Simultaneously improving the thermal conductivity and flame resistance of epoxy composite is still a challenge. Herein, a novel epoxy composite with high thermal conductivity and greatly enhanced flame retardancy was developed through constructing integrated three-dimensional (3D) network based on boron nitride (BN), talc, ammonium polyphosphate (APP). The thermal conductivity of the composite with filler network reached 3.04 Wm−1K−1, which was 15.2 and 3.1 times of those of pure epoxy and sample with random filler distribution. The LOI value of the composite with filler network reached 37.8%, which was 1.9 and 1.4 times of those of pure epoxy and sample with random filler distribution, respectively. In addition, the effects of various combinations of filler on the flame resistance of the epoxy composite were also evaluated. The prepared composite with filler network exhibited excellent shape stability and mechanical strength even after ablation at 1000°C. The network structure constructed by BN had a positive effect on heat transfer, while APP led to the formation of phosphoric acid at high temperature, adhering to talc and other residues together. A ceramic-like residue was formed on the firing surface, which enhanced the barrier effect of char layer and flame resistance of the composite.
LiYDengCLongJ, et al.Improving fire retardancy of ceramifiable polyolefin system via a hybrid of zinc borate@melamine cyanurate. Polym Degrad Stab2018; 153: 325–332.
6.
GongXWuTMaJ, et al.Improved self-supporting property of ceramifying silicone rubber composites by forming crystalline phase at high temperatures. J Alloy Compd2017; 706: 322–329.
7.
ShiYQianXZhouK, et al.CuO/graphene nanohybrids: preparation and enhancement on thermal stability and smoke suppression of polypropylene. Ind Eng Chem Res2013; 52: 13654–13660.
8.
ZhangLTuSWangH, et al.Preparation of polymer/graphene oxide nanocomposites by a two-step strategy composed of in situ polymerization and melt processing. Compos Sci Technol2018; 154: 1–7.
9.
GuJLiangCZhaoX, et al.Highly thermally conductive flame-retardant epoxy nanocomposites with reduced ignitability and excellent electrical conductivities. Compos Sci Technol2017; 139: 83–89.
10.
HullTStecA. Polymer and fire. London: Royal Society of Chemistry, 2009.
11.
Di BlasiC. Modeling of solid- and gas-phase processes during thermal degradation of composite materials. Polym Degrad Stab1996; 54: 241–248.
12.
NelsonG. Fire and polymers: an overview. Washington, DC: ACS Publication, 1995.
13.
WangJJiCYanY, et al.Mechanical and ceramifiable properties of silicone rubber filled with different inorganic fillers. Polym Degrad Stab2015; 121: 149–156.
14.
LuoSShenYYuS, et al.Construction of a 3D-BaTiO3 network leading to significantly enhanced dielectric permittivity and energy storage density of polymer composites. Energy Environ Sci2017; 10: 137–144.
15.
ChenJHuangXZhuY, et al.Cellulose nanofiber supported 3D interconnected BN nanosheets for epoxy nanocomposites with ultrahigh thermal management capability. Adv Funct Mater2017; 27: 1604754.
16.
HuJHuangYYaoY, et al.Polymer composite with improved thermal conductivity by constructing a hierarchically ordered three-dimensional interconnected network of BN. Acs Appl Mater Inter2017; 9: 13544–13553.
17.
WangDMuXCaiW, et al.Constructing phosphorus, nitrogen, silicon-co-contained boron nitride nanosheets to reinforce flame retardant properties of unsaturated polyester resin. Composites Part A-Appl S2018; 109: 546–554.
18.
QiuSHouYXingW, et al.Self-assembled supermolecular aggregate supported on boron nitride nanoplatelets for flame retardant and friction application. Chem Eng J2018; 349: 223–234.
19.
QuTYangNHouJ, et al.Flame retarding epoxy composites with poly(phosphazene-co-bisphenol A)-coated boron nitride to improve thermal conductivity and thermal stability. RSC Adv2017; 7: 6140–6151.
20.
JinWYuanLLiangG, et al.Multifunctional Cyclotriphosphazene/hexagonal boron nitride hybrids and their flame retarding bismaleimide resins with high thermal conductivity and thermal stability. Acs Appl Mater Inter2014; 6: 14931–14944.
21.
YuBXingWGuoW, et al.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. J Mater Chem A2016; 4: 7330–7340.
22.
CaiWHongNFengX, et al.A facile strategy to simultaneously exfoliate and functionalize boron nitride nanosheets via Lewis acid-base interaction. Chem Eng J2017; 330: 309–321.
23.
LiuWZhaoDPanZ, et al.Enhanced residue stability and strength of epoxy-based coating for fire protection via ceramifiable strategy. Prog Org Coating2021; 154: 106211.
24.
XuXHuRChenM, et al.3D boron nitride foam filled epoxy composites with significantly enhanced thermal conductivity by a facial and scalable approach. Chem Eng J2020; 397: 125447.
25.
