Carbon-Based Nanomaterials for Flame Retardant Polymers
Md. Enamul Kabir, Most. Israt Jahan, Muhammed Shah Miran
Polymers are frequently employed materials; however, they are exceedingly combustible, which presents significant fire hazards. Many conventional flame retardants (FRs), particularly halogenated ones, are harmful to the environment and reduce mechanical qualities. A multipurpose alternative, carbon nanotubes, graphene, Fullerene, and carbon black improve flame resistance, thermal stability, mechanical strength, and conductivity at low loadings. This chapter covers carbon reinforced polymer composites’ flame retardancy mechanisms, synthesis methods, and synergistic effects with typical FRs. Addressing present issues and future research objectives, it emphasizes the potential of carbon nanomaterials to produce flame-retardant polymers that are safer, more performant, and less harmful to the environment.
Keywords
Carbon-based Materials, Limiting Oxygen Index, Peak Heat Release Rate, Flame Retardant Polymers, Carbon Nanotubes
Published online 5/1/2026, 35 pages
Citation: Md. Enamul Kabir, Most. Israt Jahan, Muhammed Shah Miran, Carbon-Based Nanomaterials for Flame Retardant Polymers, Materials Research Foundations, Vol. 190, pp 118-152, 2026
DOI: https://doi.org/10.21741/9781644904077-5
Part of the book on Flame Retardant Materials
References
[1] S. Araby, B. Philips, Q. Meng, J. Ma, T. Laoui, C.H. Wang, Recent advances in carbon-based nanomaterials for flame retardant polymers and composites, Compos. B: Eng. 212 (2021) 108675. https://doi.org/10.1016/j.compositesb.2021.108675
[2] J. Giebułtowicz, M. Rużycka, P. Wroczyński, D.A. Purser, A.A. Stec, Analysis of fire deaths in Poland and influence of smoke toxicity, Forensic Sci. Int. 277 (2017) 77-87. https://doi.org/10.1016/j.forsciint.2017.05.018
[3] G. Beyer, Nanocomposites: a new class of flame retardants for polymers. Plastics, Additives and Compounding 4 (2002) 22-28. https://doi.org/10.1016/S1464-391X(02)80151-9
[4] T. Kurauchi, A. Okada, T. Nomura, T. Nishio, S. Saegusa, R. Deguchi, R. Degushi, Nylon 6-clay hybrid-synthesis, properties and application to automotive timing belt cover. SAE Transactions (1991) 571-577. https://doi.org/10.4271/910584
[5] E.P. Giannelis, Polymer layered silicate nanocomposites. Adv. Mater. 8 (1996) 29-35. https://doi.org/10.1002/adma.19960080104
[6] S. Araby, J. Li, G. Shi, Z. Ma, J. Ma, Graphene for flame-retarding elastomeric composite foams having strong interface. Compos. A: Appl. Sci. Manuf. 101 (2017) 254-264. https://doi.org/10.1016/j.compositesa.2017.06.022
[7] H. Huang, D. Dong, W. Li, X. Zhang, L. Zhang, Y. Chen, X. Lu, Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly (lactic acid) composites. Chin. J. Chem. Eng. 28 (2020) 1981-1993. https://doi.org/10.1016/j.cjche.2020.04.014
[8] X. Wang, E.N. Kalali, J.T. Wan, D.Y. Wang, Carbon-family materials for flame-retardant polymeric materials. Prog. Polym. Sci. 69 (2017) 22-46. https://doi.org/10.1016/j.progpolymsci.2017.02.001
[9] S. Bourbigot, M. Le Bras, R. Delobel, L. Gengembre, XPS study of an intumescent coating: II. Application to the ammonium polyphosphate/pentaerythritol/ethylenic terpolymer fire retardant system with and without synergistic agent. Appl. Surf. Sci. 120(1997) 15-29.
