Atomistic modeling framework for a cyclobutane-based mechanophore-embedded nanocomposite for damage precursor detection

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Abstract

An atomistic modeling framework is developed to simulate mechanophore activation and evaluate the sensitivity of cyclobutane-based mechanophores. Mechanophores are force-responsive functional units, which when embedded in an epoxy-based thermoset polymer matrix provide self-sensing capability in polymeric composites. In the presence of damage or damage precursors, covalent bond dissociation of the mechanophore generates fluorescence, which is referred to as the mechanophore activation. A Tris-(Cinnamoyloxymethyl)-Ethane (TCE) monomer is used to synthesize the cyclobutane structure through ultra-violet (UV) dimerization; the synthesized cyclobutanes are incorporated into the thermoset polymer matrix. A hybrid molecular dynamics (MD) simulation framework is developed by integrating two force-fields: a classical force-field, Merck Molecular Force Field (MMFF) and a bond-order based force-field, Reactive Force Field (ReaxFF). The hybrid MD methodology enables construction of the molecular model of the cyclobutane-based mechanophore embedded nanocomposite and simulation of the mechanophore activation. The synthesis of epoxy network and cyclobutane structure is numerically simulated by a covalent bond generation method employing MMFF. Through this numerical synthesis, the physical entanglement between the epoxy network and cyclobutane chain is also captured, which determines the local force distribution within the novel nanocomposite. Covalent bond dissociation due to the applied local force on the mechanophore is simulated using ReaxFF and results from the virtual deformation tests show successful mechanophore activation. A local work analysis method is developed to evaluate the sensitivity of mechanophore. Results from the simulation framework show increment in the number of activated cyclobutanes during the deformation test. Good agreement is observed with experimental results: the intensity of fluorescence was found to be directly proportional to the deformation.

Original languageEnglish (US)
Pages (from-to)135-141
Number of pages7
JournalComputational Materials Science
Volume120
DOIs
StatePublished - Jul 1 2016

Fingerprint

Cyclobutanes
cyclobutane
Nanocomposites
Force Field
Precursor
Covalent bonds
nanocomposites
field theory (physics)
Damage
Chemical activation
damage
Activation
Epoxy
Thermosets
Polymer matrix
Modeling
covalent bonds
Molecular dynamics
activation
Simulation Framework

Keywords

  • Cyclobutane-based mechanophore
  • Epoxy-based thermoset
  • Local work analysis
  • Molecular dynamics
  • Reactive force field

ASJC Scopus subject areas

  • Materials Science(all)
  • Chemistry(all)
  • Computer Science(all)
  • Physics and Astronomy(all)
  • Computational Mathematics
  • Mechanics of Materials

Cite this

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title = "Atomistic modeling framework for a cyclobutane-based mechanophore-embedded nanocomposite for damage precursor detection",
abstract = "An atomistic modeling framework is developed to simulate mechanophore activation and evaluate the sensitivity of cyclobutane-based mechanophores. Mechanophores are force-responsive functional units, which when embedded in an epoxy-based thermoset polymer matrix provide self-sensing capability in polymeric composites. In the presence of damage or damage precursors, covalent bond dissociation of the mechanophore generates fluorescence, which is referred to as the mechanophore activation. A Tris-(Cinnamoyloxymethyl)-Ethane (TCE) monomer is used to synthesize the cyclobutane structure through ultra-violet (UV) dimerization; the synthesized cyclobutanes are incorporated into the thermoset polymer matrix. A hybrid molecular dynamics (MD) simulation framework is developed by integrating two force-fields: a classical force-field, Merck Molecular Force Field (MMFF) and a bond-order based force-field, Reactive Force Field (ReaxFF). The hybrid MD methodology enables construction of the molecular model of the cyclobutane-based mechanophore embedded nanocomposite and simulation of the mechanophore activation. The synthesis of epoxy network and cyclobutane structure is numerically simulated by a covalent bond generation method employing MMFF. Through this numerical synthesis, the physical entanglement between the epoxy network and cyclobutane chain is also captured, which determines the local force distribution within the novel nanocomposite. Covalent bond dissociation due to the applied local force on the mechanophore is simulated using ReaxFF and results from the virtual deformation tests show successful mechanophore activation. A local work analysis method is developed to evaluate the sensitivity of mechanophore. Results from the simulation framework show increment in the number of activated cyclobutanes during the deformation test. Good agreement is observed with experimental results: the intensity of fluorescence was found to be directly proportional to the deformation.",
keywords = "Cyclobutane-based mechanophore, Epoxy-based thermoset, Local work analysis, Molecular dynamics, Reactive force field",
author = "Bonsung Koo and Aditi Chattopadhyay and Lenore Dai",
year = "2016",
month = "7",
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doi = "10.1016/j.commatsci.2016.04.003",
language = "English (US)",
volume = "120",
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T1 - Atomistic modeling framework for a cyclobutane-based mechanophore-embedded nanocomposite for damage precursor detection

