSTI ID: 1396502

Report Number(s):: LLNL-JRNL-717003

Journal Information:: Polymer, Vol. 114, Issue C; ISSN 0032-3861

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

X-ray diffraction study of poly(p-phenylene terephthalamide) fibres Northolt, M. G. European Polymer Journal, Vol. 10, Issue 9 https://doi.org/10.1016/0014-3057(74)90131-1	journal	September 1974
Direct observation of structure in high-modulus aromatic fibers Dobb, M. G.; Johnson, D. J.; Saville, B. P. Journal of Polymer Science: Polymer Symposia, Vol. 58, Issue 1 https://doi.org/10.1002/polc.5070580117	journal	January 1977
Supramolecular structure of a high-modulus polyaromatic fiber (Kevlar 49) Dobb, M. G.; Johnson, D. J.; Saville, B. P. Journal of Polymer Science: Polymer Physics Edition, Vol. 15, Issue 12 https://doi.org/10.1002/pol.1977.180151212	journal	December 1977
Morphology of poly(p-phenylene terephthalamide) fibers Panar, M.; Avakian, P.; Blume, R. C. Journal of Polymer Science: Polymer Physics Edition, Vol. 21, Issue 10 https://doi.org/10.1002/pol.1983.180211006	journal	October 1983
The relationship between the physical structure and the microscopic deformation and failure processes of poly(p-phenylene terephthalamide) fibers Morgan, Roger J.; Pruneda, Cesar O.; Steele, Wayne J. Journal of Polymer Science: Polymer Physics Edition, Vol. 21, Issue 9 https://doi.org/10.1002/pol.1983.180210913	journal	September 1983
On the morphology of aromatic polyamide fibers (Kevlar, Kevlar-49, and PRD-49) Li, L. S.; Allard, L. F.; Bigelow, W. C. Journal of Macromolecular Science, Part B, Vol. 22, Issue 2 https://doi.org/10.1080/00222348308215504	journal	January 1983
Chain orientation distribution and elastic properties of poly (p-phenylene terephthalamide), a “rigid rod” polymer Northolt, M. G.; van Aartsen, J. J. Journal of Polymer Science: Polymer Symposia, Vol. 58, Issue 1 https://doi.org/10.1002/polc.5070580120	journal	January 1977
Tensile deformation of poly(p-phenylene terephthalamide) fibres, an experimental and theoretical analysis Northolt, M. G. Polymer, Vol. 21, Issue 10 https://doi.org/10.1016/0032-3861(80)90088-9	journal	October 1980
Elastic extension of an oriented crystalline fibre Northolt, M. G.; Hout, R. v. d. Polymer, Vol. 26, Issue 2 https://doi.org/10.1016/0032-3861(85)90047-3	journal	February 1985
Computer simulation of aromatic polyesters including molecular dynamics Depner, M.; Schürmann, B. L. Polymer, Vol. 33, Issue 2 https://doi.org/10.1016/0032-3861(92)91000-R	journal	January 1992
Elastic Moduli and Molecular Structures of Several Crystalline Polymers, Including Aromatic Polyamides Tashiro, Kohji; Kobayashi, Masamichi; Tadokoro, Hiroyuki Macromolecules, Vol. 10, Issue 2 https://doi.org/10.1021/ma60056a033	journal	March 1977
Thermal expansion and temperature dependence of elastic moduli of aromatic polyamides Lacks, Daniel J.; Rutledge, Gregory C. Macromolecules, Vol. 27, Issue 24 https://doi.org/10.1021/ma00102a031	journal	November 1994
Structure and properties of crystalline polymers Tadokoro, Hiroyuki Polymer, Vol. 25, Issue 2 https://doi.org/10.1016/0032-3861(84)90321-5	journal	February 1984
Molecular simulation of compressive failure in poly(p-phenylene teraphthalamide) crystals Lacks, D. J. Journal of Materials Science, Vol. 31, Issue 22 https://doi.org/10.1007/BF01152137	journal	November 1996