[10] X. Wang, H. Yang, L. Song, Y. Hu, W. Xing, H. Lu, Morphology, mechanical and thermal properties of graphene-reinforced poly (butylene succinate) nanocomposites. Compos. Sci. Technol. 72 (2011) 1-6. https://doi.org/10.1016/j.compscitech.2011.05.007
[11] Y. Yang, J.L. Díaz Palencia, N. Wang, Y. Jiang, D.Y. Wang, Nanocarbon-based flame retardant polymer nanocomposites. Molecules 26 (2021) 4670. https://doi.org/10.3390/molecules26154670
[12] H. Parsimehr, M. Enayati, A.E. Langroudi, Recent Developments in Green Flame Retardants Based on Carbon Nanotubes. Materials and Chemistry of Flame-Retardant Polyurethanes Volume 2: Green Flame Retardants, 2021, p. 47-63. https://doi.org/10.1021/bk-2021-1400.ch004
[13] X. Wang, E.N. Kalali, J.T. Wan, D.Y. Wang, Carbon-family materials for flame-retardant polymeric materials. Prog. Polym. Sci. 69 (2017) 22-46. https://doi.org/10.1016/j.progpolymsci.2017.02.001
[14] A.N. Muranov, V.R. Lysenko, M.A. Kocharov, Rheological behavior features of feedstocks with a two-component wax-polyolefin binder compared to analogs based on polyoxymethylene. J. Compos. Sci. 8 (2024) 199. https://doi.org/10.3390/jcs8060199
[15] M. Ciesielski, B. Burk, C. Heinzmann, M. Döring, Fire-retardant high-performance epoxy-based materials. In Novel Fire Retardant Polymers and Composite Materials, Woodhead Publishing, 2017, pp. 3-51. https://doi.org/10.1016/B978-0-08-100136-3.00002-9
[16] Y. Yang, J.L. Díaz Palencia, N. Wang, Y. Jiang, D.Y. Wang, Nanocarbon-based flame retardant polymer nanocomposites. Molecules 26 (2021) 4670. https://doi.org/10.3390/molecules26154670
[17] X. Wang, W. Xing, X. Feng, B. Yu, L. Song, Y. Hu, Functionalization of graphene with grafted polyphosphamide for flame-retardant epoxy composites: synthesis, flammability, and mechanism. Polym. Chem. 5 (2014) 1145-1154. https://doi.org/10.1039/C3PY00963G
[18] Q. Leng, J. Li, Y. Wang, Structural analysis of α-zirconium phosphate/cerium phosphate/graphene oxide nanocomposites with flame-retardant properties in polyvinyl alcohol. New J. Chem. 44 (2020) 4568-4577. https://doi.org/10.1039/C9NJ06253J
[19] W. Luo, Y. Li, H. Zou, M. Liang, Study of different-sized sulfur-free expandable graphite on morphology and properties of water-blown semi-rigid polyurethane foams. RSC Adv. 4 (2014) 37302-37310. https://doi.org/10.1039/C4RA05559D
[20] B. Yu, Y. Shi, B. Yuan, S. Qiu, W. Xing, W. Hu, Y. Hu, Enhanced thermal and flame retardant properties of flame-retardant-wrapped graphene/epoxy resin nanocomposites. J. Mater. Chem. 3 (2015) 8034-8044. https://doi.org/10.1039/C4TA06613H
[21] F. Fang, S. Ran, Z. Fang, P. Song, H. Wang, Improved flame resistance and thermo-mechanical properties of epoxy resin nanocomposites from functionalized graphene oxide via self-assembly in water. Compos. B: Eng. 165 (2019). 406-416. https://doi.org/10.1016/j.compositesb.2019.01.086
[22] W. Du, Y. Jin, S. Lai, L. Shi, Y. Shen, H. Yang, Multifunctional light-responsive graphene-based polyurethane composites with shape memory, self-healing, and flame retardancy properties. Compos. A: Appl. Sci. Manuf. 128 (2020) 105686. https://doi.org/10.1016/j.compositesa.2019.105686
[23] M.J. Kim, I.Y. Jeon, J.M. Seo, L. Dai, J.B. Baek, Graphene phosphonic acid as an efficient flame retardant. ACS nano. 8 (3) 2820-2825. https://doi.org/10.1021/nn4066395
[24] G. Huang, S. Huo, X. Xu, W. Chen, Y. Jin, R. Li, H. Wang, Realizing simultaneous improvements in mechanical strength, flame retardancy and smoke suppression of ABS nanocomposites from multifunctional graphene. Compos. B: Eng. 177 (2019) 107377. https://doi.org/10.1016/j.compositesb.2019.107377
