A strategy to synthesize phosphorus-containing nickel phyllosilicate whiskers to enhance the flame retardancy of epoxy composites with excellent mechanical and dry-friction properties

Abstract

To enhance the fire safety and wear resistance of epoxy, phosphorus-containing nickel phyllosilicate whiskers (FP-NiPS) were synthesized using a facile hydrothermal technology, with 9,10-dihydro-9-oxa-10-phosphaphenanthrene as the organic modifier. The impacts of FP-NiPS on the thermal stability, flame retardancy, and mechanical and tribological properties of EP composites were explored. The findings demonstrated that 5 wt % FP-NiPS elevated the limiting oxygen index of the EP composite from 23.8% to 28.4%, achieving a V-0 rating during vertical burning tests. FP-NiPS could enhance the thermal stability of epoxy resin (EP) and facilitate the development of a dense and continuous carbon layer, thereby significantly improving the fire safety of the EP composites. The FP-NiPS led to an 8.2% increase in the tensile strength and a 38.8% increase in the elastic modulus of the EP composite, showing outstanding mechanical properties. Furthermore, FP-NiPS showed remarkable potential in enhancing the wear resistance of EP. The wear rate of 1 wt % FP-NiPS is 2.34 × 10⁻⁵ mm³·N^–1·m^–1, a decrease of 66.7% compared to EP. This work provides a novel promising modification method to enhance the fire safety, mechanical and wear resistance properties of EP.

Key words： nickel phyllosilicate; epoxy resin; flame retardant; wear resistance; mechanical property

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

The authors gratefully acknowledge outstanding Youth Scientific Research Project in Anhui Province (Grant No. 2022AH020055), the Key Research and Development Projects in Anhui Province (Grant Nos. 2022i01020016, 2023g07020001), the National Natural Science Foundation of China (Grant No. 52074011), the University Synergy innovation Program of Anhui Province (Grant No. GXXT-2022-018).

References

1 Peng C H , Chen T , Zeng B R , Chen G R , Yuan C H , Xu Y T , Dai L Z . Anderson-type polyoxometalate-based hybrid with high flame retardant efficiency for the preparation of multifunctional epoxy resin nanocomposites. Composites. Part B, Engineering, 2020, 186: 107780

2 Liu Z , Qiu Y , Qian L J , Chen Y J , Xu B . Strengthen flame retardancy of epoxy thermoset by montmorillonite particles adhering phosphorus-containing fragments. Journal of Applied Polymer Science, 2020, 137(1): 47500

3 Becker C M , Gabbardo A D , Wypych F , Amico S C . Mechanical and flame-retardant properties of epoxy/Mg-Al LDH composites. Composites. Part A, Applied Science and Manufacturing, 2011, 42(2): 196–202

4 Kalali E N , Wang X , Wang D Y . Functionalized layered double hydroxide-based epoxy nanocomposites with improved flame retardancy and mechanical properties. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2015, 3(13): 6819–6826

5 Cai W , Guo W W , Pan Y , Wang J L , Mu X W , Feng X M , Yuan B H , Wang B B , Hu Y . Polydopamine-bridged synthesis of ternary h-BN@PDA@SnO₂ as nanoenhancers for flame retardant and smoke suppression of epoxy composites. Composites. Part A, Applied Science and Manufacturing, 2018, 111: 94–105

6 Wang X , Xing W Y , Feng X M , Song L , Hu Y . MoS₂/polymer nanocomposites: preparation, properties, and applications. Polymer Reviews, 2017, 57(3): 440–466

7 Zhi M Y , Liu Q Y , Zhao Y L , Gao S S , Zhang Z , He Y H . Novel MoS₂-DOPO hybrid for effective enhancements on flame retardancy and smoke suppression of flexible polyurethane foams. ACS Omega, 2020, 5(6): 2734–2746

8 Zhou K Q , Gao R , Qian X D . Self-assembly of exfoliated molybdenum disulfide (MoS₂) nanosheets and layered double hydroxide (LDH): towards reducing fire hazards of epoxy. Journal of Hazardous Materials, 2017, 338: 343–355

