POSS as Fire Retardant

  • Ming Hui Chua
  • Hui Zhou
  • Jianwei XuEmail author
Part of the Springer Series on Polymer and Composite Materials book series (SSPCM)


Many common petroleum-based polymeric materials used in our daily life are highly flammable and thus essential for introduction of fire-retardant properties for a greater safety purpose. Recently, polyhedral oligomeric silsesquioxanes (POSS) have received great attention in the application of fire-retardant materials by incorporating proper POSS compounds either physically or chemically into common polymer systems to offer hybrid composites with improved fire-retardant properties. This chapter will summarize the latest development on the POSS-based fire-retardant polymer composite materials mainly in terms of the class of polymers including epoxy resins, polycarbonates, polyesters, polyolefins, polystyrene, polyurethanes, vinyl esters, acrylics, and cotton fabrics. Not only will the effects of POSS on the fire-retardant properties, for example, the peak heat release rate, the total heat release, the time of ignition, and the fire ratings, obtained from key flammability tests such as cone calorimetry and UL94 testing be reviewed, but the structural diversity of POSS, process of making composites as well as mechanism for improvement in fire-retardant properties will also be holistically discussed. Finally, perspectives on potentials, challenges, and further development of POSS as fire-retardant additives are commented.


POSS Fire retardant Flammability, polymer composites Hybrid composites 


  1. 1.
    Alongi J, Han Z, Bourbigot S (2014) Intumescence: tradition versus novelty. a comprehensive review. Prog Polym Sc 51:28–73. Scholar
  2. 2.
    Price D (2001) Introduction: polymer combustion, condensed phase pyrolysis and smoke formation. In: Fire retardant materials. Woodhead Publishing, pp 1–30Google Scholar
  3. 3.
    Georlette P, Simons J, Costa L (2000) Halogen-contining fire-retardant compounds. In: Grand AF, Wilkie CA (eds) Fire retardancy of polymeric materials. Marcel Dekker Inc, Basel, New York, pp 245–284Google Scholar
  4. 4.
    Scharte B (2010) Phosphorus-based flame retardancy mechanisms-old hat or a starting point for future development? Mater Basel 3:4710–4745. Scholar
  5. 5.
    Brown SC (1998) Flame retardants: inorganic oxide and hydroxide systems. In: Pritchard G (ed) Plastics additives. Springer, Dordrecht, Netherlands, pp 287–296CrossRefGoogle Scholar
  6. 6.
    Wei G-L, Li D-Q, Zhuo M-N, Liao Y-S, Xie Z-Y, Guo T-L, Li J-J, Zhang S-Y, Liang Z-Q (2015) Organophosphorus flame retardants and plasticizers: Sources, occurrence, toxicity and human exposure. Environ Pollut 196:29–46. Scholar
  7. 7.
    Shaw SD, Blum A, Weber R, Kannan K, Rich D, Lucas D, Koshland CP, Dobraca D, Hanson S, Birnbaum LS (2010) Halogenated flame retardants: do the fire safety benefits justify the risks? Rev Environ Health 25:261–305. Scholar
  8. 8.
    Gnanasekaran D, Madhavan K, Reddy BSR (2009) Developments of polyhedral oligomeric silsesquioxanes (PaSS), pass nanocomposites and their applications: a review. J Sci Ind Res 68:437–464Google Scholar
  9. 9.
    Kuo SW, Chang FC (2011) POSS related polymer nanocomposites. Prog Polym Sci 36:1649–1696. Scholar
  10. 10.
    Kausar A (2017) State-of-the-Art overview on polymer/POSS nanocomposite. Polym—Plast Technol Eng 56:1401–1420. Scholar
  11. 11.
    Qian Y, Wei P, Zhao X, Jiang P, Yu H (2013) Flame retardancy and thermal stability of polyhedral oligomeric silsesquioxane nanocomposites. Fire Mater 37:1–16. Scholar
  12. 12.
    Zhang W, Camino G, Yang R (2017) Polymer/polyhedral oligomeric silsesquioxane (POSS) nanocomposites: an overview of fire retardance. Prog Polym Sci 67:77–125. Scholar
  13. 13.
    Bottom R (2008) Thermogravimetric analysis. Principles and applications of thermal analysis. Blackwell Publishing Ltd, Oxford, pp 87–118CrossRefGoogle Scholar
