Influence of a novel biobased coating decorated with UiO-66/BN in persistent flame-retardant hybrids on the fire safety and thermal degradation of epoxy resin

Zhicong Song, Juntong Zhou, Liping Jin, Yu Guan, Wei Wang, Wenwen Guo

Front. Chem. Sci. Eng. ›› 2025, Vol. 19 ›› Issue (5) : 43.

PDF(3260 KB)
PDF(3260 KB)
Front. Chem. Sci. Eng. ›› 2025, Vol. 19 ›› Issue (5) : 43. DOI: 10.1007/s11705-025-2545-2
RESEARCH ARTICLE

Influence of a novel biobased coating decorated with UiO-66/BN in persistent flame-retardant hybrids on the fire safety and thermal degradation of epoxy resin

Author information +
History +

Abstract

To increase the fire safety of epoxy resin, this study employed a layer-by-layer self-assembly method to prepare a biologically flame-retardant coating-modified zirconium-based metal-organic framework (chitosan/phytic acid (CS/PA) @UiO-66). This study also attempted to incorporate boron nitride (BN) to enhance the flame-retardant properties of epoxy resin composites. The results from Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy confirmed the successful synthesis of UiO-66 and illustrated the assembly of CS and PA onto UiO-66 through a self-assembly strategy. Thermogravimetric analysis in conjunction with cone calorimetry and Raman spectroscopy analyses indicated that incorporating biologically-based flame-retardant coating-modified CS/PA@UiO-66 and BN nanosheets could effectively increase the flame-retardant performance of epoxy composites. Compared with pure epoxy resin, the incorporation of CS/PA@UiO-66-3 and CS/PA@UiO-66-3/BN led to a reduction in the peak heat release rate and total heat release values of 61.13% and 22.36% for EP/CS/PA@UiO-66-3 and EP/CS/PA@UiO-66-3/BN, respectively. Notably, EP/CS/PA@UiO-66-3/BN presented a continuous and dense char layer surface with increased graphite arrangement and higher residual char content after thermal degradation and combustion, thereby providing effective suppression of heat, mass, and oxygen transfer, demonstrating promising flame-retardant efficacy. Consequently, this study successfully improved the fire safety of epoxy resin and presented a new approach for the use of biologically-based flame-retardants.

Graphical abstract

Keywords

epoxy resin / metal-organic framework / flame retardant / smoke suppressant / boron nitride

Cite this article

Download citation ▾
Zhicong Song, Juntong Zhou, Liping Jin, Yu Guan, Wei Wang, Wenwen Guo. Influence of a novel biobased coating decorated with UiO-66/BN in persistent flame-retardant hybrids on the fire safety and thermal degradation of epoxy resin. Front. Chem. Sci. Eng., 2025, 19(5): 43 https://doi.org/10.1007/s11705-025-2545-2