9 Wang L , Wu S H , Dong X Y , Wang R , Zhang L Q , Wang J L , Zhong J , Wu L X , Wang X . A pre-constructed graphene-ammonium polyphosphate aerogel (GAPPA) for efficiently enhancing the mechanical and fire-safety performances of polymers. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2018, 6(10): 4449–4457

10 Wang Z , Wu W , Wagner M H , Zhang L , Bard S . Synthesis of DV-GO and its effect on the fire safety and thermal stability of bismaleimide. Polymer Degradation & Stability, 2016, 128: 209–216

11 Wang H N , Su F F , Wang Z H , Xin Y Y , Yao D D , Zheng Y P . Using phenylphosphinic acid/zinc hydroxystannate nanoparticle-decorated graphene to enhance the flame retardancy and smoke suppressive performance of epoxy resin. New Journal of Chemistry, 2023, 47(4): 1760–1766

12 Shi X H , Wu S J , Xie W M , Li X L , Liu Q Y , Jimena D L V , Wang D Y . Fabrication of layered double hydroxide@ferric decorated polyphosphazene hybrid architecture towards simultaneously improved fire safety, smoke suppression and mechanical strength of epoxy resin. Composites. Part A, Applied Science and Manufacturing, 2023, 172: 107602

13 Qiu C , Jiang J , Ai L . When layered nickel-cobalt silicate hydroxide nanosheets meet carbon nanotubes: a synergetic coaxial nanocable structure for enhanced electrocatalytic water oxidation. ACS Applied Materials & Interfaces, 2016, 8(1): 945–951

14 Jiang L , Yang J N , Dong J , Nie S B , Xu Y X , Feng X S . Facile synthesis of polyaniline nanorods to simultaneously enhance the mechanical properties and wear resistance of epoxy composites. Frontiers of Chemical Science and Engineering, 2023, 17(9): 1254–1266

15 Bian Z , Kawi S . Preparation, characterization and catalytic application of phyllosilicate: a review. Catalysis Today, 2020, 339: 3–23

16 Yang J N , Li Z Y , Xu Y X , Nie S B , Liu Y . Effect of nickel phyllosilicate on the morphological structure, thermal properties and wear resistance of epoxy nanocomposites. Journal of Polymer Research, 2020, 27(9): 274

17 Yang J N , Feng X S , Nie S B , Xu Y X , Li Z Y . Self-sacrificial templating synthesis of flower-like nickel phyllosilicates and its application as high-performance reinforcements in epoxy nanocomposites. Frontiers of Chemical Science and Engineering, 2022, 16(4): 484–497

18 Yang J N , Feng X S , Nie S B , Dong J , Jiang L , Xu Y X . Simultaneously enhanced friction and wear resistances of epoxy nanocomposites modified by nickel phyllosilicate nanoflowers under wet sliding conditions. Polymer Composites, 2023, 44(6): 3054–3067

19 Xu Y X , Dai G L , Nie S B , Yang J N , Liu S , Zhang H , Dong X . Nickel-based metal-organic framework-derived whisker-shaped nickel phyllosilicate toward efficiently enhanced mechanical, flammable and tribological properties of epoxy nanocomposites. Frontiers of Chemical Science and Engineering, 2022, 16(10): 1493–1504

20 Dong J , Yang J , Jin P , Nie S . Facile synthesizing the homogeneous hierarchical nanosheets of nickel phyllosilicate to enhance the wear resistance, mechanical response and thermal stability of epoxy composites. Journal of Materials Research and Technology, 2023, 26: 6857–6876

21 Wang L , Hu X M , Mao Z L , Wang J L , Wang X . Phosphorylated metal-organic framework for reducing fire hazards of poly(methyl methacrylate). Polymers, 2022, 14(22): 48–71

22 Zhang L , Chen S Q , Pan Y T , Zhang S D , Nie S B , Wei P , Zhang X Q , Wang R , Wang D Y . Nickel metal-organic framework derived hierarchically mesoporous nickel phosphate toward smoke suppression and mechanical enhancement of intumescent flame retardant wood fiber/poly(lactic acid) composites. ACS Sustainable Chemistry & Engineering, 2019, 7(10): 9272–9280

23 Burattin P , Che M , Louis C . Characterization of the Ni(II) phase formed on silica upon deposition-precipitation. Journal of Physical Chemistry B, 1997, 101(36): 7060–7074

