Flame Retardants: Additives in Plastic Technology

  • Soheir Youssef Tawfik
Living reference work entry

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This chapter deals with a brief account on various types of topics on flame retardant materials as additives in plastic technology. The chapter focuses on the mechanism of polymer combustion, the main mode of action, and the quality properties of flame retardant materials. It also focuses on the commonly used flammability test for polymers: they are radiant panel, limited oxygen indices (LOI), underwriter’s laboratories (UL 94), and cone calorimeter. This chapter discusses the types of flame retardant materials based on their mode of action, on their mechanism during fire, and on their functional elements. The most known flame retardant based on their functional elements are mineral flame retardants (e.g., metal hydroxide, hydroxyl carbonates, borates), halogenated flame retardants, phosphorous compounds, nitrogen-containing flame retardants, silicon-based flame retardants, and nanometric particles. Since more environmental regulations restricted to halogenated flame retardants especially the brominated ones are issued for health concern and environmental issues, fire safety versus environmental safety and current trend for replacing halogenated flame retardant were reviewed.


Fire Types of flame retardant Environmental Health concern Alternative additives Nanoflame retardant 


Glossary of Flame Retardants


Compound added after the polymer has been synthesized but before or during its conversion to final form (e.g., fiber, plastic); not covalently bound to polymer substrate

Carbon nanotubes (CNTs)

An allotrope of carbon. They take the form of cylindrical carbon molecules and have novel properties that make them potentially useful in a wide variety of applications in nanotechnology, electronics, optics, and other fields of materials science


Self-catalyzed exothermic reaction involving two reactants (fuel and oxidizer)

Fire Resistance

Capacity of a material or structure to withstand fire without losing its functional properties


Uncontrolled combustion

Flame Propagation

Spread of flame from region to region in a combustible material (burning velocity = rate of flame propagation

Flame Resistance

Property in a material of exhibiting reduced flammability

Flame Retardant

Chemical compound capable of imparting flame resistance to (reducing flammability of) a material to which it is added


Gas-phase combustion processes with emission of visible light


Tendency of a material to burn with a flame

Heat flux or thermal flux

The rate of heat energy transfer through a given surface, per unit time. The SI derived unit of heat rate is joule per second, or watt. Heat flux density is the heat rate per unit area. In SI units, heat flux density is measured in [W/m2]


Initiation of combustion


A broad class of naturally occurring inorganic minerals, of which platelike montmorillonite is the most commonly used in materials applications

SI units

International System of Units (noun): SI unit, a system of physical units (SI units) based on the meter, kilogram, second, ampere, kelvin, candela, and mole, together with a set of prefixes to indicate multiplication or division by a power of ten


Fine dispersion in air of particles of carbon and other solids and liquids resulting from incomplete combustion


Observed effectiveness of combinations of compounds greater than the sum of the effects of individual components

