Skip to main content

Reduced fire hazards of expandable polystyrene building materials via intumescent flame-retardant coatings

Journal of Materials Science volume 55, pages 7555–7572 (2020)Cite this article

Abstract

Despite great advances, fire safety is a permanent challenge in expanded polystyrene (EPS) foam specially used as the thermal insulating external wall in buildings and constructions. Herein, an effective flame-retardant architecture consisting of phenolic epoxy resin (PER), ammonium polyphosphate (APP) and tannic acid functionalized graphene (TGE) was successfully fabricated and coated on the surface of EPS foam plate (EPS/ATG) to achieve excellent flame retardancy and thermally insulating properties. This surface coating is equivalent to protective “shield” for expanded polystyrene foam plate. The PER/APP/TGE paintcoat with a ratio of 20:20:0.65 imparted superior fire safety to EPS foam, exhibiting a high limiting oxygen index value of 35.50%, and a UL-94 V-0 classification was achieved with only 300 um of flame-retardant layer thickness. Cone calorimeter test results showed that EPS/ATG20 foam plate was more efficient in decreasing the peak heat release rate by 53.8% and prolonging ignition time by 75.7 times in comparison with the EPS foam plate. Thermal conductivity of the EPS/ATG20 foam plate just increased from 0.048 W/m K of EPS foam plate to 0.053 W/m K. The PER/APP/TGE paintcoat not only endowed excellent flame retardancy to EPS/ATG foam plates, but maintained desirable thermal insulation properties.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

USD 39.95

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Scheme 1
Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9
Figure 10
Figure 11

References

  1. Wang JL, Zhang DC, Zhang Y, Cai W, Yao CX, Hu Y, Hu WZ (2019) Construction of multifunctional boron nitride nanosheet towards reducing toxic volatiles (CO and HCN) generation and fire hazard of thermoplastic polyurethane. J Hazard Mater 362:482–494

    Article  CAS  Google Scholar 

  2. Wang JL, Ma C, Mu XW, Cai W, Liu LX, Zhou X, Hu WZ, Hu Y (2018) Construction of multifunctional MoSe2 hybrid towards the simultaneous improvements in fire safety and mechanical property of polymer. J Hazard Mater 352:36–46. https://doi.org/10.1016/j.jhazmat.2018.03.003

    Article  CAS  Google Scholar 

  3. Yuan BH, Sun YR, Chen XF, Shi YQ, Dai HM, He S (2018) Poorly-well-dispersed graphene: abnormal influence on flammability and fire behavior of intumescent flame retardant. Compos A Appl Sci Manuf 109:345–354

    Article  CAS  Google Scholar 

  4. Jiao CM, Wang HZ, Li SX, Chen XL (2017) Fire hazard reduction of hollow glass microspheres in thermoplastic polyurethane composites. J Hazard Mater 332:176–184

    Article  CAS  Google Scholar 

  5. Shi YQ, Yu B, Zhou KQ, Yuen RKK, Gui Z, Hu Y, Jiang SH (2015) Novel CuCo2O4/graphitic carbon nitride nanohybrids: Highly effective catalysts for reducing CO generation and fire hazards of thermoplastic polyurethane nanocomposites. J Hazard Mater 293:87–96. https://doi.org/10.1016/j.jhazmat.2015.03.041

    Article  CAS  Google Scholar 

  6. Chen XL, Jiang YF, Jiao CM (2014) Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate. J Hazard Mater 266:114–121. https://doi.org/10.1016/j.jhazmat.2013.12.025

    Article  CAS  Google Scholar 

  7. Xiao YL, Jin ZY, He LX, Ma SC, Wang CY, Mu XW, Song L (2020) Synthesis of a novel graphene conjugated covalent organic framework nanohybrid for enhancing the flame retardancy and mechanical properties of epoxy resins through synergistic effect. Compos B Eng 182:107616–107626. https://doi.org/10.1016/j.compositesb.2019.107616

    Article  CAS  Google Scholar 

  8. Demirel B (2013) Optimization of the composite brick composed of expanded polystyrene and pumice blocks. Constr Build Mater 40:306–313. https://doi.org/10.1016/j.conbuildmat.2012.11.008

