DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Crazing of nanocomposites with polymer-tethered nanoparticles

Abstract

The crazing behavior of polymer nanocomposites formed by blending polymer grafted nanoparticles with an entangled polymer melt is studied by molecular dynamics simulations. We focus on the three key differences in the crazing behavior of a composite relative to the pure homopolymer matrix, namely, a lower yield stress, a smaller extension ratio, and a grafted chain length dependent failure stress. The yield behavior is found to be mostly controlled by the local nanoparticle-grafted polymer interfacial energy, with the grafted polymer-polymer matrix interfacial structure being of little to no relevance. Increasing the attraction between nanoparticle core and the grafted polymer inhibits void nucleation and leads to a higher yield stress. In the craze growth regime, the presence of “grafted chain” sections of ≈100 monomers alters the mechanical response of composite samples, giving rise to smaller extension ratios and higher drawing stresses than for the homopolymer matrix. As a result, the dominant failure mechanism of composite samples depends strongly on the length of the grafted chains, with disentanglement being the dominant mechanism for short chains, while bond breaking is the failure mode for chain lengths >10Ne, where Ne is the entanglement length.

Authors:
 [1];  [2];  [3];  [4]; ORCiD logo [5]
  1. Columbia Univ., New York, NY (United States); Mississippi State Univ., Starkville, MS (United States)
  2. Columbia Univ., New York, NY (United States)
  3. Univ. of North Carolina, Chapel Hill, NC (United States)
  4. Johns Hopkins Univ., Baltimore, MD (United States)
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1326058
Alternate Identifier(s):
OSTI ID: 1321036
Report Number(s):
SAND-2016-5736J
Journal ID: ISSN 0021-9606; JCPSA6; 643404
Grant/Contract Number:  
AC04-94AL85000; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; polymers; crazing; bond cleavage; nanocomposites; nucleation

Citation Formats

Meng, Dong, Kumar, Sanat K., Ge, Ting, Robbins, Mark O., and Grest, Gary S. Crazing of nanocomposites with polymer-tethered nanoparticles. United States: N. p., 2016. Web. doi:10.1063/1.4961872.
Meng, Dong, Kumar, Sanat K., Ge, Ting, Robbins, Mark O., & Grest, Gary S. Crazing of nanocomposites with polymer-tethered nanoparticles. United States. https://doi.org/10.1063/1.4961872
Meng, Dong, Kumar, Sanat K., Ge, Ting, Robbins, Mark O., and Grest, Gary S. Wed . "Crazing of nanocomposites with polymer-tethered nanoparticles". United States. https://doi.org/10.1063/1.4961872. https://www.osti.gov/servlets/purl/1326058.
@article{osti_1326058,
title = {Crazing of nanocomposites with polymer-tethered nanoparticles},
author = {Meng, Dong and Kumar, Sanat K. and Ge, Ting and Robbins, Mark O. and Grest, Gary S.},
abstractNote = {The crazing behavior of polymer nanocomposites formed by blending polymer grafted nanoparticles with an entangled polymer melt is studied by molecular dynamics simulations. We focus on the three key differences in the crazing behavior of a composite relative to the pure homopolymer matrix, namely, a lower yield stress, a smaller extension ratio, and a grafted chain length dependent failure stress. The yield behavior is found to be mostly controlled by the local nanoparticle-grafted polymer interfacial energy, with the grafted polymer-polymer matrix interfacial structure being of little to no relevance. Increasing the attraction between nanoparticle core and the grafted polymer inhibits void nucleation and leads to a higher yield stress. In the craze growth regime, the presence of “grafted chain” sections of ≈100 monomers alters the mechanical response of composite samples, giving rise to smaller extension ratios and higher drawing stresses than for the homopolymer matrix. As a result, the dominant failure mechanism of composite samples depends strongly on the length of the grafted chains, with disentanglement being the dominant mechanism for short chains, while bond breaking is the failure mode for chain lengths >10Ne, where Ne is the entanglement length.},
doi = {10.1063/1.4961872},
journal = {Journal of Chemical Physics},
number = 9,
volume = 145,
place = {United States},
year = {Wed Sep 07 00:00:00 EDT 2016},
month = {Wed Sep 07 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Structural and mechanical properties of polymer nanocomposites
journal, August 2006


Growth, microstructure, and failure of crazes in glassy polymers
journal, July 2003


