Effect of organically intercalation modified layered double hydroxides-graphene oxide hybrids on flame retardancy of thermoplastic polyurethane nanocomposites

  • Long LiEmail author
  • Kangjia Jiang
  • Yi QianEmail author
  • Haoyue Han
  • Peng Qiao
  • Haiming Zhang


Flame retardant thermoplastic polyurethane (TPU) nanocomposites were prepared by melt blending using organically intercalation modified layered double hydroxides-graphene oxide hybrids (LDHs-GO). Modification process of LDHs-GO was carried out by using sodium dodecyl sulfate (SDS) in water/ethanol medium. X-ray diffraction, Fourier transform infrared spectra and scanning electron microscope micrograph results showed the SDS intercalation modified LDHs-GO (SDS-LDHs-GO) was synthesized successfully. Flame retardancy, suppression smoke and thermal stability properties of the well-dispersed TPU nanocomposites were evaluated and compared with each other. The CCT results showed that the pHRR was significantly decreased after incorporating SDS-LDHs-GO nanoparticles. In particular, the pHRR of the TPU5 containing 20 mass% SDS-LDHs-5%GO hybrid was decreased by 77.2% compared to that of pure TPU. The addition of SDS-LDHs-GO hybrids can enhance the suppression smoke performance of TPU nanocomposites as well, and the efficiency was dependent on the catalytic carbonization of lamellar LDHs and both the adsorption and barrier effect of GO. The TG results confirmed that GO can improve the thermal stability of nanocomposites by promoting char formation. This work provides a novel modification strategy for enhancing the dispersion and flame retardant efficiency of LDHs.


Thermoplastic polyurethane Layered double hydroxides Graphene oxide Sodium dodecyl sulfate Flame retardancy 



The authors gratefully acknowledge the National Natural Science Foundation of China (No. 51572138), the Key R & D Project of Shandong Province (Nos. 2019GSF109001, 2019CSF109080), the Shandong Provincial Natural Science Foundation, China (No. ZR2018BB072), the Original Innovation Project of Qingdao City (No. 19-6-2-23-cg), the Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering (Nos. 2018-K09 and 2018-K43), Key Laboratory of Coastal Environmental Processes and Ecological Remediation, YICCAS (No. 2018KFJJ02) and Opening Project of Shandong Ecochemical Engineering Collaborative Innovation Center (No. XTCXQN02).