References

[1]
Cui M, Ren S, Zhao H, Xue Q, Wang L. Polydopamine coated graphene oxide for anticorrosive reinforcement of water-borne epoxy coating. Chemical Engineering Journal, 2018, 335: 255–266
CrossRef Google scholar
[2]
GuoQ. Thermosets: Structure, Properties, and Applications. Cambridge: Woodhead Publishing, 2017, 30–35
[3]
Kong Q, Sun Y, Zhang C, Guan H, Zhang J, Wang D Y, Zhang F. Ultrathin iron phenyl phosphonate nanosheets with appropriate thermal stability for improving fire safety in epoxy. Composites Science and Technology, 2019, 182: 107748
CrossRef Google scholar
[4]
Zhou K, Tang G, Gao R, Jiang S. In situ growth of 0D silica nanospheres on 2D molybdenum disulfide nanosheets: towards reducing fire hazards of epoxy resin. Journal of Hazardous Materials, 2018, 344: 1078–1089
CrossRef Google scholar
[5]
Guo W, Wang X, Gangireddy R C S, Wang J, Pan Y, Xing W, Song L, Hu Y. Manufacturing, cardanol derived benzoxazine in combination with boron-doped graphene toward simultaneously improved toughening and flame retardant epoxy composites. Composites Part A: Applied Science and Manufacturing, 2019, 116: 13–23
CrossRef Google scholar
[6]
Zhang A, Zhang J, Liu L, Dai J, Lu X, Huo S, Hong M, Liu X, Lynch M, Zeng X. Technology, engineering phosphorus-containing lignin for epoxy biocomposites with enhanced thermal stability, fire retardancy and mechanical properties. Journal of Materials Science and Technology, 2023, 167: 82–93
CrossRef Google scholar
[7]
Wang J, Wang J, Yang S, Chen X, Chen K, Zhou G, Liu X, Xu L, Huo S, Song P. . Multifunctional phosphorus-containing imidazoliums endowing one-component epoxy resins with superior thermal latency, heat resistance, mechanical properties, and fire safety. Chemical Engineering Journal, 2024, 485: 149852
CrossRef Google scholar
[8]
Gong K, Zhou K, Yu B. Superior thermal and fire safety performances of epoxy-based composites with phosphorus-doped cerium oxide nanosheets. Applied Surface Science, 2020, 504: 144314
CrossRef Google scholar
[9]
Jiang S, Tang G, Chen J, Huang Z, Hu Y. Biobased polyelectrolyte multilayer-coated hollow mesoporous silica as a green flame retardant for epoxy resin. Applied Surface Science, 2018, 342: 689–697
[10]
Guo W, Wang X, Huang J, Zhou Y, Cai W, Wang J, Song L, Hu Y. Construction of durable flame-retardant and robust superhydrophobic coatings on cotton fabrics for water-oil separation application. Applied Surface Science, 2020, 398: 125661
[11]
Chen Z, Chen T, Yu Y, Zhang Q, Chen Z, Jiang J. Metal-organic framework MIL-53 (Fe)@C/graphite carbon nitride hybrids with enhanced thermal stability, flame retardancy, and smoke suppression for unsaturated polyester resin. Polymers for Advanced Technologies, 2019, 30(9): 2458–2467
CrossRef Google scholar
[12]
Huang R, Guo X, Ma S, Xie J, Xu J, Ma J. Novel phosphorus-nitrogen-containing ionic liquid modified metal-organic framework as an effective flame retardant for epoxy resin. Polymers, 2020, 12(1): 108
CrossRef Google scholar
[13]
Hou Y, Hu W, Gui Z, Hu Y. A novel Co(II)-based metal-organic framework with phosphorus-containing structure: build for enhancing fire safety of epoxy. Composites Science and Technology, 2017, 152: 231–242
CrossRef Google scholar
[14]
Guo W, Nie S, Kalali E N, Wang X, Wang W, Cai W, Song L, Hu Y. Construction of SiO2@UiO-66 core-shell microarchitectures through covalent linkage as flame retardant and smoke suppressant for epoxy resins. Composites Part B: Engineering, 2019, 176: 107261
CrossRef Google scholar
[15]
Wang X, Guo W, Cai W, Wang J, Song L, Hu Y. Recent advances in construction of hybrid nano-structures for flame retardant polymers application. Applied Materials Today, 2020, 20: 100762
CrossRef Google scholar
[16]
Golberg D, Bando Y, Huang Y, Terao T, Mitome M, Tang C, Zhi C. Boron nitride nanotubes and nanosheets. ACS Nano, 2010, 4(6): 2979–2993
