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Phosphorus-functionalized multi-wall carbon nanotubes as flame-retardant additives for polystyrene and poly (methyl methacrylate)

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Abstract

In the present work, we have studied the flame-retardant properties of phosphorus-functionalized multi-walled carbon nanotubes (MWCNTs) created by treating oxidized MWCNTs (O-MWCNTs) with phosphoric acid. These phosphorus MWCNTs (P-MWCNTs), along with pristine MWCNTs and O-MWCNTs, were incorporated into polystyrene (PS) and poly (methyl methacrylate) (PMMA) by solution blending at lower concentrations (0.5–10 mass%) than conventional organophosphorus flame retardants (5–30 mass%). Thermal properties of the PS and PMMA polymer nanocomposites were subsequently investigated through thermogravimetric (TG) analysis and microcombustion calorimetry. Scanning electron microscopy was used to evaluate P-MWCNT dispersion in each polymer matrix. P-MWCNTs were well-dispersed in PS, improved PS thermal stability during nitrogen pyrolysis in proportion to the phosphorus loading, and led to an improvement in PS flammability properties. In contrast, the P-MWCNTs were more aggregated in PMMA and only moderately improved PMMA thermal stability during pyrolysis. In both PS and PMMA, P-MWCNTs were more effective than either MWCNTs or O-MWCNTs at improving each polymer’s thermal oxidative stability during combustion in air. Characterization of the P-MWCNT nanoparticles, the PS and PMMA nanocomposites, and TG residues indicated that P-MWCNT flame retardants primarily act in the condensed phase, encouraging char formation of the dispersed MWCNT network as a route to protecting the polymer. By comparing results of polymer composites containing MWCNTs, O-MWCNTs or P-MWCNTs at comparable loadings, data from the current study indicate that phosphorus incorporation can improve the fire-retardant properties of MWCNTs, although optimizing P-MWCNT dispersion in different polymers remains critical to optimizing the flame-retardant effect.

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Acknowledgements

We acknowledge funds from the Johns Hopkins University (JHU) Water SEED Grant, the Air Force Office of Scientific Research (AFOSR), and the National Institute of Standards and Technology (NIST). We are grateful to the National Institute of Standards and Technology (NIST), the U.S. Naval Academy (USNA), and the JHU McQueen Lab (Kathyrn Arpino and Benjamin Trump) for facilities support. Particular thanks go to Dr. Joe Lomax, Dr. Maria Schroeder, Dr. Jeff Fitzgerald, and Dr. Patrick Fahey at USNA for many helpful discussions throughout the study.

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Authors and Affiliations

  1. Department of Chemistry, Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD, 21218, USA

    David P. Durkin, Miranda J. Gallagher, Benjamin P. Frank & D. Howard Fairbrother

  2. Department of Chemistry, American University, 4400 Massachusetts Ave, NW, Washington, DC, 20016, USA

    Elizabeth D. Knowlton & Douglas M. Fox

  3. Department of Chemistry, United States Naval Academy, 572M Holloway Rd, Annapolis, MD, 21402, USA

    Paul C. Trulove

  4. Engineering Laboratory- Fire Research Division, National Institute of Standards and Technology, 100 Bureau Drive MS-8665, Building 224, Gaithersburg, MD, 20899, USA

    Elizabeth D. Knowlton & Douglas M. Fox

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  1. David P. Durkin
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Correspondence to Douglas M. Fox.

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The authors declare no competing financial interest. Any opinions, findings and conclusions, or recommendations expressed in this manuscript are those of the authors and do not reflect the views of the US Air Force or the US Navy.

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Durkin, D.P., Gallagher, M.J., Frank, B.P. et al. Phosphorus-functionalized multi-wall carbon nanotubes as flame-retardant additives for polystyrene and poly (methyl methacrylate). J Therm Anal Calorim 130, 735–753 (2017). https://doi.org/10.1007/s10973-017-6432-z

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