Nature inspired hierarchical structures in nano-cellular epoxy/graphene-Fe3O4 nanocomposites with ultra-efficient EMI and robust mechanical strength

doi:10.1016/j.jmst.2021.06.030

Abstract

Abstract:

Hierarchical layered structures, whether in a compact form like nacre or a porous manner like bone, are well known for their combined features of high stiffness, strength, and lightweight, inspiring many man-made materials and structures for high performance applications. The use of nacre/bone like hierarchical structures in polymer nanocomposites can achieve excellent mechanical and functional properties with high filler volume fractions after carefully aligning functional nanofillers, although the fabrication and processing remain a great challenge. In this work, a bio-inspired lightweight nano-cellular epoxy/graphene-Fe₃O₄ nanocomposite with high nanofiller loading of 75 wt.% was successfully fabricated by combining features from both nacre and bone structures, via a simple compression molding process together with an eco-friendly supercritical CO₂ foaming process to achieve robust mechanical strength and excellent electromagnetic interference (EMI) shielding effectiveness (SE) simultaneously. Highly aligned graphene-Fe₃O₄ nanoplatelets with well controlled nanoscale porous structures (52.6 nm) enabled both low density (1.26 g/cm³) and high specific EMI SE >5200 dB/cm²/g, as well as preserved tensile strength of 67 MPa. This study provides a sustainable route to fabricate nature mimicked structures with high performance and high flexibility for a wide range of applications, from portable electronics to healthcare devices.

Key words: Epoxy foam, Layered nano-cellular structures, Graphene-Fe₃O₄ nanocomposites, Electromagnetic interference shielding

Xun Fan, Fengchao Wang, Qiang Gao, Yu Zhang, Fei Huang, Ronglin Xiao, Jianbin Qin, Han Zhang, Xuetao Shi, Guangcheng Zhang. Nature inspired hierarchical structures in nano-cellular epoxy/graphene-Fe₃O₄ nanocomposites with ultra-efficient EMI and robust mechanical strength[J]. J. Mater. Sci. Technol., 2022, 103: 177-185.

Figures/Tables 5

Fig. 1. Reduced graphene oxide-Fe3O4 (rGO-Fe3O4) hybrid nanoparticle: (A) schematic of fabrication process of rGO-Fe3O4 aerogel (graphene oxide (GO) suspension concentration: 5.0 mg/ml, GO:Fe3O4=1: 1.3, stirring speed: 2000 r/min and GO:N2H4=1:1); (B) magnetic rGO-Fe3O4 aerogel digital photograph and SEM images with different magnifications; (C) SEM image of rGO-Fe3O4 nanoparticle (c-1) and the corresponding element mapping images of C (red, c-2), O (cyan, c-3) and Fe (yellow, c-4) elements; TEM images of (D) GO, (E) rGO, (F) Fe3O4 and (G) rGO-Fe3O4 nanoparticles.

Fig. 2. Fabrication process and nacre-like morphologies of bio-inspired m-EP/rGO and m-EP/rGO-Fe3O4 nanocomposites: (A) (a-1) natural nacre shell with hierarchical microstructure [40], and (a-2) schematic illustrations of layered nanocomposite film fabricated by compression molding; (B) digital photographs of (b-1) m-EP/rGO-Fe3O4 film with length of 75 mm and thickness of 100 μm, (b-2) good magnetic property, (b-3 and 4) flexible layered microstructure examined by SEM; TEM images demonstrating the dispersion of (C) 4.76 wt.% rGO in m-EP/rGO film and (E) 13.04 wt.% rGO-Fe3O4 in m-EP/rGO-Fe3O4 film; SEM images of cross-sectional fractures of nanocomposite films with (D) 50.00 wt.% rGO and (F) 75.00 wt.% rGO-Fe3O4.

Fig. 3. Foamability of neat epoxy and epoxy modified with hyperbranched epoxy (E102) and organic precursor (KM) : (A) (a-1) SEM and (a-2) TEM images of cured neat epoxy, (a-3) cross-sectional fracture of neat epoxy after foaming; (B) nanoindentation measurement: (b-1) load-displacement curves, (b-2) the corresponding elasticity modulus and (b-3) hardness values of specimens of various epoxy-based matrices (weight ratios of epoxy, E102 and KM are: 100:0:0, 100:0:5, 100:30:0, 100:30:5); (C) (c-1) SEM, (c-2) TEM for modified-epoxy (m-EP) matrix (100: 30: 5) and (c-3) cross-sectional fracture with statistical average cell size of m-EP foam.

Fig. 4. Micro-structures and properties of layered m-EP/rGO and m-EP/rGO-Fe3O4 nanocomposite foams: SEM images of (A) m-EP/rGO foams with (a-1) 9.09 wt.% rGO and (a-2) 50.00 wt.% rGO content, and (B) m-EP/rGO-Fe3O4 foams with (b-1) 23.08 wt.% and (b-2) 75.00 wt.% rGO-Fe3O4 content; (C) average cell size and cell density as a function of rGO (c-1) and rGO-Fe3O4 (c-2) loading; (D) densities of (d-1) m-EP/rGO and (d-2) m-EP/rGO-Fe3O4 nanocomposites and foams as a function of rGO and rGO-Fe3O4 loading (foaming time is 5s); (E) tensile stress-strain curves of m-EP foam under different foaming time, showing optimized mechanical performance based on 5s foaming time; tensile strength and modulus of (F) m-EP/rGO and (G) m-EP/rGO-Fe3O4 films with different filler contents before and after foaming.

Fig. 5. Functional performance of bio-inspired hierarchical m-EP/rGO and m-EP/rGO-Fe3O4 solids and foams: (A) electrical conductivity of m-EP/rGO solids and foams, (A' and A'') total SE (SET) of m-EP/rGO solid and foams; (B) electrical conductivity of m-EP/ rGO-Fe3O4 solids and foams, (B' and B'') SET of m-EP/ rGO-Fe3O4 solid and foams; reflected SE (SER), absorbed SE (SEA), SET and specific SET/thickness (SSET/t) properties of (C) m-EP/rGO and (C') m-EP/rGO-Fe3O4 solids and foams; (D) permittivity and (D') permeability of m-EP/rGO-Fe3O4 foams with different rGO-Fe3O4 contents (23.08 wt.%, 47.37 wt.% and 75.00 wt.%); (E) comparison of EMI performance of the nanocomposite solids and foams with previously reported shielding materials from traditional methods; (F) schematic illustration of the shieling mechanism of current layered nanocomposites with nano-porous structure.

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Nature inspired hierarchical structures in nano-cellular epoxy/graphene-Fe₃O₄ nanocomposites with ultra-efficient EMI and robust mechanical strength

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