Journal of Materials Science

, Volume 50, Issue 6, pp 2451–2458 | Cite as

Intumescing multilayer thin film deposited on clay-based nanobrick wall to produce self-extinguishing flame retardant polyurethane

  • K. M. Holder
  • M. E. Huff
  • M. N. Cosio
  • J. C. GrunlanEmail author
Original Paper


Significant loss of life and property results each year from fires fueled by polyurethane found in household furnishings. Established layer-by-layer flame retardant systems were combined to produce a stacked nanocoating for flame retarding polyurethane foam. A bilayer system of chitosan (CH) and vermiculite provides a nanobrick wall exoskeleton, protecting the polyurethane long enough for an intumescing system of CH and ammonium polyphosphate to activate and form a bubbled char layer. Stacking these two recipes allows the foam to self-extinguish when exposed to a butane torch without any flame spread or shrinking of the foam, two things commonly observed with either coating alone. Cone calorimetry revealed a significant peak heat release rate reduction of 66 % relative to the uncoated foam. This study demonstrates the ability to combine flame retardant mechanisms sequentially. This nanocoating acts as an environmentally benign template for flame retarding various complex substrates, especially those found in household furnishings.


Foam Chitosan Flame Retardant Heat Release Rate Flame Spread 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



The authors acknowledge Great Lakes Solutions (a division of Chemtura) for financial support of this work through their Greener Innovation Grant (GIG) program. The Microscopy & Imaging Center (MIC) at Texas A&M is acknowledged for TEM assistance and the Materials Characterization Facility (MCF) at Texas A&M is acknowledged for SEM assistance.

Supplementary material

10853_2014_8800_MOESM1_ESM.pdf (113 kb)
Supplementary material 1 (PDF 112 kb)

Supplementary material 2 (MPG 880 kb)

Supplementary material 3 (MPG 790 kb)

Supplementary material 4 (MPG 1602 kb)

Supplementary material 5 (MPG 1024 kb)

Supplementary material 6 (MPG 1174 kb)

Supplementary material 7 (MPG 492 kb)