CrossRef Google scholar
[17]
Yu B, Xing W, Guo W, Qiu S, Wang X, Lo S, Hu Y. Thermal exfoliation of hexagonal boron nitride for effective enhancements on thermal stability, flame retardancy and smoke suppression of epoxy resin nanocomposites via sol-gel process. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2016, 4(19): 7330–7340
CrossRef Google scholar
[18]
Guerra V, Wan C, McNally T. Thermal conductivity of 2D nano-structured boron nitride (BN) and its composites with polymers. Progress in Materials Science, 2019, 100: 170–186
CrossRef Google scholar
[19]
Morishita T, Okamoto H. Facile exfoliation and noncovalent superacid functionalization of boron nitride nanosheets and their use for highly thermally conductive and electrically insulating polymer nanocomposites. ACS Applied Materials & Interfaces, 2016, 8(40): 27064–27073
CrossRef Google scholar
[20]
Qiu S, Hou Y, Xing W, Ma C, Zhou X, Liu L, Kan Y, Yuen R K K, Hu Y. Self-assembled supermolecular aggregate supported on boron nitride nanoplatelets for flame retardant and friction application. Chemical Engineering Journal, 2018, 349: 223–234
CrossRef Google scholar
[21]
Yin L, Gong K, Zhou K, Qian X, Shi C, Gui Z, Qian L. Flame-retardant activity of ternary integrated modified boron nitride nanosheets to epoxy resin. Journal of Colloid and Interface Science, 2022, 608: 853–863
CrossRef Google scholar
[22]
Lin Z, Mcnamara A, Liu Y, Moon K, Wong C. Technology, exfoliated hexagonal boron nitride-based polymer nanocomposite with enhanced thermal conductivity for electronic encapsulation. Composites Science and Technology, 2014, 90: 123–128
CrossRef Google scholar
[23]
Fang F, Chen X, Zhang X, Cheng C, Xiao D, Meng Y, Ding X, Zhang H, Tian X. Environmentally friendly assembly multilayer coating for flame retardant and antimicrobial cotton fabric. Progress in Organic Coatings, 2016, 90: 258–266
CrossRef Google scholar
[24]
Fang Y, Sun W, Li J, Liu H, Liu X. Eco-friendly flame retardant and dripping-resistant of polyester/cotton blend fabrics through layer-by-layer assembly fully bio-based chitosan/phytic acid coating. Composites Science and Technology, 2021, 175: 140–146
[25]
Hou F, Zhu M, Liu Y, Zhu K, Xu J, Jiang Z, Wang C, Wang H. A self-assembled bio-based coating with phytic acid and DL-arginine used for a flame-retardant and antibacterial cellulose fabric. Progress in Organic Coatings, 2022, 173: 107179
CrossRef Google scholar
[26]
Yang Q, Jobic H, Salles F, Kolokolov D, Guillerm V, Serre C, Maurin G. Probing the dynamics of CO2 and CH4 within the porous zirconium terephthalate UiO-66 (Zr): a synergic combination of neutron scattering measurements and molecular simulations. Chemistry-A European Journal, 2011, 17(32): 8882–8889
CrossRef Google scholar
[27]
Yang Z, Xiao G, Chen C, Chen C, Zhong F, Cao M, Wang M, Zou R, Li R, Shang S. A novel P, N doped organic-inorganic hierarchical core-shell nanostructures: reducing the fire risk of epoxy resin. Progress in Organic Coatings, 2023, 183: 107776
CrossRef Google scholar
[28]
Cao M, Xiao G, Chen C, Chen C, Yang Z, Zhong F, Shang S, Wang M, Zou R. Synergetic modification of graphitic carbon nitride by Zr-based metal-organic framework and tetraethoxysilane for improving fire performance in composite coatings. Progress in Organic Coatings, 2023, 183: 107756
CrossRef Google scholar
[29]
Liu X, Gu X, Sun J, Zhang S. Preparation and characterization of chitosan derivatives and their application as flame retardants in thermoplastic polyurethane. Carbohydrate Polymers, 2017, 167: 356–363
CrossRef Google scholar
[30]
Lu Y, Feng J, Chu T, Huo S, Xie H, Xu Z, Wang H, Song P. Technology, a 2D biobased P/N-containing aggregate for boosting fire retardancy of PA6/aluminum diethylphosphinate via synergy. Journal of Materials Science and Technology, 2024, 198: 73–82
CrossRef Google scholar
[31]