  1. 1.
    Oliveira SV, Araújo EM, Pereira CMC, Leite AMD. Polyethylene/bentonite clay nanocomposite with flame retardant properties. Polímeros. 2017;27:91–8.CrossRefGoogle Scholar
  2. 2.
    Xu WZ, Li AJ, Liu YC, Chen R, Li W. CuMoO4@hexagonal boron nitride hybrid: an ecofriendly flame retardant for polyurethane elastomer. J Mater Sci. 2018;53(16):11265–79.CrossRefGoogle Scholar
  3. 3.
    Zhou KQ, Zhang QJ, Liu JJ, Wang B, Jiang SH, Shi YQ, Hu Y, Gui Z. Synergetic effect of ferrocene and MoS2 in polystyrene composites with enhanced thermal stability, flame retardant and smoke suppression properties. RSC Adv. 2014;4(26):1320513214.Google Scholar
  4. 4.
    Wang XR, Li Y, Tang LP, Gan W, Zhou W, Zhao YF, Bai DS. Fabrication of Zn-Ti layered double hydroxide by varying cationic ratio of Ti4+ and its application as UV absorbent. Chin Chem Lett. 2017;28:256–61.Google Scholar
  5. 5.
    Parida KM, Mohapatra L. Carbonate intercalated Zn/Fe layered double hydroxide: a novel photocatalyst for the enhanced photo degradation of azo dyes. Chem Eng J. 2012;179:131–9.CrossRefGoogle Scholar
  6. 6.
    Jagadale AD, Guan GQ, Li XM, Du X, Ma XL, Hao XG, Abudula A. Ultrathin nanoflakes of cobalt–manganese layered double hydroxide with high reversibility for asymmetric supercapacitor. J Power Sources. 2016;306:526–34.CrossRefGoogle Scholar
  7. 7.
    Ma LJ, Wang Q, Islam SM, Liu YC, Ma SL, Kanatzidis MG. Highly selective and efficient removal of heavy metals by layered double hydroxide intercalated with the MoS4 2− ion. J Am Chem Soc. 2016;138:2858–66.PubMedCrossRefGoogle Scholar
  8. 8.
    Cai J, Heng HM, Hu XP, Xu QK, Miao F. A facile method for the preparation of novel fire-retardant layered double hydroxide and its application as nanofiller in UP. Polym Degrad Stab. 2016;126:47–57.CrossRefGoogle Scholar
  9. 9.
    Poonoosamya J, Brandta F, Stekielb M, Keglera P, Klinkenberga M, Winklerb B, Vinograda V, Bosbacha D, Deissmann G. Zr-containing layered double hydroxides: synthesis, characterization, and evaluation of thermodynamic properties. Appl Clay Sci. 2018;151:54–65.CrossRefGoogle Scholar
  10. 10.
    Kuila T, Acharya H, Srivastava SK, Bhowmick AK. Effect of vinyl acetate content on the mechanical and thermal properties of ethylene vinyl acetate/MgAl layered double hydroxide nanocomposites. J Appl Polym Sci. 2008;108(2):1329–35.CrossRefGoogle Scholar
  11. 11.
    Conterosito E, Gianotti V, Palin L, Boccaleri E, Viterbo D, Milanesio M. Facile preparation methods of hydrotalcite layered materials and their structural characterization by combined techniques. Inorg Chim Acta. 2018;47:36–50.CrossRefGoogle Scholar
  12. 12.
    Katsuomi T. Recent development of layered double hydroxide-derived catalysts -Rehydration, reconstitution, and supporting, aiming at commercial application-. Appl Clay Sci. 2017;136:112–41.CrossRefGoogle Scholar
  13. 13.
    Zhou M, Yan LC, Ling H, Diao YP, Pang XL, Wang YL, Gao KW. Design and fabrication of enhanced corrosion resistance Zn–Al layered double hydroxides films based anion-exchange mechanism on magnesium alloys. Appl Surf Sci. 2017;404:246–53.CrossRefGoogle Scholar
  14. 14.
    Zheng YL, Chen YH. Preparation of polypropylene/Mg–Al layered double hydroxides nanocomposites through wet pan-milling: formation of a second-staging structure in LDHs intercalates. RSC Adv. 2017;7:1520–30.CrossRefGoogle Scholar
  15. 15.
    Allou NB, Saikia P, Borah A, Goswamee RL. Hybrid nanocomposites of layered double hydroxides: an update of their biological applications and future prospects. Colloid Polym Sci. 2017;295(5):725–47.CrossRefGoogle Scholar
  16. 16.
    Du BX, Ma HY, Fang ZP. How nano-fillers affect thermal stability and flame retardancy of intumescent flame retarded polypropylene. Polym Adv Technol. 2011;22(7):1139–46.CrossRefGoogle Scholar
  17. 17.
    Gao YS, Wang Q, Wang JY, Huang L, Yan XR, Zhang X, He QL, Xing ZP, Guo ZH. Synthesis of highly efficient flame retardant high-density polyethylene nanocomposites with inorgano-layered double hydroxides as nanofiller using solvent mixing method. ACS Appl Mater Interfaces. 2014;6(7):5094–104.PubMedCrossRefPubMedCentralGoogle Scholar
  18. 18.
    Yu JF, Wang Q, O’Hare D, Sun LY. Preparation of two dimensional layered double hydroxide nanosheets and their applications. Chem Soc Rev. 2017;46:5950–74.PubMedCrossRefPubMedCentralGoogle Scholar
  19. 19.
    Sun MZ, Zhang P, Wu DS, Frost RL. Novel approach to fabricate organo-LDH hybrid by the intercalation of sodium hexadecyl sulfate into tricalcium aluminate. Appl Clay Sci. 2017;140:25–30.CrossRefGoogle Scholar
  20. 20.
    Elbasuney S. Surface engineering of layered double hydroxide (LDH) nanoparticles for polymer flame retardancy. Powder Technol. 2015;277:63–73.CrossRefGoogle Scholar
  21. 21.
    Kalali EN, Wang X, Wang DY. Functionalized layered double hydroxide-based epoxy nanocomposites with improved flame retardancy and mechanical properties. J Mater Chem A. 2015;3:6819–26.CrossRefGoogle Scholar
  22. 22.