    Article  Google Scholar 

  9. Raps D, Hossieny N, Park CB, Altstädt V (2015) Past and present developments in polymer bead foams and bead foaming technology. Polymer 56:5–19. https://doi.org/10.1016/j.polymer.2014.10.078

    Article  CAS  Google Scholar 

  10. Schellenberg J, Wallis M (2010) Dependence of properties of expandable polystyrene particle foam on degree of fusion. J Appl Polym Sci 115:2986–2990. https://doi.org/10.1022/app.31397

    Article  CAS  Google Scholar 

  11. Hong Y, Fang X, Yao D (2015) Processing of composite polystyrene foam with a honeycomb structure. Polym Eng Sci 55:1494–1503. https://doi.org/10.1002/pen.24099

    Article  CAS  Google Scholar 

  12. Wang S, Chen H, Liu N (2015) Ignition of expandable polystyrene foam by a hot particle: an experimental and numerical study. J Hazard Mater 283:536–543. https://doi.org/10.1016/j.jhazmat.2014.09.033

    Article  CAS  Google Scholar 

  13. Heibl J, Vetter W (2007) Detection of hexabromocyclododecane and its metabolite pentabromocyclodedecane in chicken egg and fish from the official food control. J Agric Food Chem 55:3319–3324. https://doi.org/10.1021/jf063428b

    Article  CAS  Google Scholar 

  14. Covaci A, Gerecke AC, Law RJ, Voorspoels S, Kohler M, Heeb NV, Leslie H, Allchin CR, De Boer J (2006) Hexabromocyclododecanes (HBCDs) in the environment and humans: a review. Environ Sci Technol 40:3679–3688. https://doi.org/10.1021/es0602492

    Article  CAS  Google Scholar 

  15. 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. https://doi.org/10.1515/reveh.2010.25.4.261

    Article  CAS  Google Scholar 

  16. Wu D, Zhao P, Zhang M, Liu Y (2013) Preparation and properties of flame retardant rigid polyurethane foam with phosphorus-nitrogen intumescent flame retardant. High Perform Polym 25:868–875. https://doi.org/10.1177/0954008313489997

    Article  CAS  Google Scholar 

  17. Chen X, Liu Y, Bai S, Wang Q (2014) Macromolecular nitrogen-phosphorous compound/expandable graphite synchronous expansion flame retardant polystyrene foam. Polym Plast Technol Eng 53:1402–1407. https://doi.org/10.1080/03602559.2014.909473

    Article  CAS  Google Scholar 

  18. Wang LY, Wang C, Liu PW, Jing ZJ, Ge XS, Jiang YJ (2018) The flame resistance properties of expandable polystyrene foams coated with a cheap and effective barrier layer. Constr Build Mater 176:403–414. https://doi.org/10.1016/j.conbuildmat.2018.05.023

    Article  CAS  Google Scholar 

  19. Zhu ZM, Xu YJ, Liao W, Xu SM, Wang YZ (2017) Highly flame retardant expanded polystyrene foams from phosphorus-nitrogen-silicon synergistic adhesives. Ind Eng Chem Res 56:4649–4658. https://doi.org/10.1021/acs.iecr.6b05065

    Article  CAS  Google Scholar 

  20. Kandola BK, Krishnan L, Ebdon JR (2014) Blends of unsaturated polyester and phenolic resins for application as fire-resistant matrices in fire-reinforced composites: effects of added flame retardants. Polym Degrad Stabil 106:129–137. https://doi.org/10.1016/j.polymdegradstab.2013.12.021

    Article  CAS  Google Scholar 

  21. Holder KM, Smith RJ, Grunlan JC (2017) A review of flame retardant nanocoatings prepared using layer-by-layer assembly of polyelectrolytes. J Mater Sci 52:12923–12959. https://doi.org/10.1007/s10853-017-1390-1

    Article  CAS  Google Scholar 

  22. Richardson JJ, Bjornmalm M, CarusoMultilayer F (2015) Assembly, Technology-driven layer-by-layer assembly of nanofilms. Science 348:2491–2501. https://doi.org/10.1126/science.aaa2491