Thermal degradation

Irreversible chemical decomposition due to increase in temperature


Harmful effect on a biological system caused by a chemical or physical agent


  1. A summary of this technology and its capabilities can be found in Wikipedia at Accessed 1 Apr 2013
  2. Aaron C, Small CCT-M, Thomas P, Martin R, Frances D, Lisa S (2008) A non-halogenated flame retardant additive for pultrusion. Compos Res J 2:15Google Scholar
  3. Alaeea M, Arias P, Sjodin A, Bergmand A (2003) An overview of commercially used brominated flame retardants. Their applications, their use patterns in different countries/regions and possible modes of release. Environ Int 29:683–689CrossRefGoogle Scholar
  4. Andersson Ö, Blomkvist G (1981) Polybrominated aromatic pollutants found in fish in Sweden. Chem Rev 10:1051–1060Google Scholar
  5. Belousova RG, Schwartz EM, Zariņa IE, Valdniece DJ (2010) Low-toxicity boron-containing flame-retardant additives for polymeric coatings. Russ J Appl Chem 83:328–331CrossRefGoogle Scholar
  6. Bocchini S, Frache A, Camino G, Claes M (2007) Polyethylene thermal oxidative stabilization in carbon nanotubes based nanocomposites. Eur Polym J 43:3222CrossRefGoogle Scholar
  7. Camino G, Maffezzoli A, Braglia M, De Lazzaro M, Zammarano M (2001) Effect of hydroxides and hydroxy carbonate structure on flame retardant effectiveness and mechanical properties in ethylene-vinyl acetate copolymer. Polym Degrad Stab 74:457–464CrossRefGoogle Scholar
  8. Camino G, Costa L, Luda di Cortemiglia MP (1991) Overview of fire retardant mechanisms. Polym Degrad Stab 33(2):131–154CrossRefGoogle Scholar
  9. Chang YL, Wang YZ, Ban DM, Yang B, Zhao GM (2004) A novel phosphorus-containing polymer as a highly effective flame retardant. Macromol Mater Eng 289:703–707CrossRefGoogle Scholar
  10. Chen SJ, Ma YJ, Wang J, Chen D, Luo XJ, Mai BX (2009) Brominated flame retardants in children’s toys: concentration, composition, and children’s exposure and risk assessment. Environ Sci Technol 43(11):4200–4206CrossRefGoogle Scholar
  11. Cordner A, Brown P (2013) Moments of uncertainty: ethical considerations and emerging contaminants. Sociol Forum 28(3):469–494CrossRefGoogle Scholar
  12. Covaci A, Muenhor D, Harrad S, Ali N (2010) Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ Int 36(7):690–698CrossRefGoogle Scholar
  13. Dasari A, Yu Z-Z, Mai Y-W, Cai G, Song H (2009) Roles of graphite oxide, clay and POSS during the combustion of polyamide 6. Polymer 50:1577–1587CrossRefGoogle Scholar
  14. Davis J, Huggard M (1996) The technology of halogen-free flame retardant phosphorus additives for polymeric systems. J Vinyl Addit Technol 2(1):69–75CrossRefGoogle Scholar
  15. Davis R, Li YC, Gervasio M, Luu J, Kim YS (2015) One-Pot, bioinspired coatings to reduce the flammability of flexible polyurethane foams. ACS Appl Mater Interfaces 7(11):6082–6092CrossRefGoogle Scholar
  16. Dittrich B, Wartig KA, Hofmann D, Mülhaupt R, Schartela B (2013) Flame retardancy through carbon nanomaterials: carbon black. Multiwall nanotubes, expanded graphite, multi-layer graphene and graphene in polypropylene. Polym Degrad Stab 98:1495–1505CrossRefGoogle Scholar
  17. Eriksson P, Jakobsson E, Fredriksson A (2001) Brominated flame retardants: a novel class of developmental neurotoxicants in our environment? Environ Health Perspect 109:903–908CrossRefGoogle Scholar
  18. Franchini E, Galy J, Gerard J-F, Tabuani D, Medici A (2009) Influence of POSS structure on the flame retardant properties of epoxy hybrid networks. Polymer Degrad Stab 94:1728–1736CrossRefGoogle Scholar