[25] J. Li, W. Meng, W. Wu, Z. Zhou, W. Zhang, P. Song, H. Qu, Nickel ammonium phosphate and reduced graphene oxide two‐dimensional hybrid material for improving the fire safety and mechanical properties of poly (vinyl chloride). Polym. Int. 69 (2020) 1227-1236. https://doi.org/10.1002/pi.6066
[26] N. Hong, Y. Pan, J. Zhan, B. Wang, K. Zhou, L. Song, Y. Hu, Fabrication of graphene/Ni-Ce mixed oxide with excellent performance for reducing fire hazard of polypropylene. RSC Adv. 3 (2013) 16440-16448. https://doi.org/10.1039/c3ra42095g
[27] S.D. Jiang, Z.M. Bai, G. Tang, L. Song, A.A. Stec, T.R. Hull, Y. Hu, Fabrication of Ce-doped MnO2 decorated graphene sheets for fire safety applications of epoxy composites: flame retardancy, smoke suppression and mechanism. J. Mater. Chem. 2 (2014) 17341-17351. https://doi.org/10.1039/C4TA02882A
[28] X. Wang, S. Zhou, W. Xing, B. Yu, X. Feng, L. Song, Y. Hu, Self-assembly of Ni-Fe layered double hydroxide/graphene hybrids for reducing fire hazard in epoxy composites. J. Mater. Chem. 1 (2013) 4383-4390. https://doi.org/10.1039/c3ta00035d
[29] T. Kashiwagi, F. Du, J.F. Douglas, K.I. Winey, R.H. Harris Jr, J.R. Shields, Nanoparticle networks reduce the flammability of polymer nanocomposites. Nat. mater. 4 (2005) 928-933. https://doi.org/10.1038/nmat1502
[30] J.F. Colomer, L. Henrard, G. Van Tendeloo, A. Lucas, P. Lambin, Study of the packing of double-walled carbon nanotubes into bundles by transmission electron microscopy and electron diffraction. J. Mateপ. Chem. 14 (2004) 603-606. https://doi.org/10.1039/b311551h
[31] I.V. Obronov, V.I. Kleshch, E.A. Smolnikova, D.A. Bandurin, A.N. Obraztsov, Field emission properties of single-walled carbon nanotube films. J. nanoelectron. Optoelectron. 8 (2013) 71-74. https://doi.org/10.1166/jno.2013.1438
[32] T. Kashiwagi, F. Du, K.I. Winey, K.M. Groth, J.R. Shields, S.P. Bellayer, J.F. Douglas, Flammability properties of polymer nanocomposites with single-walled carbon nanotubes: effects of nanotube dispersion and concentration. Polymer. 46 (2005)471-481. https://doi.org/10.1016/j.polymer.2004.10.087
[33] S. Peeterbroeck, F. Laoutid, J.M. Taulemesse, F. Monteverde, J.M. Lopez‐Cuesta, J.B. Nagy, P. Dubois, Mechanical properties and flame‐retardant behavior of ethylene vinyl acetate/high‐density polyethylene coated carbon nanotube nanocomposites. Adv. Funct. Mater. 17 (2007) 2787-2791. https://doi.org/10.1002/adfm.200600936
[34] H. Yang, L. Ye, J. Gong, M. Li, Z. Jiang, X. Wen, T. Tang, Simultaneously improving the mechanical properties and flame retardancy of polypropylene using functionalized carbon nanotubes by covalently wrapping flame retardants, followed by linking polypropylene. Mater. Chem. Front. 1 (2017) 716-726. https://doi.org/10.1039/C6QM00172F
[35] B.H. Cipiriano, T. Kashiwagi, S.R. Raghavan, Y. Yang, E.A. Grulke, K. Yamamoto, J. F. Douglas, Effects of aspect ratio of MWNT on the flammability properties of polymer nanocomposites. Polymer. 48 (2007) 6086-6096. https://doi.org/10.1016/j.polymer.2007.07.070
[36] S. Bourbigot, G. Fontaine, A. Gallos, S. Bellayer, Reactive extrusion of PLA and of PLA/carbon nanotubes nanocomposite: processing, characterization and flame retardancy. Polym. Adv. Technol. 22 (2011) 30-37. https://doi.org/10.1002/pat.1715
[37] R. Verdejo, F. Barroso-Bujans, M.A. Rodriguez-Perez, J.A. de Saja, M. Arroyo, M.A. Lopez-Manchado, Carbon nanotubes provide self-extinguishing grade to silicone-based foams. J. of Mater. Chem. 18 (2008) 3933-3939. https://doi.org/10.1039/b805943h
