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Title: The bond rupture force for sulfur chains calculated from quantum chemistry simulations and its relevance to the tensile strength of vulcanized rubber

Abstract

From quantum chemistry simulations using density functional theory, we obtain the total electronic energy of an eight-atom sulfur chain as its end-to-end distance is extended until S–S bond rupture occurs. We find that a sulfur chain can be extended by about 40% beyond its nominally straight conformation, where it experiences rupture at an end-to-end tension of about 1.5 nN. Using this rupture force as the chain failure limit in an explicit polymer network simulation model (EPnet), we predict the tensile failure stress for sulfur crosslinked (vulcanized) natural rubber. Furthermore, quantitative agreement with published experimental data for the failure stress is obtained in these simulations if we assume that only about 30% of the sulfur chains produce viable network crosslinks. Surprisingly, we also find that the failure stress of a rubber network does not scale linearly with the chain failure force limit.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1410622
Report Number(s):
LA-UR-17-25485
Journal ID: ISSN 1463-9076; TRN: US1800142
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 20; Journal Issue: 13; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science; Rubber Quantum Chemistry

Citation Formats

Hanson, David Edward, and Barber, John L. The bond rupture force for sulfur chains calculated from quantum chemistry simulations and its relevance to the tensile strength of vulcanized rubber. United States: N. p., 2017. Web. doi:10.1039/C7CP06730E.
Hanson, David Edward, & Barber, John L. The bond rupture force for sulfur chains calculated from quantum chemistry simulations and its relevance to the tensile strength of vulcanized rubber. United States. doi:10.1039/C7CP06730E.
Hanson, David Edward, and Barber, John L. Mon . "The bond rupture force for sulfur chains calculated from quantum chemistry simulations and its relevance to the tensile strength of vulcanized rubber". United States. doi:10.1039/C7CP06730E. https://www.osti.gov/servlets/purl/1410622.
@article{osti_1410622,
title = {The bond rupture force for sulfur chains calculated from quantum chemistry simulations and its relevance to the tensile strength of vulcanized rubber},
author = {Hanson, David Edward and Barber, John L.},
abstractNote = {From quantum chemistry simulations using density functional theory, we obtain the total electronic energy of an eight-atom sulfur chain as its end-to-end distance is extended until S–S bond rupture occurs. We find that a sulfur chain can be extended by about 40% beyond its nominally straight conformation, where it experiences rupture at an end-to-end tension of about 1.5 nN. Using this rupture force as the chain failure limit in an explicit polymer network simulation model (EPnet), we predict the tensile failure stress for sulfur crosslinked (vulcanized) natural rubber. Furthermore, quantitative agreement with published experimental data for the failure stress is obtained in these simulations if we assume that only about 30% of the sulfur chains produce viable network crosslinks. Surprisingly, we also find that the failure stress of a rubber network does not scale linearly with the chain failure force limit.},
doi = {10.1039/C7CP06730E},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 13,
volume = 20,
place = {United States},
year = {2017},
month = {11}
}

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Works referenced in this record:

Quantum chemistry and molecular dynamics studies of the entropic elasticity of localized molecular kinks in polyisoprene chains
journal, August 2010

  • Hanson, David E.; Martin, Richard L.
  • The Journal of Chemical Physics, Vol. 133, Issue 8
  • DOI: 10.1063/1.3475522

Measurement of Tensile Strength of Natural Rubber Vulcanizates at Elevated Temperature
journal, March 1982

  • Bell, C. L. M.; Stinson, D.; Thomas, A. G.
  • Rubber Chemistry and Technology, Vol. 55, Issue 1
  • DOI: 10.5254/1.3535876

Stress-strain data for vulcanised rubber under various types of deformation
journal, January 1944


The entropy of the rotational conformations of (poly)isoprene molecules and its relationship to rubber elasticity and temperature increase for moderate tensile or compressive strains
journal, December 2013

  • Hanson, David E.; Barber, John L.; Subramanian, Gopinath
  • The Journal of Chemical Physics, Vol. 139, Issue 22
  • DOI: 10.1063/1.4840096

The theoretical strength of rubber: numerical simulations of polyisoprene networks at high tensile strains evidence the role of average chain tortuosity
journal, October 2013

  • Hanson, David E.; Barber, John L.
  • Modelling and Simulation in Materials Science and Engineering, Vol. 21, Issue 7
  • DOI: 10.1088/0965-0393/21/7/075013

A new paradigm for the molecular basis of rubber elasticity
journal, February 2015


Elasticity of Natural Rubber Networks
journal, January 1996

  • Mott, P. H.; Roland, C. M.
  • Macromolecules, Vol. 29, Issue 21
  • DOI: 10.1021/ma960189s

Influence of Preparation Conditions on Network Parameters of Sulfur-Cured Natural Rubber
journal, November 2001

  • Klüppel, M.; Menge, H.; Schmidt, H.
  • Macromolecules, Vol. 34, Issue 23
  • DOI: 10.1021/ma010490v

Tensile strengths of pure gum natural rubber compounds
journal, October 1947


How far can a rubber molecule stretch before breaking? Ab initio study of tensile elasticity and failure in single-molecule polyisoprene and polybutadiene
journal, February 2009

  • Hanson, David E.; Martin, Richard L.
  • The Journal of Chemical Physics, Vol. 130, Issue 6
  • DOI: 10.1063/1.3071196