Yang Q, Wang J, Chen X, Yang S, Huo S, Chen Q, Guo P, Wang X, Liu F, Chen W. . A phosphorus-containing tertiary amine hardener enabled flame retardant, heat resistant and mechanically strong yet tough epoxy resins. Chemical Engineering Journal, 2023, 468: 143811
CrossRef Google scholar
[32]
Guo W, Zhao Y, Wang X, Cai W, Wang J, Song L, Hu Y. Multifunctional epoxy composites with highly flame retardant and effective electromagnetic interference shielding performances. Composites Part B: Engineering, 2020, 192: 107990
CrossRef Google scholar
[33]
Zhang H, Mao J, Li M, Cai Q, Li W, Huang C, Yuan C, Xu Y, Zeng B, Dai L. Manufacturing, design of h-BN@boronate polymer core-shell nanoplates to simultaneously enhance the flame retardancy and mechanical properties of epoxy resin through the interficial regulation. Composites Part A: Applied Science and Manufacturing, 2020, 130: 105751
CrossRef Google scholar
[34]
Qiu X, Li Z, Li X, Yu L, Zhang Z. Construction and flame-retardant performance of layer-by-layer assembled hexagonal boron nitride coatings on flexible polyurethane foams. Journal of Applied Polymer Science, 2019, 136(29): 47839
CrossRef Google scholar
[35]
Dogan M, Dogan S D, Savas L A, Ozcelik G, Tayfun U. Flame retardant effect of boron compounds in polymeric materials. Composites Part B: Engineering, 2021, 222: 109088
CrossRef Google scholar
[36]
Cai W, Mu X, Pan Y, Guo W, Wang J, Yuan B, Feng X, Tai Q, Hu Y. Facile fabrication of organically modified boron nitride nanosheets and its effect on the thermal stability, flame retardant, and mechanical properties of thermoplastic polyurethane. Polymers for Advanced Technologies, 2018, 29(9): 2545–2552
CrossRef Google scholar
[37]
Wang J, Zhang D, Zhang Y, Cai W, Yao C, Hu Y, Hu W. Construction of multifunctional boron nitride nanosheet towards reducing toxic volatiles (CO and HCN) generation and fire hazard of thermoplastic polyurethane. Polymers for Advanced Technologies, 2019, 362: 482–494
[38]
Wang X, Hu W, Hu Y. Enhanced flame retardancy of poly (vinyl alcohol) with zinc molybdate nanoparticles decorated boron nitride nanosheets. Materials Express, 2020, 10(12): 2094–2100
[39]
Ambekar R S, Deshmukh A, Suarez-Villagran M Y, Das R, Pal V, Dey S, Miller J H Jr, Machado L D, Kumbhakar P, Tiwary C. Interfaces, 2D hexagonal boron nitride-coated cotton fabric with self-extinguishing property. ACS Applied Materials & Interfaces, 2020, 12(40): 45274–45280
CrossRef Google scholar
[40]
Wang X, Kalali E N, Wang D. Engineering, renewable cardanol-based surfactant modified layered double hydroxide as a flame retardant for epoxy resin. ACS Applied Materials & Interfaces, 2015, 3(12): 3281–3290
[41]
Wang X, Zhou S, Guo W, Wang P, Xing W, Song L, Hu Y. Engineering, renewable cardanol-based phosphate as a flame retardant toughening agent for epoxy resins. ACS Sustainable Chemistry & Engineering, 2017, 5(4): 3409–3416
CrossRef Google scholar
[42]
Chen W, Jiang Y, Qiu R, Xu W, Hou Y. Investigation of UiO-66 as flame retardant and its application in improving fire safety of polystyrene. Macromolecular Research, 2020, 28(1): 42–50
CrossRef Google scholar
[43]
Li P, Liu C, Wang B, Tao Y, Xu Y, Liu Y, Zhu P. Eco-friendly coating based on an intumescent flame-retardant system for viscose fabrics with multi-function properties: flame retardancy, smoke suppression, and antibacterial properties. Progress in Organic Coatings, 2021, 159: 106400
CrossRef Google scholar
[44]
Liu Y, Zhang A, Cheng Y, Li M, Cui Y, Li Z. Recent advances in biomass phytic acid flame retardants. Polymer Testing, 2023, 124: 108100
CrossRef Google scholar
[45]
Yang S, Wang J, Huo S, Cheng L, Wang M. Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle. Polymer Degradation & Stability, 2015, 119: 251–259
CrossRef Google scholar
[46]
