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.
- 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. https://doi.org/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. https://doi.org/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 = {Mon Nov 20 00:00:00 EST 2017},
month = {Mon Nov 20 00:00:00 EST 2017}
}
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