Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments

Yang, Dali; Hubbard, Kevin M.; Henderson, Kevin C.; Labouriau, Andrea

doi:10.1002/app.41450

Title: Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments

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Abstract

Here, we compare the aging behaviors of cross-linked ethylene/vinyl acetate/vinyl alcohol terpolymers, also referred to as EVA-OH, when they are either immersed in nitroplasticizer (NP) liquid or exposed to NP vapor at different temperatures. And while thermogravimetric analysis and differential scanning calorimetry are used to probe the thermal stability of aged NP and polymers, Fourier transform infrared, gel permeation chromatography, ultra-violet/vis, and nuclear magnetic resonance are used to probe their structural changes over the aging process. Our study confirms that NP degrades through C[BOND]N cleavage, and releases HONO molecules at a slightly elevated temperature (<75°C). As these molecules accumulate in the vapor phase, they react among themselves to create an acidic environment. Therefore, these chemical constituents in the NP vapor significantly accelerate the hydrolysis of EVA-OH polymer. When the hydrolysis occurs in both vinyl acetate and urethane groups and the scission at the cross-linker progresses, EVA-OH becomes vulnerable to further degradation in the NP vapor environment. Finally, through the comprehensive characterization, the possible degradation mechanisms of the terpolymers are proposed.

Authors:

Yang, Dali ^[1]; Hubbard, Kevin M. ^[1]; Henderson, Kevin C. ^[1]; Labouriau, Andrea ^[2]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology, Polymers and Coatings
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry, Chemical Diagnostics and Engineering

Publication Date:: Wed Sep 17 00:00:00 EDT 2014

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1304701

Report Number(s):: LA-UR-14-24345
Journal ID: ISSN 0021-8995

Grant/Contract Number:: AC52-06NA25396

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of Applied Polymer Science

Additional Journal Information:: Journal Volume: 132; Journal Issue: 7; Journal ID: ISSN 0021-8995

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ageing; degradation; EVA-OH; hydrolysis; plasticizer; thermogravimetric analysis (TGA)

Citation Formats


                    Yang, Dali, Hubbard, Kevin M., Henderson, Kevin C., and Labouriau, Andrea. Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments.  United States: N. p., 2014. 
        Web.  doi:10.1002/app.41450.

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                    Yang, Dali, Hubbard, Kevin M., Henderson, Kevin C., & Labouriau, Andrea. Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments.  United States.  https://doi.org/10.1002/app.41450

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                    Yang, Dali, Hubbard, Kevin M., Henderson, Kevin C., and Labouriau, Andrea. 2014.  
        "Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments".  United States.  https://doi.org/10.1002/app.41450.  https://www.osti.gov/servlets/purl/1304701.

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@article{osti_1304701,

  title        = {Thermal and chemical stabilization of ethylene/vinyl acetate/vinyl alcohol (EVA-OH) terpolymers under nitroplasticizer environments},

  author       = {Yang, Dali and Hubbard, Kevin M. and Henderson, Kevin C. and Labouriau, Andrea},

  abstractNote = {Here, we compare the aging behaviors of cross-linked ethylene/vinyl acetate/vinyl alcohol terpolymers, also referred to as EVA-OH, when they are either immersed in nitroplasticizer (NP) liquid or exposed to NP vapor at different temperatures. And while thermogravimetric analysis and differential scanning calorimetry are used to probe the thermal stability of aged NP and polymers, Fourier transform infrared, gel permeation chromatography, ultra-violet/vis, and nuclear magnetic resonance are used to probe their structural changes over the aging process. Our study confirms that NP degrades through C[BOND]N cleavage, and releases HONO molecules at a slightly elevated temperature (<75°C). As these molecules accumulate in the vapor phase, they react among themselves to create an acidic environment. Therefore, these chemical constituents in the NP vapor significantly accelerate the hydrolysis of EVA-OH polymer. When the hydrolysis occurs in both vinyl acetate and urethane groups and the scission at the cross-linker progresses, EVA-OH becomes vulnerable to further degradation in the NP vapor environment. Finally, through the comprehensive characterization, the possible degradation mechanisms of the terpolymers are proposed.},

  doi          = {10.1002/app.41450},

  url          = {https://www.osti.gov/biblio/1304701},
  journal      = {Journal of Applied Polymer Science},

  issn         = {0021-8995},

  number       = 7,

  volume       = 132,

  place        = {United States},

  year         = {Wed Sep 17 00:00:00 EDT 2014},

  month        = {Wed Sep 17 00:00:00 EDT 2014}

}

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