  1. 1.
    Ahrens M (2013) Home Structure Fires, National Fire Protection AssociationGoogle Scholar
  2. 2.
    United States Fire Administration (2014) Accessed 20 May 2014
  3. 3.
    Gharehbagh A, Ahmadi Z (2012) Polyurethane flexible foam fire behavior, polyurethane. pp 101–120. InTech, RijekaGoogle Scholar
  4. 4.
    Hull TR, Kandola BK (2009) Fire retardance of polymers: new strategies and mechanisms. Royal Society of Chemistry, LondonGoogle Scholar
  5. 5.
    Wilson WE, O’Donovan JT, Fristrom RM (1969) Flame inhibition by halogen compounds. Int Symp Combust 12:929–942CrossRefGoogle Scholar
  6. 6.
    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 63:100–125CrossRefGoogle Scholar
  7. 7.
    Buser HR (1986) Polybrominated dibenzofurans and dibenzo-p-dioxins: thermal reaction products of polybrominated diphenyl ether flame retardants. Environ Sci and Technol 20:404–408CrossRefGoogle Scholar
  8. 8.
    Rahman F, Langford KH, Scrimshaw MD, Lester JN (2001) Polybrominated diphenyl ether (PBDE) flame retardants. Sci Total Environ 275:1–17CrossRefGoogle Scholar
  9. 9.
    Darnerud PO (2003) Toxic effects of brominated flame retardants in man and in wildlife. Environ Int 29:841–853CrossRefGoogle Scholar
  10. 10.
    Laufer G, Kirkland C, Cain AA, Grunlan JC (2012) Clay-chitosan nanobrick walls: completely renewable gas barrier and flame-retardant nanocoatings. ACS Appl Mater Interfaces 4:1643–1649CrossRefGoogle Scholar
  11. 11.
    Cain AA, Nolen CR, Li YC, Davis R, Grunlan JC (2013) Phosphorous-filled nanobrick wall multilayer thin film eliminates polyurethane melt dripping and reduces heat release associated with fire. Polym Degrad Stab 98:2645–2652CrossRefGoogle Scholar
  12. 12.
    Carosio F, Di Blasio A, Alongi J, Malucelli G (2013) Green DNA-based flame retardant coatings assembled through layer by layer. Polymer 54:5148–5153CrossRefGoogle Scholar
  13. 13.
    Carosio F, Di Blasio A, Cuttica F, Alongi J, Malucelli G (2014) Self-assembled hybrid nanoarchitectures deposited on poly(urethane) foams capable of chemically adapting to extreme heat. RSC Adv 4:16674–16680CrossRefGoogle Scholar
  14. 14.
    Kim YS, Li YC, Pitts WM, Werrel M, Davis RD (2014) Rapid growing clay coatings to reduce the fire threat of furniture. ACS Appl Mater Interfaces 6:2146–2152CrossRefGoogle Scholar
  15. 15.
    Cain AA, Murray S, Holder KM, Nolen CR, Grunlan JC (2014) Intumescent nanocoating extinguishes flame on fabric using aqueous polyelectrolyte complex deposited in single step. Macromol Mater Eng 299:1180–1187CrossRefGoogle Scholar
  16. 16.
    Guin T, Krecker M, Milhorn A, Grunlan JC (2014) Maintaining hand and improving fire resistance of cotton fabric through ultrasonication rinsing of multilayer nanocoating. Cellulose 21:3023–3030CrossRefGoogle Scholar
  17. 17.
    Apaydin K, Laachachi A, Ball V, Jimenez M, Bourbigot S, Toniazzo V, Ruch D (2014) Intumescent coating of (polyallylamine-polyphosphates) deposited on polyamide fabrics via layer-by-layer technique. Polym Degrad Stab 106:158–164CrossRefGoogle Scholar
  18. 18.
    Cain AA, Plummer MGB, Murray SE, Bolling L, Regev O, Grunlan JC (2014) Iron-containing, high aspect ratio clay as nanoarmor that imparts substantial thermal/flame protection to polyurethane with a single electrostatically-deposited bilayer. J Mater Chem A 2:17609–17617CrossRefGoogle Scholar
  19. 19.
    Wolska A, Gozdzikiewicz M, Ryszkowska J (2012) Thermal and mechanical behavior of flexible polyurethane foams modified with graphite and phosphorous fillers. J Mater Sci 47:5627–5634. doi: 10.1007/s10853-012-6433-z CrossRefGoogle Scholar
  20. 20.
    Gavgani JN, Adelnia H, Gudarzi MM (2014) Intumescent flame retardant polyurethane/reduced graphene oxide composites with improved mechanical, thermal, and barrier properties. J Mater Sci 49:243–254. doi: 10.1007/s10853-013-7698-6 CrossRefGoogle Scholar
  21. 21.
    Lvov Y, Ariga K, Ichinose I, Kunitake T (1996) Molecular film assembly via layer-by-layer adsorption of oppositely charged macromolecules (linear polymer, protein and clay) and concanavalin a and glycogen. Thin Solid Films 284:797–801CrossRefGoogle Scholar
  22. 22.
    Podsiadlo P, Liu ZQ, Paterson D, Messersmith PB, Kotov NA (2007) Fusion of seashell nacre and marine bioadhesive analogs: high-strength nanocomposite by layer-by-layer assembly of clay and L-3,4-dihydroxyphenylainanine polymer. Adv Mater 19:949–955CrossRefGoogle Scholar
  23. 23.
    Srivastava S, Kotov NA (2008) Composite layer-by-layer (LBL) assembly with inorganic nanoparticles and nanowires. Acc Chem Res 41:1831–1841CrossRefGoogle Scholar
  24. 24.
    Laachachi A, Ball V, Apaydin K, Toniazzo V, Ruch D (2011) Diffusion of polyphosphates into (poly(allylamine)-montmorillonite) multilayer films: flame retardant-intumescent films with improved oxygen barrier. Langmuir 27:13879–13887CrossRefGoogle Scholar