  14. 14.
    Mngomezulu ME, John MJ, Jacobs V, Luyt AS (2014) Review on flammability of biofibres and biocomposites. Carbohydr Polym 111:149–182. Scholar
  15. 15.
    Carvel R, Steinhaus T, Rein G, Torero JL (2011) Determination of the flammability properties of polymeric materials: A novel method. Polym Degrad Stab 96:314–319. Scholar
  16. 16.
    Schartel B, Hull TR (2007) Development of fire-retarded materials—Interpretation of cone calorimeter data. Fire Mater 31:327–354. Scholar
  17. 17.
    Lyon RE, Walters RN (2004) Pyrolysis combustion flow calorimetry. J Anal Appl Pyrol 71:27–46. Scholar
  18. 18.
    Laoutid F, Bonnaud L, Alexandre M, Lopez-Cuesta JM, Dubois P (2009) New prospects in flame retardant polymer materials: from fundamentals to nanocomposites. Mater Sci Eng R Reports 63:100–125. Scholar
  19. 19.
    Dupretz R, Fontaine G, Duquesne S, Bourbigot S (2015) Instrumentation of UL-94 test: understanding of mechanisms involved in fire retardancy of polymers. Polym Adv Technol 26:865–873. Scholar
  20. 20.
    Qiu X, Li Z, Li X, Zhang Z (2018) Flame retardant coatings prepared using layer by layer assembly: a review. Chem Eng J 334:108–122. Scholar
  21. 21.
    Lu T, Chen T, Liang G (2007) Synthesis, thermal properties, and flame retardance of the epoxy-silsesquioxane hybrid resins. Polym Eng Sci 47:225–234. Scholar
  22. 22.
    Lu T, Liang G, Peng Y, Chen T (2007) Blended hybrids based on silsesquioxane–OH and epoxy resins. J Appl Polym Sci 106:4117–4123. Scholar
  23. 23.
    Wu K, Song L, Hu Y, Lu H, Kandola BK, Kandare E (2009) Synthesis and characterization of a functional polyhedral oligomeric silsesquioxane and its flame retardancy in epoxy resin. Prog Org Coatings 65:490–497. Scholar
  24. 24.
    Wu K, Kandola BK, Kandare E, Hu Y (2011) Flame retardant effect of polyhedral oligomeric silsesquioxane and triglycidyl isocyanurate on glass fibre-reinforced epoxy composites. Polym Compos 32:378–389. Scholar
  25. 25.
    Franchini E, Galy J, Gérard J-F, Tabuani D, Medici A (2009) Influence of POSS structure on the fire retardant properties of epoxy hybrid networks. Polym Degrad Stab 94:1728–1736. Scholar
  26. 26.
    Schartel B, Braun U, Balabanovich AI, Artner J, Ciesielski M, Döring M, Perez RM, Sandler JKW, Altstädt V (2008) Pyrolysis and fire behaviour of epoxy systems containing a novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based diamino hardener. Eur Polym J 44:704–715. Scholar
  27. 27.
    Qian X, Song L, Jiang S, Tang G, Xing W, Wang B, Hu Y, Yuen RKK (2013) Novel flame retardants containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and unsaturated bonds: synthesis, characterization, and application in the flame retardancy of epoxy acrylates. Ind Eng Chem Res 52:7307–7315. Scholar
  28. 28.
    Artner J, Ciesielski M, Walter O, Döring M, Perez RM, Sandler JKW, Altstädt V, Schartel B (2008) A novel DOPO-Based diamine as hardener and flame retardant for epoxy resin systems. Macromol Mater Eng 293:503–514. Scholar
  29. 29.
    Ciesielski M, Schäfer A, Döring M (2008) Novel efficient DOPO-based flame-retardants for PWB relevant epoxy resins with high glass transition temperatures. Polym Adv Technol 19:507–515. Scholar
  30. 30.
    Perret B, Schartel B, Stöβ K, Ciesielski M, Diederichs J, Döring M, Krämer J, Altstädt V (2011) Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation. Eur Polym J 47:1081–1089. Scholar
  31. 31.
    Schartel B, Balabanovich AI, Braun U, Knoll U, Artner J, Ciesielski M, Döring M, Perez R, Sandler JKW, Altstädt V, Hoffmann T, Pospiech D (2007) Pyrolysis of epoxy resins and fire behavior of epoxy resin composites flame-retarded with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide additives. J Appl Polym Sci 104:2260–2269. Scholar
  32. 32.