SongSWangJLiuC, et al.A facile route to fabricate thermally conductive and electrically insulating polymer composites with 3D interconnected graphene at an ultralow filler loading. Nanoscale2019; 11: 15234–15244.
26.
WuYYeKLiuZ, et al.Cotton candy-templated fabrication of three-dimensional ceramic pathway within polymer composite for enhanced thermal conductivity. Acs Appl Mater Inter2019; 11: 44700–44707.
27.
YoonHMatteiniPHwangB. Review on three-dimensional ceramic filler networking composites for thermal conductive applications. J Non-Cryst Solids2022; 576: 121272.
28.
BaoCSongLXingW, et al.Preparation of graphene by pressurized oxidation and multiplex reduction and its polymer nanocomposites by masterbatch-based melt blending. J Mater Chem2012; 22: 6088–6696.
29.
YuanHWangYLiT, et al.Fabrication of thermally conductive and electrically insulating polymer composites with isotropic thermal conductivity by constructing a three-dimensional interconnected network. Nanoscale2019; 11: 11360–11368.
30.
WangJQianLHuangZ, et al.Synergistic flame-retardant behavior and mechanisms of aluminum poly-hexamethylenephosphinate and phosphaphenanthrene in epoxy resin. Polym Degrad Stab2016; 130: 173–181.
31.
TianCYuanLLiangG, et al.High thermal conductivity and flame-retardant phosphorus-free bismaleimide resin composites based on 3D porous boron nitride framework. J Mater Sci2019; 54: 7651–7664.
32.
SunYSunWHuaH, et al.Overexpression of miR-127 predicts poor prognosis and contributes to the progression of papillary thyroid cancer by targeting REPIN1. Chem Adhes2021; 53: 197–203.
33.
LengYXuMSunY, et al.Simultaneously improving the thermal conductive and flame retardant performance for epoxy resins thermosets by constructing core‐shell‐brush structure and distributing of MWCNTs in brush intervals. Polym Adv Technol2019; 31: 589–601.
34.
LiuZ. Preparation and properties of thermally conductive flame retardant PA6 composites. MS Thesis. Qingdao, China: Qingdao University of Science and Technology, 2020.
35.
ChenP. Preparation of thermally conductive flame retardant epoxy composites. MS Thesis. Guangzhou, China: South China University of Technology, 2015.
36.
LengY. Preparation and properties of epoxy resins thermosets and wood composites with thermal conductive and flame retardant performance. MS Thesis. Harbin, China: Northeast Forestry University, 2020.
37.
LiZ. Preparation of thermal conductive and flame retardant polyurethane composite. MS Thesis. Guangzhou, China: South China University of Technology, 2015.
38.
GuanFGuiCZhangH, et al.Enhanced thermal conductivity and satisfactory flame retardancy of epoxy/alumina composites by combination with graphene nanoplatelets and magnesium hydroxide. Compos Part B-Eng2016; 98: 134–140.
39.
WangFShiWMaiY, et al.Effect of thermal conductive fillers on the flame retardancy, thermal conductivity, and thermal behavior of flame-retardant and thermal conductive polyamide 6. Materials2019; 12: 4114.
40.
ZhangLWangLFischerA, et al.Effect of graphite on the flame retardancy and thermal conductivity of P-N flame retarding PA6. J Appl Polym Sci2018; 135: 46559.
41.
Hazwani DzulkafliHAhmadFUllahS, et al.Effects of talc on fire retarding, thermal degradation and water resistance of intumescent coating. Appl Clay Sci2017; 146: 350–361.
IsitmanNAKaynakC. Nanoclay and carbon nanotubes as potential synergists of an organophosphorus flame-retardant in poly(methyl methacrylate). Polym Degrad Stab2010; 95: 1523–1532.
44.
WangGYangJ. Influences of glass flakes on fire protection and water resistance of waterborne intumescent fire resistive coating for steel structure. Prog Org Coating2011; 70: 150–156.
45.
LiYDengCShiX, et al.Simultaneously improved flame retardance and ceramifiable properties of polymer-based composites via the formed crystalline phase at high temperature. Acs Appl Mater Inter2019; 11: 7459–7471.
46.
XinhaoGYucaiSTingweiW. Improved ceramifiable properties of EVA composites with whitened and capsulized red phosphorus (WCRP). Rsc Adv2016; 6: 96984–96989.
47.
HonmaTSatoAItoN, et al.Crystallization behavior of sodium iron phosphate glass Na2−Fe1+0.5P2O7 for sodium ion batteries. J Non-Cryst Solids2014; 404: 26–31.
48.
GaoCZhuZShenY, et al.Efficient construction of boron nitride network in epoxy composites combining reaction-induced phase separation and three-roll milling. Compos Part B-Eng2020; 198: 108232.
49.
CarosioFAlongiJ. Influence of layer by layer coatings containing octapropylammonium polyhedral oligomeric silsesquioxane and ammonium polyphosphate on the thermal stability and flammability of acrylic fabrics. J Anal Appl Pyrol2016; 119: 114–123.