    Article  CAS  Google Scholar 

  23. Li L, Liu XL, Shao XM, Jiang LC, Huang K, Zhao S (2020) Synergistic effects of a highly effective intumescent flame retardant based on tannic acid functionalized graphene on the flame retardancy and smoke suppression properties of natural rubber. Compos A 129:105715–105725. https://doi.org/10.1016/j.compositesa.2019.105715

    Article  CAS  Google Scholar 

  24. Gu J, Yang X, Li C, Kou K (2016) Synthesis of cyanate ester microcapsules via solvent evaporation technique and its application in epoxy resins as a healing agent. Ind Eng Chem Res 55:10941–10946. https://doi.org/10.1021/acs.iecr.6b03093

    Article  CAS  Google Scholar 

  25. Shi YQ, Yu B, Zheng YY, Yang J, Duan ZP, Hu Y (2018) Design of reduced graphene oxide decorated with DOPO phosphanomidate for enhanced fire safety of epoxy resin. J Colloid Interface Sci 521:160–171. https://doi.org/10.1016/j.jcis.2018.02.054

    Article  CAS  Google Scholar 

  26. Zhao S, Xie SC, Zhao Z, Zhang JL, Li L, Xin ZX (2018) Green and high-efficiency production of graphene by tannic acid assisted exfoliation of graphite in water. ACS Sustain Chem Eng 6:7652–7661. https://doi.org/10.1021/acssuschemeng.8b00497

    Article  CAS  Google Scholar 

  27. Zhao Z, Li L, Shao XM, Liu XL, Zhao S, Xie SC, Xin ZX (2018) Tannic acid-assisted green fabrication of functionalized graphene towards its enhanced compatibility in NR nanocomposite. Polym Test 70:396–402. https://doi.org/10.1016/j.polymertesting.2018.07.020

    Article  CAS  Google Scholar 

  28. Kim YO, Cho J, Yeo H, Lee BW, Moon BJ, Ha YM, Jung YC (2019) Flame retardant epoxy derived from tannic acid as bio-based hardener. ACS Sustain Chem Eng 7:3858–3865. https://doi.org/10.1021/acssuschemeng.8b04851

    Article  CAS  Google Scholar 

  29. Liu G, Chen W, Yu J (2010) A novel process to prepare ammonium polyphosphate with crystalline form II and its comparison with melamine polyphosphate. Ind Eng Chem Res 49:12148–12155. https://doi.org/10.1021/ie1014102

    Article  CAS  Google Scholar 

  30. Laoutid F, Karaseva V, Costes L, Brohez S, Mincheva R, Dubois P (2018) Novel bio-based flame retardant systems derived from tannic acid. J Renew Mater 6:559–572. https://doi.org/10.32604/jrm.2018.00004

    Article  CAS  Google Scholar 

  31. Shao ZB, Deng C, Tan Y, Yu L, Chen MJ (2014) Ammonium polyphosphate chemically-modified with ethanolamine as an efficient intumescent flame retardant for polypropylene. J Mater Chem A 2:13955–13965. https://doi.org/10.1039/c4ta02778g

    Article  CAS  Google Scholar 

  32. Schartel B, Hull TR (2007) Development of fire-retarded materials-interpretation of cone calorimeter data. Fire Mater 31:327–354. https://doi.org/10.1002/fam.949

    Article  CAS  Google Scholar 

  33. Bourbigot S, Bras ML, Delobel R, Bréant P, Trémillon JM (1995) Carbonization mechanisms resulting from intumescence-part II. Association with an ethylene terpolymer and the ammonium polyphosphate-pentaerythritol fire retardant system. Carbon 33:283–294. https://doi.org/10.1016/0008-6223(94)00131-I

    Article  CAS  Google Scholar 

  34. Lewin M (2001) Synergism and catalysis in flame retardancy of polymers. Polym Adv Technol 12:215–222. https://doi.org/10.1002/pat.132