Failure mechanisms of polymer interfaces reinforced with block copolymers
journal, June 1992

  • Creton, Costantino; Kramer, Edward J.; Hui, Chung Yuen
  • Macromolecules, Vol. 25, Issue 12
  • DOI: 10.1021/ma00038a010

Polymer Nanocomposites: The “Nano” Effect on Mechanical Properties
journal, April 2007


Cavitation and Crazing in Rod-Containing Nanocomposites
journal, July 2011

  • Toepperwein, Gregory N.; de Pablo, Juan J.
  • Macromolecules, Vol. 44, Issue 13
  • DOI: 10.1021/ma200541s

Anisotropic self-assembly of spherical polymer-grafted nanoparticles
journal, March 2009

  • Akcora, Pinar; Liu, Hongjun; Kumar, Sanat K.
  • Nature Materials, Vol. 8, Issue 4
  • DOI: 10.1038/nmat2404

Equilibration of long chain polymer melts in computer simulations
journal, December 2003

  • Auhl, Rolf; Everaers, Ralf; Grest, Gary S.
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1628670

Shear yielding of amorphous glassy solids: Effect of temperature and strain rate
journal, July 2003


Theory and simulation studies of effective interactions, phase behavior and morphology in polymer nanocomposites
journal, January 2014


Surface-tethered chains entangled in a polymer melt: Effects on adhesion dynamics
journal, October 2001


Failure Mechanism of Glassy Polymer−Nanoparticle Composites
journal, August 2007

  • Lee, Jong-Young; Zhang, Qingling; Wang, Jia-Yu
  • Macromolecules, Vol. 40, Issue 17
  • DOI: 10.1021/ma0710479

Polymer-Grafted-Nanoparticles Nanocomposites: Dispersion, Grafted Chain Conformation, and Rheological Behavior
journal, January 2011

  • Chevigny, Chloé; Dalmas, Florent; Di Cola, Emanuela
  • Macromolecules, Vol. 44, Issue 1
  • DOI: 10.1021/ma101332s

Strategies for Dispersing Nanoparticles in Polymers
journal, April 2007


Nanoplastic Flows of Glassy Polymer Chains Interacting with Multiwalled Carbon Nanotubes in Nanocomposites
journal, July 2008

  • Lin, C. -W.; Huang, L. C.; Ma, C. -C. M.
  • Macromolecules, Vol. 41, Issue 13
  • DOI: 10.1021/ma702342z

Nanoparticle Alignment and Repulsion during Failure of Glassy Polymer Nanocomposites
journal, October 2006

  • Lee, Jong-Young; Zhang, Qingling; Emrick, Todd
  • Macromolecules, Vol. 39, Issue 21
  • DOI: 10.1021/ma061210k

Molecular Mechanisms of Failure in Polymer Nanocomposites
journal, July 2002


Entanglement network in nanoparticle reinforced polymers
journal, June 2009

  • Riggleman, Robert A.; Toepperwein, Gregory; Papakonstantopoulos, George J.
  • The Journal of Chemical Physics, Vol. 130, Issue 24
  • DOI: 10.1063/1.3148026

A review of particulate reinforcement theories for polymer composites
journal, December 1990

  • Ahmed, S.; Jones, F. R.
  • Journal of Materials Science, Vol. 25, Issue 12
  • DOI: 10.1007/BF00580110

Flow-induced chain fracture of isolated linear macromolecules in solution
journal, September 1986


Cracks and Crazes: On Calculating the Macroscopic Fracture Energy of Glassy Polymers from Molecular Simulations
journal, September 2002


Nanocomposites: Structure, Phase Behavior, and Properties
journal, June 2010


Identifying the primitive path mesh in entangled polymer liquids
journal, January 2005

  • Sukumaran, Sathish K.; Grest, Gary S.; Kremer, Kurt
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 43, Issue 8
  • DOI: 10.1002/polb.20384

Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements, and Crazing
journal, September 2014

  • Ge, Ting; Grest, Gary S.; Robbins, Mark O.
  • Macromolecules, Vol. 47, Issue 19
  • DOI: 10.1021/ma501473q

Manipulating Connectivity to Control Fracture in Network Polymer Adhesives
journal, February 2001


A molecular interpretation of the toughness of glassy polymers
journal, May 1991


Entanglements of an End-Grafted Polymer Brush in a Polymeric Matrix
journal, November 2007