  25. 25.
    Zhuk A, Mirza R, Sukhishvili S (2011) Multiresponsive clay-containing layer-by-layer films. ACS Nano 5:8790–8799CrossRefGoogle Scholar
  26. 26.
    Holder KM, Priolo MA, Secrist KE, Greenlee SM, Nolte AJ, Grunlan JC (2012) Humidity-responsive gas barrier of hydrogen-bonded polymer-clay multilayer thin films. J Phys Chem C 116:19851–19856CrossRefGoogle Scholar
  27. 27.
    Priolo MA, Holder KM, Greenlee SM, Grunlan JC (2012) Transparency, Gas barrier, and moisture resistance of large-aspect-ratio vermiculite nanobrick wall thin films. ACS Appl Mater Interfaces 4:5529–5533CrossRefGoogle Scholar
  28. 28.
    Apaydin K, Laachachi A, Ball V, Jimenez M, Bourbigot S, Toniazzo V, Ruch D (2013) Polyallylamine-montmorillonite as super flame retardant coating assemblies by layer-by-layer deposition on polyamide. Polym Degrad Stab 98:627–634CrossRefGoogle Scholar
  29. 29.
    Tzeng P, Maupin CR, Grunlan JC (2014) Influence of polymer interdiffusion and clay concentration on gas barrier of polyelectrolyte/clay nanobrick wall quadlayer assemblies. J Membr Sci 452:46–53CrossRefGoogle Scholar
  30. 30.
    Li YC, Kim YS, Shields J, Davis R (2013) Controlling polyurethane foam flammability and mechanical behaviour by tailoring the composition of clay-based multilayer nanocoatings. J Mater Chem A 1:12987–12997CrossRefGoogle Scholar
  31. 31.
    Decher G, Schlenoff JB (2012) Multilayer thin films: sequential assembly of nanocomposite materials, 2nd edn. Wiley-VCH, WeinheimCrossRefGoogle Scholar
  32. 32.
    Bartholmai M, Schartel B (2004) Layered silicate polymer nanocomposites: new approach or illusion for fire retardancy? Investigations of the potentials and the tasks using a model system. Polym Adv Technol 15:355–364CrossRefGoogle Scholar
  33. 33.
    Morgan AB, Gilman JW (2013) An overview of flame retardancy of polymeric materials: application, technology, and future directions. Fire Mater 37:259–279CrossRefGoogle Scholar
  34. 34.
    Li YC, Mannen S, Morgan AB, Chang SC, Yang YH, Condon B, Grunlan JC (2011) Intumescent all-polymer multilayer nanocoating capable of extinguishing flame on fabric. Adv Mater 23:3926–3931CrossRefGoogle Scholar
  35. 35.
    Laufer G, Kirkland C, Morgan AB, Grunlan JC (2012) Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton. Biomacromolecules 13:2843–2848CrossRefGoogle Scholar
  36. 36.
    Zhang T, Yan HQ, Wang LL, Fang ZP (2013) Controlled formation of self-extinguishing intumescent coating on ramie fabric via layer-by-layer assembly. Ind Eng Chem Res 52:6138–6146CrossRefGoogle Scholar
  37. 37.
    Montaudo G, Scamporrino E, Puglisi C, Vitalini D (1985) Intumescent Flame-Retardant for Polymers. III. The polypropylene-ammonium polyphosphate-polyurethane system. J Appl Polym Sci 30:1449–1460CrossRefGoogle Scholar
  38. 38.
    Camino G, Costa L, Martinasso G (1989) Intumescent fire-retarding systems. Polym Degrad Stab 23:359–376CrossRefGoogle Scholar
  39. 39.
    Ravey M, Pearce EM (1997) Flexible polyurethane foam. I. Thermal decomposition of a polyether-based, water-blown commercial type of flexible polyurethane foam. J Appl Polym Sci 63:47–74CrossRefGoogle Scholar
  40. 40.
    Levchik SV, Weil ED (2004) Thermal decomposition, combustion and flame-retardancy of epoxy resins—a review of the recent literature. Polym Int 53:1901–1929CrossRefGoogle Scholar
  41. 41.
    Babrauskas V (1984) Development of the cone calorimeter—a bench-scale heat release rate apparatus based on oxygen-consumption. Fire and Mater 8:81–95CrossRefGoogle Scholar
  42. 42.
    Schartel B, Hull TR (2007) Development of fire-retarded materials—interpretation of cone calorimeter data. Fire Mater 31:327–354CrossRefGoogle Scholar
  43. 43.
    Babrauskas V, Peacock RD (1992) Heat release rate—the single most important variable in fire hazard. Fire Saf J 18:255–272CrossRefGoogle Scholar
  44. 44.
    Zanetti M, Kashiwagi T, Falqui L, Camino G (2002) Cone calorimeter combustion and gasification studies of polymer layered silicate nanocomposites. Chem Mater 14:881–887CrossRefGoogle Scholar
  45. 45.
    Morgan AB, Liu WD (2011) Flammability of thermoplastic carbon nanofiber nanocomposites. Fire Mater 35:43–60CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  • K. M. Holder
    • 1
  • M. E. Huff
    • 3
  • M. N. Cosio
    • 3
  • J. C. Grunlan
    • 1
    • 2
    • 3
    Email author
  1. 1.Department of Materials Science and EngineeringTexas A&M UniversityCollege StationUSA
  2. 2.Department of Mechanical EngineeringTexas A&M UniversityCollege StationUSA
  3. 3.Department of ChemistryTexas A&M UniversityCollege StationUSA

Personalised recommendations