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Title: A new paradigm for the molecular basis of rubber elasticity

Abstract

The molecular basis for rubber elasticity is arguably the oldest and one of the most important questions in the field of polymer physics. The theoretical investigation of rubber elasticity began in earnest almost a century ago with the development of analytic thermodynamic models, based on simple, highly-symmetric configurations of so-called Gaussian chains, i.e. polymer chains that obey Markov statistics. Numerous theories have been proposed over the past 90 years based on the ansatz that the elastic force for individual network chains arises from the entropy change associated with the distribution of end-to-end distances of a free polymer chain. There are serious philosophical objections to this assumption and others, such as the assumption that all network nodes undergo affine motion and that all of the network chains have the same length. Recently, a new paradigm for elasticity in rubber networks has been proposed that is based on mechanisms that originate at the molecular level. Using conventional statistical mechanics analyses, quantum chemistry, and molecular dynamics simulations, the fundamental entropic and enthalpic chain extension forces for polyisoprene (natural rubber) have been determined, along with estimates for the basic force constants. Concurrently, the complex morphology of natural rubber networks (the joint probability density distributionsmore » that relate the chain end-to-end distance to its contour length) has also been captured in a numerical model. When molecular chain forces are merged with the network structure in this model, it is possible to study the mechanical response to tensile and compressive strains of a representative volume element of a polymer network. As strain is imposed on a network, pathways of connected taut chains, that completely span the network along strain axis, emerge. Although these chains represent only a few percent of the total, they account for nearly all of the elastic stress at high strain. Here we provide a brief review of previous elasticity theories and their deficiencies, and present a new paradigm with an emphasis on experimental comparisons.« less

Authors:
 [1];  [1]
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  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1239115
Report Number(s):
LA-UR-14-27776
Journal ID: ISSN 0010-7514
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Contemporary Physics
Additional Journal Information:
Journal Volume: 56; Journal Issue: 3; Journal ID: ISSN 0010-7514
Publisher:
Taylor and Francis
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; natural rubber; elasticity theory; networks; polymer modeling

Citation Formats

Hanson, David E., and Barber, John L. A new paradigm for the molecular basis of rubber elasticity. United States: N. p., 2015. Web. doi:10.1080/00107514.2015.1006810.
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Hanson, David E., & Barber, John L. A new paradigm for the molecular basis of rubber elasticity. United States. https://doi.org/10.1080/00107514.2015.1006810
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Hanson, David E., and Barber, John L. Thu . "A new paradigm for the molecular basis of rubber elasticity". United States. https://doi.org/10.1080/00107514.2015.1006810. https://www.osti.gov/servlets/purl/1239115.
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@article{osti_1239115,
title = {A new paradigm for the molecular basis of rubber elasticity},
author = {Hanson, David E. and Barber, John L.},
abstractNote = {The molecular basis for rubber elasticity is arguably the oldest and one of the most important questions in the field of polymer physics. The theoretical investigation of rubber elasticity began in earnest almost a century ago with the development of analytic thermodynamic models, based on simple, highly-symmetric configurations of so-called Gaussian chains, i.e. polymer chains that obey Markov statistics. Numerous theories have been proposed over the past 90 years based on the ansatz that the elastic force for individual network chains arises from the entropy change associated with the distribution of end-to-end distances of a free polymer chain. There are serious philosophical objections to this assumption and others, such as the assumption that all network nodes undergo affine motion and that all of the network chains have the same length. Recently, a new paradigm for elasticity in rubber networks has been proposed that is based on mechanisms that originate at the molecular level. Using conventional statistical mechanics analyses, quantum chemistry, and molecular dynamics simulations, the fundamental entropic and enthalpic chain extension forces for polyisoprene (natural rubber) have been determined, along with estimates for the basic force constants. Concurrently, the complex morphology of natural rubber networks (the joint probability density distributions that relate the chain end-to-end distance to its contour length) has also been captured in a numerical model. When molecular chain forces are merged with the network structure in this model, it is possible to study the mechanical response to tensile and compressive strains of a representative volume element of a polymer network. As strain is imposed on a network, pathways of connected taut chains, that completely span the network along strain axis, emerge. Although these chains represent only a few percent of the total, they account for nearly all of the elastic stress at high strain. Here we provide a brief review of previous elasticity theories and their deficiencies, and present a new paradigm with an emphasis on experimental comparisons.},
doi = {10.1080/00107514.2015.1006810},
journal = {Contemporary Physics},
number = 3,
volume = 56,
place = {United States},
year = {Thu Feb 19 00:00:00 EST 2015},
month = {Thu Feb 19 00:00:00 EST 2015}
}
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    An Elastic Autonomous Self-Healing Capacitive Sensor Based on a Dynamic Dual Crosslinked Chemical System
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    Parallel Replica Dynamics of Bead-Spring Elastomers at Low Strain Rates
    journal, May 2018

    Elastocaloric effect dependence on pre-elongation in natural rubber
    journal, August 2015

    • Xie, Zhongjian; Sebald, Gael; Guyomar, Daniel
    • Applied Physics Letters, Vol. 107, Issue 8
    • DOI: 10.1063/1.4929395
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