    Nyambo C, Songtipya P, Manias E, Jimenez-Gascoc MM, Wilkie CA. Effect of MgAl-layered double hydroxide exchanged with linear alkyl carboxylates on fire-retardancy of PMMA and PS. J Mater Chem. 2008;18(40):4827–38.CrossRefGoogle Scholar
  23. 23.
    Wang LL, Li B, Zhang XC, Chen CX, Zhang F. Effect of intercalated anions on the performance of Ni–Al LDH nanofiller of ethylene vinyl acetate composites. Appl Clay Sci. 2012;56:110–9.CrossRefGoogle Scholar
  24. 24.
    Surudzic R, Jankovic A, Mitric M, Matic I, Juranic ZD, Zivkovic L, Miskovic-Stankovic V, Rhee KY, Park SJ, Hui D. The effect of graphene loading on mechanical, thermal and biological properties of poly(vinyl alcohol)/graphene nanocomposites. J Ind Eng Chem. 2016;34:250–7.CrossRefGoogle Scholar
  25. 25.
    Wang R, Zhuo DX, Weng ZX, Wu LX, Cheng XY, Zhou Y, Wang JL, Xuan BW. A novel nanosilica/graphene oxide hybrid and its flame retarding epoxy resin with simultaneously improved mechanical, thermal conductivity, and dielectric properties. J Mater Chem A. 2015;3:9826–36.CrossRefGoogle Scholar
  26. 26.
    Wang X, Song L, Pornwannchai W, Hu Y, Kandola B. The effect of graphene presence in flame retarded epoxy resin matrix on the mechanical and flammability properties of glass fiber-reinforced composites. Compos A Appl Sci Manuf. 2013;53:88–96.CrossRefGoogle Scholar
  27. 27.
    Wicklein B, Kocjan A, Salazar-Alvarez G, Carosio F, Camino G, Antonietti M, Bergström L. Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide. Nat Nanotechnol. 2015;10:277–83.PubMedCrossRefGoogle Scholar
  28. 28.
    Zhao MQ, Zhang Q, Huang JQ, Wei F. Hierarchical nanocomposites derived from nanocarbons and layered double hydroxides-properties, synthesis, and applications. Adv Funct Mater. 2012;22(4):675–94.CrossRefGoogle Scholar
  29. 29.
    Yuan BH, Bao CL, Song L, Hong NN. Preparation of functionalized graphene oxide/polypropylene nanocomposite with significantly improved thermal stability and studies on the crystallization behavior and mechanical properties. Chem Eng J. 2014;237:411–20.CrossRefGoogle Scholar
  30. 30.
    Sang B, Li ZW, Li XH, Yu LG, Zhang ZJ. Graphene-based flame retardants: a review. J Mater Sci. 2016;51(18):8271–95.CrossRefGoogle Scholar
  31. 31.
    Chen XL, Jiang YF, Jiao CM. Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate. J Hazard Mater. 2014;266:114–21.PubMedCrossRefPubMedCentralGoogle Scholar
  32. 32.
    Zhang H, Zhang J, Yun RP, Jiang ZG, Liu HM, Yan DP. Nanohybrids of organo-modified layered double hydroxides and polyurethanes with enhanced mechanical, damping and UV absorption properties. Rsc Adv. 2016;6(41):34288–96.CrossRefGoogle Scholar
  33. 33.
    Zhang Y, Wang BB, Yuan BH, Yuan Y, Liew KM, Song L, Hu Y. Preparation of large size reduced graphene oxide wrapped ammonium polyphosphate and its enhancement on the mechanical and flame retardant properties of thermoplastic polyurethane. Ind Eng Chem Res. 2017;56:7468–77.CrossRefGoogle Scholar
  34. 34.
    Krishnamoorthy K, Veerapandian M, Yun K, Kim SJ. The chemical and structural analysis of graphene oxide with different degrees of oxidation. Carbon. 2013;53:38–49.CrossRefGoogle Scholar
  35. 35.
    Xu WZ, Zhang BL, Xu BL, Li AJ. The flame retardancy and smoke suppression effect of heptaheptamolybdate modified reduced graphene oxide/layered double hydroxide hybrids on polyurethane elastomer. Compos A. 2016;91:30–40.CrossRefGoogle Scholar
  36. 36.
    Wang X, Zhou S, Xing WY, Yu B, Feng XM, Song L, Hu Y. Self-assembly of Ni–Fe layered double hydroxide/graphene hybrids for reducing fire hazard in epoxy composites. J Mater Chem A. 2013;1(13):4383–90.CrossRefGoogle Scholar
  37. 37.
    Ahmed NS, Menzel R, Wang YF, Garcia-Gallastegui A, Bawaked SM, Obaid AY, Basahel SN, Mokhtar M. Graphene-oxide-supported CuAl and CoAl layered double hydroxides as enhanced catalysts for carbon-carbon coupling via Ullmann reaction. J Solid State Chem. 2017;246:130–7.CrossRefGoogle Scholar
  38. 38.
    Hong NN, Song L, Wang BB, Stec AA, Hull TR, Zhan J, Hu Y. Co-precipitation synthesis of reduced graphene oxide/NiAl-layered double hydroxide hybrid and its application in flame retarding poly(methyl methacrylate). Mater Res Bull. 2014;49:657–64.CrossRefGoogle Scholar
  39. 39.
    Qian Y, Li SQ, Chen XL. Preparation of mesoporous silica-LDHs system and its coordinated flame-retardant effect on EVA. J Therm Anal Calorim. 2017;130(1):2055–67.CrossRefGoogle Scholar
  40. 40.
    Jiao CM, Wang HZ, Li SX, Chen XL. Fire hazard reduction of hollow glass microspheres in thermoplastic polyurethane composites. J Hazard Mater. 2017;332:176–84.PubMedCrossRefPubMedCentralGoogle Scholar
  41. 41.
    Dong YY, Gui Z, Hu Y, Wu Y, Jiang SH. The influence of titanate nanotube on the improved thermal properties and the smoke suppression in poly(methyl methacrylate). J Hazard Mater. 2012;209–210:34–9.PubMedCrossRefPubMedCentralGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2020

Authors and Affiliations

  1. 1.College of Environment and Safety EngineeringQingdao University of Science and TechnologyQingdaoChina
  2. 2.College of Chemical EngineeringQingdao University of Science and TechnologyQingdaoChina

Personalised recommendations