24 Melo M A Jr , Pires C , Airoldi C . The influence of the leaving iodine atom on phyllosilicate syntheses and useful application in toxic metal removal with favorable energetic effects. RSC Advances, 2014, 4(77): 41028–41038

25 Fonseca M G , Airoldi C . Calorimetric study of amino modified talc matrices and copper salts. An evidence of the chelate effect. Journal of Thermal Analysis and Calorimetry, 2001, 64(1): 273–280

26 Burkett S L , Press A , Mann S . Synthesis, characterization, and reactivity of layered inorganic organic nanocomposites based on 2:1 trioctahedral phyllosilicates. Chemistry of Materials, 1997, 9(5): 1071–1073

27 Ni S Z , Wang C J , Bian H Y , Yu Z H , Jiao L , Fang G G , Dai H Q . Enhancing physical performance and hydrophobicity of paper-based cellulosic material via impregnation with starch and PEI-KH560. Cellulose, 2018, 25(2): 1365–1375

28 Kundu C K , Song L , Hu Y . Sol-gel coatings from DOPO-alkoxysilanes: efficacy in fire protection of polyamide 66 textiles. European Polymer Journal, 2020, 125: 109483

29 Wang Q P , Xiong L , Liang H B , Chen L , Huang S M . Synthesis of a novel polysiloxane containing phosphorus, and boron and its effect on flame retardancy, mechanical, and thermal properties of epoxy resin. Polymer Composites, 2018, 39(3): 807–814

30 Yang J N , Liu Y , Xu Y X , Nie S B , Li Z Y . Property investigations of epoxy composites filled by nickel phyllosilicate-decorated graphene oxide. Journal of Materials Science, 2020, 55(24): 10593–10610

31 Burattin P , Che M , Louis C . Characterization of the Ni(II) phase formed on silica upon deposition-precipitation. Journal of Physical Chemistry B, 1997, 101(36): 7060–7074

32 Adam F , Chew T . A facile template-free room temperature synthesis of mesoporous wormlike nickel phyllosilicate. Open Colloid Science Journal, 2012, 5(1): 1–4

33 Fonseca M G , Silva C R , Barone J S , Airoldi C . Layered hybrid nickel phyllosilicates and reactivity of the gallery space. Journal of Materials Chemistry, 2000, 10(3): 789–795

34 Rajaei M , Wang D Y , Bhattacharyya D . Combined effects of ammonium polyphosphate and talc on the fire and mechanical properties of epoxy/glass fabric composites. Composites. Part B, Engineering, 2017, 113: 381–390

35 Luo H Q , Rao W H , Zhao P , Wang L , Liu Y L , Yu C B . An efficient organic/inorganic phosphorus-nitrogen-silicon flame retardant towards low-flammability epoxy resin. Polymer Degradation & Stability, 2020, 178: 109–195

36 Yuan B H , Hu Y , Chen X F , Shi Y Q , Niu Y , Zhang Y , He S , Dai H M . Dual modification of graphene by polymeric flame retardant and Ni(OH)₂ nanosheets for improving flame retardancy of polypropylene. Composites. Part A, Applied Science and Manufacturing, 2017, 100: 106–117

37 Hou Y B , Hu W Z , Gui Z , Hu Y . Bi₂Se₃ nanosheets: advanced nanofillers for reinforcing and flame retarding polyethylene nanocomposites. Composites. Part A, Applied Science and Manufacturing, 2017, 100: 371–380

38 Kim H , Abdala A A , Macosko C W . Graphene/polymer nanocomposites. Macromolecules, 2010, 43(16): 6515–6530

39 Wang K , Wu J , Ye L , Zeng H . Mechanical properties and toughening mechanisms of polypropylene/barium sulfate composites. Composites. Part A, Applied Science and Manufacturing, 2003, 34(12): 1199–1205

40 Gupta S , Hammann T , Johnson R , Riyad M F . Tribological behavior of novel Ti₃SiC₂ (natural nanolaminates)-reinforced epoxy composites during dry sliding. Tribology Transactions, 2015, 58(3): 560–566

41 Myshkin N , Kovalev A . Adhesion and surface forces in polymer tribology: a review. Friction, 2018, 6(2): 143–155