[38] B. Dittrich, K.A. Wartig, D. Hofmann, R. Mülhaupt, B. Schartel, Flame retardancy through carbon nanomaterials: Carbon black, multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polym. Degrad. Stab. 98 (2013) 1495-1505. https://doi.org/10.1016/j.polymdegradstab.2013.04.009
[39] G. Huang, S. Wang, P.A. Song, C. Wu, S. Chen, X. Wang, Combination effect of carbon nanotubes with graphene on intumescent flame-retardant polypropylene nanocomposites. Compos. – A: Appl. Sci. Manuf. 59 (2014) 18-25. https://doi.org/10.1016/j.compositesa.2013.12.010
[40] M. Bhattacharya, Polymer nanocomposites-a comparison between carbon nanotubes, graphene, and clay as nanofillers. Materials. 9 (2016) 262. https://doi.org/10.3390/ma9040262
[41] J. Sandler, J.E. Kirk, I.A. Kinloch, M.S.P. Shaffer, A.H. Windle, Ultra-low electrical percolation threshold in carbon-nanotube-epoxy composites. Polymer. 44 (2003). 5893-5899. https://doi.org/10.1016/S0032-3861(03)00539-1
[42] X. Wen, Y. Wang, J. Gong, J. Liu, N. Tian, Y. Wang, T. Tang, Thermal and flammability properties of polypropylene/carbon black nanocomposites. Polym. Degrad. Stab. 97 (2012) 793-801. https://doi.org/10.1016/j.polymdegradstab.2012.01.031
[43] X. Wen, K. Szymańska, X. Chen, E. Mijowska, Nanosized carbon black as synergist in PP/POE-MA/IFR system for simultaneously improving thermal, electrical and mechanical properties. J. Therm. Anal. Calorim. 139 (2020) 1091-1098. https://doi.org/10.1007/s10973-019-08466-4
[44] X. Wen, Z. Liu, Z. Li, J. Zhang, D.Y. Wang, K. Szymańska, T. Tang, Constructing multifunctional nanofiller with reactive interface in PLA/CB-g-DOPO composites for simultaneously improving flame retardancy, electrical conductivity and mechanical properties. Compos. Sci. Technol. 188 (2020) 107988. https://doi.org/10.1016/j.compscitech.2019.107988
[45] J. Liu, Y. Zhang, Y. Guo, C. Lu, B. Pan, S. Peng, Q. Niu, Effect of carbon black on the thermal degradation and flammability properties of flame‐retarded high impact polystyrene/magnesium hydroxide/microencapsulated red phosphorus composite. Polym. Compos. 39 (2018) 770-782. https://doi.org/10.1002/pc.23998
[46] L. Liu, X. Zhao, C. Ma, X. Chen, S. Li, C. Jiao, Smoke suppression properties of carbon black on flame-retardant thermoplastic polyurethane based on ammonium polyphosphate. J. Therm. Anal. Calorim. 126 (2016) 1821-1830. https://doi.org/10.1007/s10973-016-5815-x
[47] Y. Pan, Z. Guo, S. Ran, Z. Fang, Influence of fullerenes on the thermal and flame‐retardant properties of polymeric materials. J. Appl. Polym. Sci. 137 (2020) 47538. https://doi.org/10.1002/app.47538
[48] Ü. Tayfun, M. Doğan, Flame-retardant properties of fullerene and nanodiamond-based polymer nanocomposites. In Flame Retardant Nanocomposites, Woodhead Publishing, pp. 263-286, 2024. https://doi.org/10.1016/B978-0-443-15421-8.00004-5
[49] Z. Fang, P. Song, L. Tong, Z. Guo, Thermal degradation and flame retardancy of polypropylene/C60 nanocomposites. Thermochim. Acta. 473 (2008) 106-108. https://doi.org/10.1016/j.tca.2008.04.019
[50] G.H. Yeoh, I.M. De Cachinho Cordeiro, W. Wang, C. Wang, A.C.Y. Yuen, T.B.Y. Chen, H.T. Chua, Carbon‐based flame retardants for polymers: A bottom‐up review. Adv. Mater. 36 (2024) 2403835. https://doi.org/10.1002/adma.202403835
[51] P.A. Song, H. Liu, Y. Shen, B. Du, Z. Fang, Y. Wu, Fabrication of dendrimer-like fullerene (C 60)-decorated oligomeric intumescent flame retardant for reducing the thermal oxidation and flammability of polypropylene nanocomposites. J. Mater. Chem. 19 (2009) 1305-1313. https://doi.org/10.1039/b815610g