    Zhang W, Li X, Yang R (2011) Pyrolysis and fire behaviour of epoxy resin composites based on a phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS). Polym Degrad Stab 96:1821–1832. Scholar
  33. 33.
    Zhang W, Li X, Yang R (2011) Novel flame retardancy effects of;DOPO-POSS on epoxy resins. Polym Degrad Stab 96:2167–2173. Scholar
  34. 34.
    Zhang W, Li X, Yang R (2012) Blowing-out effect in epoxy composites flame retarded by DOPO-POSS and its correlation with amide curing agents. Polym Degrad Stab 97:1314–1324. Scholar
  35. 35.
    Zhang W, Li X, Yang R (2013) Blowing-out effect and temperature profile in condensed phase in flame retarding epoxy resins by phosphorus-containing oligomeric silsesquioxane. Polym Adv Technol 24:951–961. Scholar
  36. 36.
    Gérard C, Fontaine G, Bourbigot S (2011) Synergistic and antagonistic effects in flame retardancy of an intumescent epoxy resin. Polym Adv Technol 22:1085–1090. Scholar
  37. 37.
    Zhang W, Li X, Fan H, Yang R (2012) Study on mechanism of phosphorus e silicon synergistic flame retardancy on epoxy resins. Polym Degrad Stab 97:2241–2248. Scholar
  38. 38.
    Zhang W, Li X, Jiang Y, Yang R (2013) Investigations of epoxy resins flame-retarded by phenyl silsesquioxanes of cage and ladder structures. Polym Degrad Stab 98:246–254. Scholar
  39. 39.
    Zhang W, Li X, Li L, Yang R (2012) Study of the synergistic effect of silicon and phosphorus on the blowing-out effect of epoxy resin composites. Polym Degrad Stab 97:1041–1048. Scholar
  40. 40.
    Wu Q, Zhang C, Liang R, Wang B (2010) Combustion and thermal properties of epoxy/phenyltrisilanol polyhedral oligomeric silsesquioxane nanocomposites. J Therm Anal Calorim 100:1009–1015. Scholar
  41. 41.
    Yang H, Wang X, Yu B, Song L, Hu Y, Yuen RKK (2012) Effect of borates on thermal degradation and flame retardancy of epoxy resins using polyhedral oligomeric silsesquioxane as a curing agent. Thermochim Acta 535:71–78. Scholar
  42. 42.
    Levchik SV, Weil ED (2005) Overview of recent developments in the flame retardancy of polycarbonates. Polym Int 54:981–998. Scholar
  43. 43.
    Li L, Li X, Yang R (2012) Mechanical, thermal properties, and flame retardancy of PC/ultrafine octaphenyl-POSS composites. J Appl Polym Sci 124:3807–3814. Scholar
  44. 44.
    Song L, He Q, Hu Y, Chen H, Liu L (2008) Study on thermal degradation and combustion behaviors of PC/POSS hybrids. Polym Degrad Stab 93:627–639. Scholar
  45. 45.
    Zhang W, Li X, Yang R (2012) Flame retardant mechanisms of phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) in polycarbonate composites. J Appl Polym Sci 124:1848–1857. Scholar
  46. 46.
    Zhang W, Li X, Guo X, Yang R (2010) Mechanical and thermal properties and flame retardancy of phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS)/polycarbonate composites. Polym Degrad Stab 95:2541–2546. Scholar
  47. 47.
    Zhang W, Li X, Yang R (2012) Flame retardancy mechanisms of phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS) in polycarbonate/acrylonitrile-butadiene-styrene blends. Polym Adv Technol 23:588–595. Scholar
  48. 48.
    He Q, Song L, Hu Y, Zhou S (2009) Synergistic effects of polyhedral oligomeric silsesquioxane (POSS) and oligomeric bisphenyl a bis(diphenyl phosphate) (BDP) on thermal and flame retardant properties of polycarbonate. J Mater Sci 44:1308–1316. Scholar
  49. 49.
    Vahabi H, Eterradossi O, Ferry L, Longuet C, Sonnier R, Lopez-Cuesta J-M (2013) Polycarbonate nanocomposite with improved fire behavior, physical and psychophysical transparency. Eur Polym J 49:319–327. Scholar
  50. 50.
    Wang X, Hu Y, Song L, Yang H, Yu B, Kandola B, Deli D (2012) Comparative study on the synergistic effect of POSS and graphene with melamine phosphate on the flame retardance of poly(butylene succinate). Thermochim Acta 543:156–164. Scholar
  51. 51.
    Louisy J, Bourbigot S, Duquesne S, Desbois P, König A, Klatt M (2013) Novel synergists for flame retarded glass-fiber reinforced poly(1,4-butylene terephthalate). Polim Polym 58:403–412. Scholar