AU - Koo, Bonsung

AU - Chattopadhyay, Aditi

AU - Dai, Lenore

PY - 2016/7/1

Y1 - 2016/7/1

N2 - An atomistic modeling framework is developed to simulate mechanophore activation and evaluate the sensitivity of cyclobutane-based mechanophores. Mechanophores are force-responsive functional units, which when embedded in an epoxy-based thermoset polymer matrix provide self-sensing capability in polymeric composites. In the presence of damage or damage precursors, covalent bond dissociation of the mechanophore generates fluorescence, which is referred to as the mechanophore activation. A Tris-(Cinnamoyloxymethyl)-Ethane (TCE) monomer is used to synthesize the cyclobutane structure through ultra-violet (UV) dimerization; the synthesized cyclobutanes are incorporated into the thermoset polymer matrix. A hybrid molecular dynamics (MD) simulation framework is developed by integrating two force-fields: a classical force-field, Merck Molecular Force Field (MMFF) and a bond-order based force-field, Reactive Force Field (ReaxFF). The hybrid MD methodology enables construction of the molecular model of the cyclobutane-based mechanophore embedded nanocomposite and simulation of the mechanophore activation. The synthesis of epoxy network and cyclobutane structure is numerically simulated by a covalent bond generation method employing MMFF. Through this numerical synthesis, the physical entanglement between the epoxy network and cyclobutane chain is also captured, which determines the local force distribution within the novel nanocomposite. Covalent bond dissociation due to the applied local force on the mechanophore is simulated using ReaxFF and results from the virtual deformation tests show successful mechanophore activation. A local work analysis method is developed to evaluate the sensitivity of mechanophore. Results from the simulation framework show increment in the number of activated cyclobutanes during the deformation test. Good agreement is observed with experimental results: the intensity of fluorescence was found to be directly proportional to the deformation.

AB - An atomistic modeling framework is developed to simulate mechanophore activation and evaluate the sensitivity of cyclobutane-based mechanophores. Mechanophores are force-responsive functional units, which when embedded in an epoxy-based thermoset polymer matrix provide self-sensing capability in polymeric composites. In the presence of damage or damage precursors, covalent bond dissociation of the mechanophore generates fluorescence, which is referred to as the mechanophore activation. A Tris-(Cinnamoyloxymethyl)-Ethane (TCE) monomer is used to synthesize the cyclobutane structure through ultra-violet (UV) dimerization; the synthesized cyclobutanes are incorporated into the thermoset polymer matrix. A hybrid molecular dynamics (MD) simulation framework is developed by integrating two force-fields: a classical force-field, Merck Molecular Force Field (MMFF) and a bond-order based force-field, Reactive Force Field (ReaxFF). The hybrid MD methodology enables construction of the molecular model of the cyclobutane-based mechanophore embedded nanocomposite and simulation of the mechanophore activation. The synthesis of epoxy network and cyclobutane structure is numerically simulated by a covalent bond generation method employing MMFF. Through this numerical synthesis, the physical entanglement between the epoxy network and cyclobutane chain is also captured, which determines the local force distribution within the novel nanocomposite. Covalent bond dissociation due to the applied local force on the mechanophore is simulated using ReaxFF and results from the virtual deformation tests show successful mechanophore activation. A local work analysis method is developed to evaluate the sensitivity of mechanophore. Results from the simulation framework show increment in the number of activated cyclobutanes during the deformation test. Good agreement is observed with experimental results: the intensity of fluorescence was found to be directly proportional to the deformation.

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KW - Epoxy-based thermoset

KW - Local work analysis

KW - Molecular dynamics

KW - Reactive force field

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JF - Computational Materials Science

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