    Article  CAS  Google Scholar 

  35. Horrocks AR, Smart G, Nazare S, Kandola B, Price D (2009) Quantification of zinc hydroxystannate and stannate synergies in halogen-containing flame-retardant olymeric formulations. J Fire Sci 28:217–248. https://doi.org/10.1177/0734904109344302

    Article  CAS  Google Scholar 

  36. Li ME, Yan YW, Zhao HB, Jian RK, Wang YZ (2020) A facile and efficient flame-retardant and smoke-suppressant resin coating for expanded polystyrene foams. Compos B 185:107797–107803. https://doi.org/10.1016/j.compositesb.2020.107797

    Article  CAS  Google Scholar 

  37. Jing J, Zhang Y, Fang ZP, Wang DY (2018) Core-shell flame retardant/graphene oxide hybrid: a self-assembly strategy towards reducing fire hazard and improving toughness of polylactic acid. Compos Sci Technol 165:161–167. https://doi.org/10.1016/j.compscitech.2018.06.024

    Article  CAS  Google Scholar 

  38. Guo WW, Yu B, Yuan Y, Song L, Hu Y (2017) In situ preparation of reduced graphene oxide/DOPO-based phosphonamidate hybrids towards high-performance epoxy nanocomposites. Compos B 123:154–164. https://doi.org/10.1016/j.compositesb.2017.05.024

    Article  CAS  Google Scholar 

  39. Xu WZ, Wang XL, Wu Y, Li W, Chen CY (2019) Functionalized graphene with Co-ZIF adsorbed borate ions as an effective flame retardant and smoke suppression agent for epoxy resin. J Hazard Mater 363:138–151. https://doi.org/10.1016/j.jhazmat.2018.09.086

    Article  CAS  Google Scholar 

  40. Khalili P, Liu XL, Kim YT, Rudd C, Yi XS, Kong I (2019) Development of fire retardancy of natural fiber composite encouraged by a synergy between zinc borate and ammonium polyphosphate. Compos Part B 159:165–172. https://doi.org/10.1016/j.compositesb.2018.09.036

    Article  CAS  Google Scholar 

  41. Zhao HB, Chen MJ, Chen HB (2017) Thermally insulating and flame-retardant polyaniline/pectin aerogels. ACS Sustain Chem Eng 5:7012–7019. https://doi.org/10.1021/acssuschemeng.7b01247

    Article  CAS  Google Scholar 

  42. Urquiaga I, Leighton F (2000) Plant polyphenol antioxidants and oxidative stress. Biol Res 33:55–64. https://doi.org/10.4067/s0716-97602000000200004

    Article  CAS  Google Scholar 

  43. Dresselhaus M, Dresselhaus G, Jorio A, Souza Filho A, Saito R (2002) Raman spectroscopy on isolated single wall carbon nanotubes. Carbon 40:2043–2061. https://doi.org/10.1016/S0008-6223(02)00066-0

    Article  CAS  Google Scholar 

  44. Tuinstra F, Koening JL (1970) Raman spectrum of graphite. J Chem Phys 53:1126–1130. https://doi.org/10.1063/1.1674108

    Article  CAS  Google Scholar 

  45. Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 61:14095–14107. https://doi.org/10.1103/PhysRevB.61.14095

    Article  CAS  Google Scholar 

  46. Bourbigot S, Le Bras M, Delobel R, Decressain R, Amoureux JP (1996) Synergistic effect of zeolite in an intumescence process: study of the carbonaceous structures using solid-state NMR. J Chem Soc Faraday Trans 92:149–158. https://doi.org/10.1039/FT9969200149

    Article  CAS  Google Scholar 

  47. Hu S, Song L, Pan HF, Hu Y (2012) Thermal properties and combustion behaviors of chitosan based flame retardant combining phosphorus and nickel. Ind Eng Chem Res 51:3663–3669. https://doi.org/10.1021/ie2022527

    Article  CAS  Google Scholar 

  48. Song L, Wu K, Wang Y, Wang Z, Hu Y (2009) Flammability and thermo-oxidative decomposition of epoxy resin containing ammonium polyphosphate and metallic oxide. J Macromol Sci Pure Appl Chem 46:290–295. https://doi.org/10.1080/10601320802637359