  52. 52.
    Didane N, Giraud S, Devaux E, Lemort G (2012) A comparative study of POSS as synergists with zinc phosphinates for PET fire retardancy. Polym Degrad Stab 97:383–391. Scholar
  53. 53.
    Didane N, Giraud S, Devaux E, Lemort G (2012) Development of fire resistant PET fibrous structures based on phosphinate-POSS blends. Polym Degrad Stab 97:879–885. Scholar
  54. 54.
    Didane N, Giraud S, Devaux E, Lemort G, Capon G (2012) Thermal and fire resistance of fibrous materials made by PET containing flame retardant agents. Polym Degrad Stab 97:2545–2551. Scholar
  55. 55.
    Carosio F, Alongi J, Malucelli G (2011) [small alpha]-Zirconium phosphate-based nanoarchitectures on polyester fabrics through layer-by-layer assembly. J Mater Chem 21:10370–10376. Scholar
  56. 56.
    Fina A, Tabuani D, Camino G (2010) Polypropylene–polysilsesquioxane blends. Eur Polym J 46:14–23. Scholar
  57. 57.
    Barczewski M, Chmielewska D, Dobrzyńska-Mizera M, Dudziec B, Sterzyński T (2014) Thermal stability and flammability of polypropylene-silsesquioxane nanocomposites. Int J Polym Anal Charact 19:500–509. Scholar
  58. 58.
    Fina A, Abbenhuis HCL, Tabuani D, Camino G (2006) Metal functionalized POSS as fire retardants in polypropylene. Polym Degrad Stab 91:2275–2281. Scholar
  59. 59.
    Carniato F, Boccaleri E, Marchese L, Fina A, Tabuani D, Camino G (2007) Synthesis and Characterisation of Metal Isobutylsilsesquioxanes and Their Role as Inorganic-Organic Nanoadditives for Enhancing Polymer Thermal Stability. Eur J Inorg Chem 2007:585–591. Scholar
  60. 60.
    Liu L, Hu Y, Song L, Nazare S, He S, Hull R (2007) Combustion and thermal properties of OctaTMA-POSS/PS composites. J Mater Sci 42:4325–4333. Scholar
  61. 61.
    Liu L, Hu Y, Song L, Ni Z (2011) Preparation and characterizations of novel PS composites containing octaTMA-POSS-based lamellar hybrids. Int J Polym Mater Polym Biomater 60:947–958. Scholar
  62. 62.
    Liu L, Hu Y, Song L, Ni Z (2011) Novel PS Composites by Using Artificial Lamellar Hybrid from Octa(γ-chloroaminopropyl) POSS and Surfactant. Polym Plast Technol Eng 50:73–79. Scholar
  63. 63.
    Bourbigot S, Turf T, Bellayer S, Duquesne S (2009) Polyhedral oligomeric silsesquioxane as flame retardant for thermoplastic polyurethane. Polym Degrad Stab 94:1230–1237. Scholar
  64. 64.
    Devaux E, Rochery M, Bourbigot S (2002) Polyurethane/clay and polyurethane/POSS nanocomposites as flame retarded coating for polyester and cotton fabrics. Fire Mater 26:149–154. Scholar
  65. 65.
    Kim H-J, Kim CK, Kwon Y (2014) Ablation and fire-retardant properties of hydroxyl-terminated polybutadiene-based polyurethane-g-polyhedral oligomeric silsesquioxane composites. High Perform Polym 27:749–757. Scholar
  66. 66.
    Glodek TE, Boyd SE, McAninch IM, LaScala JJ (2008) Properties and performance of fire resistant eco-composites using polyhedral oligomeric silsesquioxane (POSS) fire retardants. Compos Sci Technol 68:2994–3001. Scholar
  67. 67.
    Chigwada G, Jash P, Jiang DD, Wilkie CA (2005) Fire retardancy of vinyl ester nanocomposites: Synergy with phosphorus-based fire retardants. Polym Degrad Stab 89:85–100. Scholar
  68. 68.
    Carosio F, Alongi J (2016) Influence of layer by layer coatings containing octapropylammonium polyhedral oligomeric silsesquioxane and ammonium polyphosphate on the thermal stability and flammability of acrylic fabrics. J Anal Appl Pyrol 119:114–123. Scholar
  69. 69.
    Li Y-C, Mannen S, Schulz J, Grunlan JC (2011) Growth and fire protection behavior of POSS-based multilayer thin films. J Mater Chem 21:3060–3069. Scholar

Copyright information

© Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Institute of Materials Research and Engineering (IMRE)Agency for Science, Technology and Research (A*STAR)SingaporeSingapore

Personalised recommendations