  19. Galloa E, Schartela B, Aciernob D, Russob P (2011a) Flame retardant biocomposites: synergism between phosphinate and nanometric metal oxides. Eur Polym J 47:1390–1401CrossRefGoogle Scholar
  20. Galloa E, Schartel B, Braun U, Russo P, Acierno D (2011b) Flame retardant synergisms between nanometric Fe2O3 and aluminum phosphinate in poly (butylene terephthalate). Polym Adv Technol 22:2382–2391CrossRefGoogle Scholar
  21. Grandjean P, Landrigan PJ (2006) Developmental neurotoxicity of industrial chemicals. The Lancet 368:2167–2176CrossRefGoogle Scholar
  22. Guillaume E, Marquis D, Saragoza L (2014) Calibration of flow rate in cone calorimeter tests. Flame Mater 38:194–203Google Scholar
  23. Hamdani S, Longuet C, Perrin D, Lopez-cuesta JM, Ganachaud F (2009) Flame retardancy of silicone-based materials. Polym Degrad Stab 94:465–495CrossRefGoogle Scholar
  24. Hoh E, Zhu L, Hites RA (2006) Dechlorane plus, a chlorinated flame retardant, in the Great Lakes. Environ Sci Tech 40:1184–1189CrossRefGoogle Scholar
  25. Horrocks AR, Price RD (2001) Advances in fire retardant materials. Wood head Publishing Material/CRC Press, BostonCrossRefGoogle Scholar
  26. Jakobsson K, Thuresson K, Rylander L, Sjödin A, Hagmar L, Bergman A (2002) Exposure to polybrominated diphenyl ethers and tetrabromobisphenol A among computer technicians. Chemosphere 46(5):709–716CrossRefGoogle Scholar
  27. Jiang Z, Liu X, Jiao S, Han J (2013) Zinc hydroxystannate-coated mineral grade Mg(OH)2 as flame- retardant and smoke suppression for flexible PVC. Adv Mater Res 652:481–484Google Scholar
  28. Kandola BK (2012) Flame retardant characteristics of natural fiber composites. In: John MJ, Thomas S (eds) Natural polymers. Composites 1:86–117Google Scholar
  29. Kaprinidis N, Fuchs S (2008) Halogen-free FR systems for advanced printed circuit boards, electronics and the environment, 2008. ISEE 2008. IEEE international symposium on. doi:10.1109/ISEE.2008.4562853Google Scholar
  30. Karter MJ (2001) Fire loss in the United States fire loss during 2000. NFPA, Quincy, p 82. Accessed 10 Nov
  31. Kashiwagi T, Gilman JW (2000) In: Grand AF, Wilkie CA (eds) Flame retardancy of polymeric materials, vol 10. Marcel Dekker, New York, p 353Google Scholar
  32. Kashiwagi T, Shields JR, Harris RH, Davis J (2003) Flame-retardant mechanism of silica: effects of resin molecular weight. J Appl Polymer Sci 87:1541–1553CrossRefGoogle Scholar
  33. Kashiwagi T, Du F, Winey KI, Groth KM, Shields JR, Bellayer SP, Kim H, Douglas JF (2005) Flammability properties of polymer nanocomposites with single-walled carbon nanotubes effects of nanotube dispersion and concentration. Polymer 46:471CrossRefGoogle Scholar
  34. Klatt M (2014) Nitrogen-based flame retardants. In: Morgan AB, Wilkie CA (eds) Non-halogenated flame retardant handbook. Wiley, HobokenGoogle Scholar
  35. Laoutid F, Bonnaud L, Alexandre M, Lopez JM, Cuesta L, Dubois PH (2009) New prospects in flame retardant polymer materials: from fundamentals to nanocomposites. Mater Sci Eng 63(3):100–125CrossRefGoogle Scholar
  36. LeMasters GK, Genaidy AM, Succop P, Deddens J, Sobeih T, Barriera-Viruet H, Dunning K, Lockey J (2006) Cancer risk among firefighters; meta-analysis of 32 studies. J Occup Environ Med 48(11):1189–1202CrossRefGoogle Scholar
  37. Li B, He Jia He, Guan L, Bing B, Dai J (2009) A novel intumescent flame-retardant system for flame-retarded LDPE/Eva composites. J Appl Polymer Sci 114(6):3626–3635CrossRefGoogle Scholar