    Article  CAS  Google Scholar 

  49. Guo W, Yu B, Yuan Y, Song L, Hu Y (2017) In situ preparation of reduced graphene oxide/DOPO-based phosphonamidate hybrids towards high-performance epoxy nanocomposites. Compos Part B Eng 123:154–164. https://doi.org/10.1016/j.compositesb.2017.05.024

    Article  CAS  Google Scholar 

  50. Wang W, Yuan Y, Yu B, Liew KM, Yuen RKK, Liu J, Hu Y (2020) Controlled self-template synthesis of manganese-based cuprous oxide nanoplates towards improved fire safety properties of epoxy composites. J Hazard Mater 387:122006–122013. https://doi.org/10.1016/j.jhazmat.2019.122006

    Article  CAS  Google Scholar 

  51. Chiang CL, Ma CCM (2004) Synthesis, characterization, thermal properties and flame retardance of novel phenolic resin/silica nanocomposites. Polym Degrad Stab 83:207–214. https://doi.org/10.1016/s0141-3910(03)00262-3

    Article  CAS  Google Scholar 

  52. Isitman NA, Kaynak C (2012) Effect of partial substitution of aluminum hydroxide with colemanite in fire retarded low-density polyethylene. J Fire Sci 31:73–84. https://doi.org/10.1177/0734904112454835

    Article  CAS  Google Scholar 

  53. Zhong H, Lukes JR (2006) Interfacial thermal resistance between carbon nanotubes: molecular dynamics simulations and analytical thermal modeling. Phys Rev B Condens Matter 74:125403–125412. https://doi.org/10.1103/PhysRevB.74.125403

    Article  CAS  Google Scholar 

  54. Kim H, Abdala AA, Macosko CW (2010) Graphene/polymer nanocomposites. Macromolecules 43:6515–6530. https://doi.org/10.1021/ma100572e

    Article  CAS  Google Scholar 

  55. Yang ZJ, Liu J, Liao RJ, Yang GW, Wu XH, Tang ZH, Guo BC, Zhang LQ, Ma Y, Nie QH, Wang F (2016) Rational design of covalent interfaces for graphene/elastomer nanocomposites. Compos Sci Technol 132:68–75. https://doi.org/10.1016/j.compscitech.2016.06.015

    Article  CAS  Google Scholar 

  56. Shenogin S, Bodapati A, Xue L, Ozisik R, Keblinski P (2004) Effect of chemical functionalization on thermal transport of carbon nanotube composites. Appl Phys Lett 85:2229–2231. https://doi.org/10.1063/1.1794370

    Article  CAS  Google Scholar 

  57. Tributsch H, Fiechter S (2008) The material strategy of fire-resistant tree barks. In: De Wilde WP, Brebbia CA (eds) High performance structures and materials IV. WIT Press, Ashurst, pp 43–52

    Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledge support from National Natural Science Foundation of China [grant numbers 51703111 and 51603111] and Shandong Provincial Natural Science Foundation, China [grant numbers 2018GGX102015 and ZR2017BEM011], and China Postdoctoral Science Foundation [grant number 2018M642626].

Author information

Authors and Affiliations

  1. Key Lab of Rubber-plastics, Ministry of Education/Shandong Provincial Key Lab of Rubber-plastics, School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266042, China

    Xiaoming Shao, Yuqian Du, Xingfu Zheng, Jingchao Wang, Yuchao Wang, Shuai Zhao, Zhenxiang Xin & Lin Li

Authors
  1. Xiaoming Shao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuqian Du
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xingfu Zheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Jingchao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yuchao Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Shuai Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhenxiang Xin
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Lin Li
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Shuai Zhao or Lin Li.

Ethics declarations

Conflict of interest

We confirm that the manuscript has been read and approved by all named authors. We declare that we have no conflict of interest.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 4022 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Shao, X., Du, Y., Zheng, X. et al. Reduced fire hazards of expandable polystyrene building materials via intumescent flame-retardant coatings. J Mater Sci 55, 7555–7572 (2020). https://doi.org/10.1007/s10853-020-04548-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-020-04548-z