Filament-Level Modeling of Aramid-Based High-Performance Structural Materials Grujicic, M.; Bell, W. C.; Glomski, P. S. Journal of Materials Engineering and Performance, Vol. 20, Issue 8 https://doi.org/10.1007/s11665-010-9786-y	journal	November 2011
Multi-length scale computational derivation of Kevlar® yarn-level material model Grujicic, M.; Glomski, P. S.; Pandurangan, B. Journal of Materials Science, Vol. 46, Issue 14 https://doi.org/10.1007/s10853-011-5389-8	journal	February 2011
Multi-Length Scale-Enriched Continuum-Level Material Model for Kevlar®-Fiber-Reinforced Polymer-Matrix Composites Grujicic, M.; Pandurangan, B.; Snipes, J. S. Journal of Materials Engineering and Performance, Vol. 22, Issue 3 https://doi.org/10.1007/s11665-012-0329-6	journal	August 2012
Molecular-Level Study of the Effect of Prior Axial Compression/Torsion on the Axial-Tensile Strength of PPTA Fibers Grujicic, M.; Yavari, R.; Ramaswami, S. Journal of Materials Engineering and Performance, Vol. 22, Issue 11 https://doi.org/10.1007/s11665-013-0648-2	journal	July 2013
Axial-Compressive Behavior, Including Kink-Band Formation and Propagation, of Single p -Phenylene Terephthalamide (PPTA) Fibers Grujicic, M.; Ramaswami, S.; Snipes, J. S. Advances in Materials Science and Engineering, Vol. 2013 https://doi.org/10.1155/2013/329549	journal	January 2013
The effect of plain-weaving on the mechanical properties of warp and weft p-phenylene terephthalamide (PPTA) fibers/yarns Grujicic, M.; Yavari, R.; Snipes, J. S. Journal of Materials Science, Vol. 49, Issue 24 https://doi.org/10.1007/s10853-014-8536-1	journal	August 2014
ReaxFF: A Reactive Force Field for Hydrocarbons van Duin, Adri C. T.; Dasgupta, Siddharth; Lorant, Francois The Journal of Physical Chemistry A, Vol. 105, Issue 41 https://doi.org/10.1021/jp004368u	journal	October 2001
ReaxFF _SiO Reactive Force Field for Silicon and Silicon Oxide Systems van Duin, Adri C. T.; Strachan, Alejandro; Stewman, Shannon The Journal of Physical Chemistry A, Vol. 107, Issue 19 https://doi.org/10.1021/jp0276303	journal	May 2003
Development and Validation of a ReaxFF Reactive Force Field for Fe/Al/Ni Alloys: Molecular Dynamics Study of Elastic Constants, Diffusion, and Segregation Shin, Yun Kyung; Kwak, Hyunwook; Zou, Chenyu The Journal of Physical Chemistry A, Vol. 116, Issue 49 https://doi.org/10.1021/jp308507x	journal	November 2012
Development of the ReaxFF Reactive Force Field for Describing Transition Metal Catalyzed Reactions, with Application to the Initial Stages of the Catalytic Formation of Carbon Nanotubes Nielson, Kevin D.; van Duin, Adri C. T.; Oxgaard, Jonas The Journal of Physical Chemistry A, Vol. 109, Issue 3 https://doi.org/10.1021/jp046244d	journal	January 2005
ReaxFF- l g: Correction of the ReaxFF Reactive Force Field for London Dispersion, with Applications to the Equations of State for Energetic Materials Liu, Lianchi; Liu, Yi; Zybin, Sergey V. The Journal of Physical Chemistry A, Vol. 115, Issue 40 https://doi.org/10.1021/jp201599t	journal	October 2011
The effect of time step, thermostat, and strain rate on ReaxFF simulations of mechanical failure in diamond, graphene, and carbon nanotube Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M. Journal of Computational Chemistry, Vol. 36, Issue 21 https://doi.org/10.1002/jcc.23970	journal	June 2015
Tearing Graphene Sheets From Adhesive Substrates Produces Tapered Nanoribbons Sen, Dipanjan; Novoselov, Kostya S.; Reis, Pedro M. Small, Vol. 6, Issue 10 https://doi.org/10.1002/smll.201000097	journal	May 2010