  • Hoy, Robert S.; Grest, Gary S.
  • Macromolecules, Vol. 40, Issue 23
  • DOI: 10.1021/ma070943h

Multiscale modeling and simulation of polymer nanocomposites
journal, February 2008


Calculation of local mechanical properties of filled polymers
journal, March 2007

  • Papakonstantopoulos, George J.; Doxastakis, Manolis; Nealey, Paul F.
  • Physical Review E, Vol. 75, Issue 3
  • DOI: 10.1103/PhysRevE.75.031803

Local mechanical properties of polymeric nanocomposites
journal, September 2005

  • Papakonstantopoulos, George J.; Yoshimoto, Kenji; Doxastakis, Manolis
  • Physical Review E, Vol. 72, Issue 3
  • DOI: 10.1103/PhysRevE.72.031801

Simulations of Crazing in Polymer Glasses:  Effect of Chain Length and Surface Tension
journal, June 2001

  • Baljon, A. R. C.; Robbins, Mark O.
  • Macromolecules, Vol. 34, Issue 12
  • DOI: 10.1021/ma0012393

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength
journal, July 2014


Nanoparticle Polymer Composites: Where Two Small Worlds Meet
journal, November 2006

  • Balazs, A. C.; Emrick, T.; Russell, T. P.
  • Science, Vol. 314, Issue 5802, p. 1107-1110
  • DOI: 10.1126/science.1130557

Softer at the boundary
journal, September 2005


The Physics of Glassy Polymers
book, January 1973


A review of particulate reinforcement theories for polymer composites
journal, September 1992


The physics of glassy polymers
journal, January 1974


Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements, and Crazing
text, January 2014

  • Ting, Ge,; Mark, Robbins,; Gary, Grest,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/sk7h-sf32

Tensile Fracture of Welded Polymer Interfaces: Miscibility, Entanglements and Crazing
text, January 2014


Growth, microstructure, and failure of crazes in glassy polymers
text, January 2003


Works referencing / citing this record:

Molecular dynamics simulation study of the fracture properties of polymer nanocomposites filled with grafted nanoparticles
journal, January 2019

  • Hu, Fengyan; Nie, Yun; Li, Fanzhu
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 21
  • DOI: 10.1039/c8cp07668e

Uncovering the rupture mechanism of carbon nanotube filled cis -1,4-polybutadiene via molecular dynamics simulation
journal, January 2018

  • Zhao, Xiuying; Li, Tiantian; Huang, Lan
  • RSC Advances, Vol. 8, Issue 49
  • DOI: 10.1039/c8ra04469d

Tuning cavitation and crazing in polymer nanocomposite glasses containing bimodal grafted nanoparticles at the nanoparticle/polymer interface
journal, January 2019

  • Shi, Rui; Qian, Hu-Jun; Lu, Zhong-Yuan
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 13
  • DOI: 10.1039/c9cp00208a

Molecular dynamics simulation of thermo-mechanical behaviour of elastomer cross-linked via multifunctional zwitterions
journal, January 2019

  • Athir, Naveed; Shi, Ling; Shah, Sayyed Asim Ali
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 38
  • DOI: 10.1039/c9cp03221e

Distinguishing failure modes in oligomeric polymer nanopillars
journal, January 2019

  • Lin, Emily Y.; Riggleman, Robert A.
  • Soft Matter, Vol. 15, Issue 32
  • DOI: 10.1039/c9sm00699k

Cavitation, crazing and bond scission in chemically cross-linked polymer nanocomposites
journal, January 2019

  • Zhang, Huan; Li, Haoxiang; Hu, Fengyan
  • Soft Matter, Vol. 15, Issue 45
  • DOI: 10.1039/c9sm01664c

Mechanical properties of polymer grafted nanoparticle composites
journal, October 2018


Mechanical properties of polymer grafted nanoparticle composites
text, January 2019


Mechanical properties of polymer grafted nanoparticle composites
text, January 2019


Salt concentration dependence of the mechanical properties of LiPF6 /poly(propylene glycol) acrylate electrolyte at a graphitic carbon interface: A reactive molecular dynamics study
journal, March 2018

  • Verners, Osvalds; Lyulin, Alexey V.; Simone, Angelo
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 9
  • DOI: 10.1002/polb.24584