  38. Lin H, Han L, Dong L (2014) Thermal degradation behaviour and gas phase flame retardant mechanism of polylactide/PCPP blends. J Appl Polymer Sci 131:40480CrossRefGoogle Scholar
  39. Lin M, Li B, Li Q, Li S, Zhang S (2011) Synergistic effect of metal oxides on the flame retardancy and thermal degradation of novel intumescent flame-retardant thermoplastic polyurethanes. J Appl Polymer Sci 121:1951–1960CrossRefGoogle Scholar
  40. Lu S-Y, Hamerton I (2002) Recent developments in the chemistry of halogen-free flame retardant polymers. Prog Polymer Sci 27(8):1661–1712CrossRefGoogle Scholar
  41. Lunder S, Sharp R (2003) Mother’s milk: record levels of toxic fire retardants found in American mothers’ breast milk. Environmental Working Group. Scholar
  42. McPherson A, Thorpe B, Ann Blake A (2004) Brominated flame retardants in dust on computers: the case for safer chemicals and better computer design. Computertakeback.orgGoogle Scholar
  43. Morgan AB, Gilman JW (2013) An overview of flame retardancy of polymeric materials: application, technology, and future directions. Fire Mater 37(4):259–279CrossRefGoogle Scholar
  44. Muenhor D, Harrad S, Ali N, Covaci, A (2010) Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand. Environ Int 36(7):690–698CrossRefGoogle Scholar
  45. Ohta S, Ishizuka D, Nishimura H, Nakao T, Aozasa O, Shimidzu Y (2002) Comparison of polybrominated diphenyl ethers in fish, vegetables and meat and levels in human milk of nursing women in Japan. Chemospher 46(5):689–696CrossRefGoogle Scholar
  46. Pal G, Macskasy H (1992) Plastics: their behavior in fires. Stud Polymer Sci 6. ISBN 0-444-98766-5. Elsevier, Amsterdam/Oxford/New York/Tokyo 1991. X, 43 1 pGoogle Scholar
  47. Patel P, Hull TR, Moffatt C (2012) Peek polymer flammability and the inadequacy of the UL-94 classification. Flame Mater 36:185–201Google Scholar
  48. Pettigrew A (1993) Halogenated flame retardants. In: Kirk-Othmer Encyclopaedia of chemical technology, 4th edn, vol 10. Wiley, New York, pp 954–976Google Scholar
  49. Qiang Wu, Jianping L, Baojun Q (2003) Preparation and characterization of microcapsulated red phosphorus and its flame-retardant mechanism in halogen-free flame retardant polyolefins. Polymer Int 52(8):1326–1331CrossRefGoogle Scholar
  50. Ranganathan T, Zilberman J, Farris RJ, Coughlin EB, Emrick T (2006) Deoxybenzion-based polyarylates as halogen-free fire-resistant polymers. Macromolecules 39:3553–3558CrossRefGoogle Scholar
  51. Report written by Alexandra McPherson, Beverley Thorpe, and Ann Blake, PhD June 2004.
  52. Sawada Y, Yamaguchi J, Sakurai O, Uematsu K, Mizutani N, Kato M (1979) Thermogravimetric study on the decomposition of hydromagnesite 4 MgCO3 · Mg(OH)2 · 4 H2O. Thermochim Acta 33:127–140CrossRefGoogle Scholar
  53. Schantz SL, Widholm JJ, Rice DC (2003) Effects of PCB exposure on neuropsychological function in children. Environ Health Perspect 111(3):357–576CrossRefGoogle Scholar
  54. Schartel B (2010) Phosphorus-based flame retardancy mechanisms-old hat or a starting point for future development? Materials 3:4710–4745CrossRefGoogle Scholar
  55. Schartel B, Potschke P, Knoll U, Abdel-Goad M (2005) Flame behaviour of polyamide 6/multiwall carbon nanotube nanocomposites. Eur Polym J 41:1061CrossRefGoogle Scholar
  56. Small A, Plaisted T, Rogers M, Davis F, Sterner L (2008) A non- halogenated flame retardant additive for pultrusion. Composit Res J 2:15Google Scholar
  57. Special Chem. Flame Retardants Center: Melamine Compounds. Accessed 2007