[52] Z. Guo, Z. Wang, Z. Fang, Fabrication of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-decorated fullerene to improve the anti-oxidative and flame-retardant properties of polypropylene. Compos. B: Eng.183 (2020) 107672. https://doi.org/10.1016/j.compositesb.2019.107672
[53] R. Wang, L. Wu, D. Zhuo, Z. Wang, T.Y. Tsai, Fabrication of fullerene anchored reduced graphene oxide hybrids and their synergistic reinforcement on the flame retardancy of epoxy resin. Nanoscale Res. Lett. 13 (2018) 1-14. https://doi.org/10.1186/s11671-018-2678-z
[54] P. Song, L. Zhao, Z. Cao, Z. Fang, Polypropylene nanocomposites based on C 60-decorated carbon nanotubes: Thermal properties, flammability, and mechanical properties. J. Mater. Chem. A. 21 (2011) 7782-7788. https://doi.org/10.1039/c1jm10395d
[55] X. Zhou, S. Ran, H. Hu, Z. Fang, Improving flame-retardant efficiency by incorporation of fullerene in styrene-butadiene-styrene block copolymer/aluminum hydroxide composites. J. Therm. Anal. Calorim. 125 (2016) 199-204. https://doi.org/10.1007/s10973-016-5354-5
[56] T.Y. Tsai, N. Bunekar, C.C. Huang, Y.S. Huang, L.C. Chen, Novolac cured epoxy resin/fullerene modified clay composites: Applied to copper clad laminates. Rsc Adv. 5 (2015) 95649-95656. https://doi.org/10.1039/C5RA18073B
[57] B. Mazela, A. Batista, W. Grześkowiak, Expandable graphite as a fire retardant for cellulosic materials-A review. Forests, 11 (2020) 755-763. https://doi.org/10.3390/f11070755
[58] Q. Yang, Y. Geng, H. Dong, J. Zhang, X. Yu, L. Sun, Y. Chen, Effect of environmental regulations on China’s graphite export. J. Clean. Prod. 161 (2017). 327-334. https://doi.org/10.1016/j.jclepro.2017.05.131
[59] H.D. Tuan Nguyen, H.T. Nguyen, T.T. Nguyen, A.K. Le Thi, T.D. Nguyen, Q.T. Phuong Bui, L.G. Bach, The preparation and characterization of MnFe2O4-decorated expanded graphite for removal of heavy oils from water. Materials. 12 (2019) 1913. https://doi.org/10.3390/ma12121913
[60] C. Alonso, A. Manich, A.D. Campo, P. Felix-De Castro, N. Boisseree, L. Coderch, M. Martí, Graphite flame retardant applied on polyester textiles: Flammable, thermal and in vitro toxicological analysis. J. Ind. Text. 51 (2022) 4424S-4440S. https://doi.org/10.1177/15280837211062056
[61] M.R. Nyden, R.H. Harris, Y.S. Kim, R.D. Davis, N.D. Marsh, M. Zammarano, Characterizing particle emissions from burning polymer nanocomposites. In Proceedings of the 21st BCC Conference on Flame Retardation (Vol. 1, pp. 717-719). (2010) Gaithersburg, MD, USA: National Institute of Standards and Technology-Nanotech.
[62] J.X. Bouillard, B. R’Mili, D. Moranviller, A. Vignes, O. Le Bihan, A. Ustache, D. Fleury, Nanosafety by design: Risks from nanocomposite/nanowaste combustion. J. Nanoparticle Res. 15 (2013) 1-11. https://doi.org/10.1007/s11051-013-1519-3
[63] R. Arvidsson, D. Kushnir, B.A. Sandén, S. Molander, Prospective life cycle assessment of graphene production by ultrasonication and chemical reduction. Environ. Sci. amp; Technol. 48 (2014) 4529-4536. https://doi.org/10.1021/es405338k
[64] S. Araby, B. Philips, Q. Meng, J. Ma, T. Laoui, C.H. Wang, Recent advances in carbon-based nanomaterials for flame retardant polymers and composites. Compos. B: Eng. 212 (2021) 108675. https://doi.org/10.1016/j.compositesb.2021.108675
[65] P. Song, Y. Shen, B. Du, Z. Guo, Z. Fang, Fabrication of fullerene-decorated carbon nanotubes and their application in flame-retarding polypropylene. Nanoscale. 1 (2009) 118-121. https://doi.org/10.1039/b9nr00026g