Cai W, Feng X, Wang B, Hu W, Yuan B, Hong N, Hu Y. A novel strategy to simultaneously electrochemically prepare and functionalize graphene with a multifunctional flame retardant. Chemical Engineering Journal, 2017, 316: 514–524
CrossRef Google scholar
[47]
Tang W, Liao X, Qin Z, Zeng Y, Chen C, Zhu Q, Mo Z, Jin X. Improving the flame retardancy of epoxy resin by incorporating a bio-based flame retardant and kaolinite. Polymer Degradation & Stability, 2024, 227: 110895
CrossRef Google scholar
[48]
Wang K, Meng D, Wang S, Sun J, Li H, Gu X, Zhang S. Impregnation of phytic acid into the delignified wood to realize excellent flame retardant. Industrial Crops and Products, 2022, 176: 114364
CrossRef Google scholar
[49]
Zhang J, Li Z, Shao Z, Zhang L, Wang D. Hierarchically tailored hybrids via interfacial-engineering of self-assembled UiO-66 and prussian blue analogue: novel strategy to impart epoxy high-efficient fire retardancy and smoke suppression. Chemical Engineering Journal, 2020, 400: 125942
CrossRef Google scholar
[50]
Huang J, Guo W, Wang X, Niu H, Song L, Hu Y. Combination of cardanol-derived flame retardant with SiO2@MOF particles for simultaneously enhancing the toughness, anti-flammability and smoke suppression of epoxy thermosets. Composites Communications, 2021, 27: 100904
CrossRef Google scholar
[51]
Duan R, Wu H, Li J, Zhou Z, Meng W, Liu L, Qu H, Xu J. Phosphor nitrile functionalized UiO-66-NH2/graphene hybrid flame retardants for fire safety of epoxy. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 635: 128093
CrossRef Google scholar
[52]
Yang G, Wu W, Wang Y, Jiao Y, Lu L, Qu H, Qin X. Synthesis of a novel phosphazene-based flame retardant with active amine groups and its application in reducing the fire hazard of epoxy resin. Journal of Hazardous Materials, 2019, 366: 78–87
CrossRef Google scholar
[53]
Yu B, Tao Y, Liu L, Shi Y, Yang H, Jie G, Lo S, Tai Q, Song L, Hu Y. Thermal and flame retardant properties of transparent UV-curing epoxy acrylate coatings with POSS-based phosphonate acrylate. RSC Advances, 2015, 5(92): 75254–75262
CrossRef Google scholar
[54]
Chen Q, Liu L, Zhang A, Wang W, Wang Z, Zhang J, Feng J, Huo S, Zeng X, Song P. An iron phenylphosphinate@graphene oxide nanohybrid enabled flame-retardant, mechanically reinforced, and thermally conductive epoxy nanocomposites. RSC Advances, 2023, 454: 140424
[55]
Wang R, Zhang X, Yuan M, Wang D, Zhang J, Pan Y. Fire retardancy of epoxy composites: a comparative investigation on the influence of porous structure and transition metal of metal-organic framework. Composites Communications, 2024, 51: 102087
CrossRef Google scholar
[56]
Zhang Z, Qin J, Zhang W, Pan Y, Wang D, Yang R. Synthesis of a novel dual layered double hydroxide hybrid nanomaterial and its application in epoxy nanocomposites. Chemical Engineering Journal, 2020, 381: 122777
CrossRef Google scholar
[57]
Zhang Z, Li X, Yuan Y, Pan Y, Wang D, Yang R. Confined dispersion of zinc hydroxystannate nanoparticles into layered bimetallic hydroxide nanocapsules and its application in flame-retardant epoxy nanocomposites. ACS Applied Materials & Interfaces, 2019, 11(43): 40951–40960
CrossRef Google scholar
[58]
Sai T, Ran S, Guo Z, Fang Z. A Zr-based metal organic frameworks towards improving fire safety and thermal stability of polycarbonate. ACS Applied Materials & Interfaces, 2019, 176: 107198

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The authors would like to acknowledge the financial support of the Textile Light Applied Basic Research Project (Grant No. J202107), the Doctor Project of Innovation and Entrepreneurship in Jiangsu Province (Grant No. JSSCBS20210821), the National Natural Science Foundation of China (Grant No. 22205082) and the Natural Science Foundation of Jiangsu Province (Grant No. BK20221098).

RIGHTS & PERMISSIONS

2025 Higher Education Press
AI Summary AI Mindmap
PDF(3260 KB)

Accesses

Citations

Detail

Sections
Recommended

/