Ripping Graphene: Preferred Directions Kim, Kwanpyo; Artyukhov, Vasilii I.; Regan, William Nano Letters, Vol. 12, Issue 1 https://doi.org/10.1021/nl203547z	journal	December 2011
Mechanical properties of graphyne Cranford, Steven W.; Buehler, Markus J. Carbon, Vol. 49, Issue 13 https://doi.org/10.1016/j.carbon.2011.05.024	journal	November 2011
Extended graphynes: simple scaling laws for stiffness, strength and fracture Cranford, Steven W.; Brommer, Dieter B.; Buehler, Markus J. Nanoscale, Vol. 4, Issue 24 https://doi.org/10.1039/c2nr31644g	journal	January 2012
Multiparadigm Modeling of Dynamical Crack Propagation in Silicon Using a Reactive Force Field Buehler, Markus J.; van Duin, Adri C. T.; Goddard, William A. Physical Review Letters, Vol. 96, Issue 9 https://doi.org/10.1103/PhysRevLett.96.095505	journal	March 2006
Modeling failure mechanisms of poly(p-phenylene terephthalamide) fiber using reactive potentials Yılmaz, Dündar E. Computational Materials Science, Vol. 109 https://doi.org/10.1016/j.commatsci.2015.07.010	journal	November 2015
Shock Waves in High-Energy Materials: The Initial Chemical Events in Nitramine RDX Strachan, Alejandro; van Duin, Adri C. T.; Chakraborty, Debashis Physical Review Letters, Vol. 91, Issue 9 https://doi.org/10.1103/PhysRevLett.91.098301	journal	August 2003
An ab Initio CFF93 All-Atom Force Field for Polycarbonates Sun, Huai; Mumby, Stephen J.; Maple, Jon R. Journal of the American Chemical Society, Vol. 116, Issue 7 https://doi.org/10.1021/ja00086a030	journal	April 1994
Detailed atomistic simulation of oriented pseudocrystalline polymers and application to a stiff-chain aramid Rutledge, G. C.; Suter, U. W. Macromolecules, Vol. 24, Issue 8 https://doi.org/10.1021/ma00008a033	journal	April 1991
Calculation of mechanical properties of poly(p-phenylene terephthalamide) by atomistic modelling Rutledge, G. C.; Suter, U. W. Polymer, Vol. 32, Issue 12 https://doi.org/10.1016/0032-3861(91)90044-J	journal	January 1991
COMPASS: An ab Initio Force-Field Optimized for Condensed-Phase ApplicationsOverview with Details on Alkane and Benzene Compounds Sun, H. The Journal of Physical Chemistry B, Vol. 102, Issue 38 https://doi.org/10.1021/jp980939v	journal	September 1998
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
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Constant pressure molecular dynamics algorithms Martyna, Glenn J.; Tobias, Douglas J.; Klein, Michael L. The Journal of Chemical Physics, Vol. 101, Issue 5 https://doi.org/10.1063/1.467468	journal	September 1994
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
Charge equilibration for molecular dynamics simulations Rappe, Anthony K.; Goddard, William A. The Journal of Physical Chemistry, Vol. 95, Issue 8 https://doi.org/10.1021/j100161a070	journal	April 1991
Reactive Molecular Dynamics: Numerical Methods and Algorithmic Techniques Aktulga, Hasan Metin; Pandit, Sagar A.; van Duin, Adri C. T. SIAM Journal on Scientific Computing, Vol. 34, Issue 1 https://doi.org/10.1137/100808599	journal	January 2012
The virial theorem and stress calculation in molecular dynamics Tsai, D. H. The Journal of Chemical Physics, Vol. 70, Issue 3 https://doi.org/10.1063/1.437577	journal	February 1979
Application of molecular simulation technique to calculate structure and define deformation mechanisms of high-performance polymers Yang, Xiaozhen; Hsu, Shaw Ling Macromolecules, Vol. 24, Issue 25 https://doi.org/10.1021/ma00025a019	journal	December 1991