  58. Stapleton HM, Klosterhaus S, Keller A, Lee Ferguson P, van Bergen S, Cooper E, Webster TM, Blum A (2011) Identification of flame retardants in polyurethane foam collected from baby products. Environ Sci Tech 45(12):5323–5331CrossRefGoogle Scholar
  59. Su G, Saunders D, Yu Y, Yu H, Zhang X, Liu H, Giesy JP (2014) Occurrence of additive brominated flame retardants in aquatic organisms from Tai Lake and Yangtze River in Eastern China. Chemosphere 114:340–346CrossRefGoogle Scholar
  60. Takashi K, John RS, Richard HH, Davis J (2003) Flame-retardant mechanism of silica: effects of resin molecular weight. J Appl Polym Sci 87:1541–1553CrossRefGoogle Scholar
  61. Tian N, Wen X, Jiang Z, Gong J, Wang Y, Xue J, Tang T (2013) Synergistic effect between a novel char forming agent and ammonium polyphosphate on flame retardancy and thermal properties of polypropylene. Ind Eng Chem Res 52:10905–10915CrossRefGoogle Scholar
  62. Tkáč (1981) Radical processes in polymer burning and its retardation. I. ESR methods for studying the thermal decomposition of polymers in the pre flame and flame zones. J Poly Sci Part A Poly Chem 19(6):1475–1493CrossRefGoogle Scholar
  63. Tomy GT, Palace VP, Halldorson T, Braekevelt E, Danell R, Wautier K, Evans B, Binkworth L, Fisk AT (2004) Bioaccumulation, biotransformation, and biochemical effects of brominated diphenyl ethers in juvenile lake trout (Salvelinus namaycush). Environ Sci Technol 38(5):1496–1504CrossRefGoogle Scholar
  64. Troitzsch J (1990) International plastics flammability handbook, 2nd edn. Hanser Publishers, MunichGoogle Scholar
  65. U.S. Environmental Protection Agency (EPA) (2005) Environmental profiles of chemical flame-retardant alternatives for low-density polyurethane foam (Report). EPA 742-R-05-002A. Retrieved 4 Apr 2013Google Scholar
  66. United Nations Environment Program “Urgent Need to Prepare Developing Countries for Surge in E-Wastes”, Bali, 22 Feb 2010Google Scholar
  67. Viberg H, Fredriksson A, Jakobsson E, Orn U, Eriksson P (2003) Neurobehavioral derangements in adult mice receiving decabrominated diphenyl ether (PBDE 209) during defined period of neonatal brain development. Toxicol Sci 76(1):112–120CrossRefGoogle Scholar
  68. Walker JK, Luke E, Chen T, Ivarov A (2008) Synergies of metal hydroxides and metal molybdates in low-smoke flexible PVC. In: Proceedings of the 57th IWCS conference, ProvidenceGoogle Scholar
  69. Wang CZ, Wu WH, Ye X, Liu L (2013) Zinc hydroxystannate-coated mineral grade Mg(OH)2 as flame – retardant and smoke suppression for flexible PVC. Adv Mat Res 652:481–484CrossRefGoogle Scholar
  70. Wang ZY, Liu Y, Wang Q (2010) Flame retardant polyoxymethylene with aluminium hydroxide/melaminE/Navolac resin synergistic system. Polym Degrad Stab 95:945CrossRefGoogle Scholar
  71. Yantao Li, Bin Li, Jinfeng D, He J, Suliang G (2008) Synergistic effects of lanthanum oxide on a novel intumescent flame retardant polypropylene system. Polymer Degrad Stab 93(1):9–16CrossRefGoogle Scholar
  72. Yen YY, Wang HT, Guo WJ (2012) Synergistic flame retardant effect of metal hydroxide and nano-clay in EVA composites. Polym Degrad Stab 97:863–869CrossRefGoogle Scholar
  73. Zhang H (2004) Fire-safe polymers and polymer composites. Federal Aviation Administration technical report. U.S. Department of Transportation, Washington, DCGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.Polymers and Pigments Department, Chemical Industries DivisionNational Research CenterDokki, GizaEgypt

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