Elastic modulus in the crystalline region of poly(p-phenylene terephthalamide) Gaymans, R. J.; Tijssen, J.; Harkema, S. Polymer, Vol. 17, Issue 6 https://doi.org/10.1016/0032-3861(76)90133-6	journal	June 1976
Paracrystallinity-modulus relationships in kevlar aramid fibers Barton, Randolph Journal of Macromolecular Science, Part B, Vol. 24, Issue 1-4 https://doi.org/10.1080/00222348508248020	journal	March 1985
Relationship between structure and mechanical properties for aramid fibres Young, R. J.; Lu, D.; Day, R. J. Journal of Materials Science, Vol. 27, Issue 20 https://doi.org/10.1007/BF00541602	journal	January 1992
X-ray study of lattice tensile properties of fully extended aromatic polyamide fibers over a wide temperature range Ii, Tadaoki.; Tashiro, Kohji.; Kobayashi, Masamichi. Macromolecules, Vol. 20, Issue 2 https://doi.org/10.1021/ma00168a020	journal	February 1987
The Ultimate Strength and Stiffness of Polymers Crist, B. Annual Review of Materials Science, Vol. 25, Issue 1 https://doi.org/10.1146/annurev.ms.25.080195.001455	journal	August 1995
ReaxFF Reactive Force Field for Molecular Dynamics Simulations of Hydrocarbon Oxidation Chenoweth, Kimberly; van Duin, Adri C. T.; Goddard, William A. The Journal of Physical Chemistry A, Vol. 112, Issue 5 https://doi.org/10.1021/jp709896w	journal	February 2008
Structure and hydrogen bond dynamics of water–dimethyl sulfoxide mixtures by computer simulations Luzar, Alenka; Chandler, David The Journal of Chemical Physics, Vol. 98, Issue 10 https://doi.org/10.1063/1.464521	journal	May 1993
Dynamical Behavior of Anion−Water and Water−Water Hydrogen Bonds in Aqueous Electrolyte Solutions: A Molecular Dynamics Study Chandra, Amalendu The Journal of Physical Chemistry B, Vol. 107, Issue 16 https://doi.org/10.1021/jp022147d	journal	April 2003
Microstructural developments of poly (p-phenylene terephthalamide) fibers during heat treatment process: a review Ahmed, Dawelbeit; Hongpeng, Zhong; Haijuan, Kong Materials Research, Vol. 17, Issue 5 https://doi.org/10.1590/1516-1439.250313	journal	September 2014
Chain Ends and the Ultimate Strength of Polyethylene Fibers O’Connor, Thomas C.; Robbins, Mark O. ACS Macro Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsmacrolett.5b00838	journal	February 2016

Cited By (1)

The introduction of asymmetric heterocyclic units into poly(p-phenylene terephthalamide) and its effect on microstructure, interactions and properties Luo, Longbo; Wang, Yazhe; Dai, Yu Journal of Materials Science, Vol. 53, Issue 18 https://doi.org/10.1007/s10853-018-2580-1	journal	June 2018

Similar Records

Molecular Dynamics Modeling of PPTA Crystals in Aramid Fibers

Thesis/Dissertation · 2016 · OSTI ID:1254392

Mercer, Brian Scott

Copolymers of poly(para-phenylene terephthalamide) containing a thermally activated cross-linking agent

Conference · 1993 · OSTI ID:141882

Spilman, G E; Markoski, L J; Walker, K A; +3 more

Structure-property-processing relationships in Kevlar fibers

Conference · 1996 · OSTI ID:602882

Lacks, D J

Related Subjects

42 ENGINEERING
36 MATERIALS SCIENCE
Kevlar®
Aramid fibers
elastic modulus
defects
molecular dynamics
reactive potentials

Title: Molecular dynamics modeling of PPTA crystallite mechanical properties in the presence of defects

Citation Formats

References (56)

Cited By (1)

Similar Records

Related Subjects