3-Phase hierarchical graphene-based epoxy nanocomposite laminates for automotive applications

doi:10.1016/j.jmst.2019.05.033

Abstract

Abstract:

Two different types of graphene flakes were produced following solution processing methods and dispersed using shear mixing in a bifunctional (A) and a multifunctional (B) epoxy resin at a concentration of 0.8 and 0.6 wt%, respectively. The graphene/epoxy resin mixtures were used to impregnate unidirectional carbon fibre tapes. These prepregs were stacked (seven plies) and cured to produce laminates. The interlaminar fracture toughness (mode-I) of the carbon fiber/graphene epoxy laminates with resin B showed over 56% improvement compared with the laminate without graphene. Single lap joints were prepared using the laminates as adherents and polyurethane adhesives (Sika 7666 and Sika 7888). The addition of graphene improved considerably the adhesion strength from 3.3 to 21 MPa (sample prepared with resin A and Sika 7888) highlighting the potential of graphene as a secondary filler in carbon fibre reinforced polymer composites.

Key words: Graphene, Carbon fibre reinforced polymer (CFRP), Fracture toughness, Shear lap joints

Ahmed Elmarakbi, Panagiotis Karagiannidis, Alessandra Ciappa, Franco Innocente, Francesco Galise, Brunetto Martorana, Francesco Bertocchi, Francesco Cristiano, Elvira Villaro ábalos, Julio Gómez. 3-Phase hierarchical graphene-based epoxy nanocomposite laminates for automotive applications[J]. J. Mater. Sci. Technol., 2019, 35(10): 2169-2177.

Figures/Tables 15

Fig. 1. Schematics of (a) double cantilever beam specimen used for interlaminar fracture toughness characterization and (b) geometry and dimensions of the single lap joints.

Fig. 2. SEM images of typical flakes (a) Gr-NAN and (b) Gr-AVA and HR-TEM images showing a typical flake thickness of (c) 14 nm for Gr-NAN and (d) 3-4 nm for Gr-AVA.

Table 1 Characteristic properties of the graphene flakes used.

	Gr-NAN	Gr-AVA
Lateral size (μm)
SEM	15-30	1-2
Thickness
TEM (nm)	14	3-4
XRD (Number of Layers)	32	9
Elemental analysis (C:O)
EDS	44:1	NA
XPS	NA	110:1

Fig. 3. (a) The epoxide group, (b) the chemical structure of Di-Glycidyl Ether of Bisphenol A (DGEBA) and (c) cure reaction mechanism of amine and epoxide [40].

Fig. 4. Viscosity as a function of curing temperature for resin A, sample A-0.8Gr-NAN, resin B and sample B-0.6Gr-NAN.

Table 2 Viscosity at 60 °C, minimum viscosity values and curing rate.

Sample	Viscosity (Pa·s) at 60 °C	Minimum viscosity (Pa·s) / (temperature)	Curing rate (Pa·s/°C)
Resin A	41	0.7 (107 °C)	12
A-0.8Gr-NAN	77	1.1 (105 °C)	15
A-0.8Gr-AVA	50	1.1 (106 °C)	11
Resin B	49	1.1 (114 °C)	10
B-0.6Gr-NAN	68	2 (115 °C)	12.5

Table 3 DSC results obtained for all examined materials.

Sample	Onset (°C)	Peak (°C)	Enthalpy ΔH (J/g)	Cured T_g (°C)
Resin A	128,4	138,6	-350	110
A-0.8Gr-NAN	128,3	139,2	-349	110
A-0.8Gr-AVA	128,6	138,8	-342	110
Resin B	135,6	147,6	-479	186
B-0.6Gr-NAN	135,3	147,5	-494	194

Fig. 5. DMA storage modulus and tanδ versus temperature of (a) Resin A and A-0.8Gr-NAN and (b) Resin B and B-0.6Gr-NAN.

Table 4 Tg values determined by DMA for all examined materials.

Graphene epoxy composites	E’ on set (°C)	tanδ peak (°C)
Resin A	143.2	150.3
A-0.8Gr-NAN	142.8	149.9
A-0.8Gr-AVA	143.6	150.5
Resin B	179.9	204.2
B-0.6Gr-NAN	198.9	217.2

Fig. 6. Representative load-displacement curves of the composite specimens under study and DCB test specimen under mode-I loading (inset).

Table 5 Initial interlaminar fracture toughness, GIC of CF/epoxy/graphene laminates under study.

Samples	G_IC (kJ/m²)	Change (%)
CF-Resin-A	0.36	-
CF-A-0.8Gr-NAN	0.39	+8.3
CF-A-0.8Gr-AVA	0.32	-11.1
CF-Resin-B	0.16	-
CF-B-0.6Gr-NAN	0.25	+56.3

Fig. 7. SEM images of fracture surfaces from GIC tests from sample (a) CF-A-0.8Gr-NAN and (b) CF-A-0.8Gr-AVA and (c) CF-B-0.6Gr-NAN.

Fig. 8. Main chemical reactions which take place during the mixing of component A and component B of Sika 7666 and 7888; production of (a) polyurethane adhesive and (b) urea units.

Fig. 9. Lap shear tests on joints made of (a) neat resins with Sika 7666 and 7888 adhesives and (b) resin A with Sika 7666 and 7888 adhesives with and without graphene.

Table 6 Maximum shear stress for the shear lap joints under study.

Sample	Maximum shear stress (MPa)
CF-Resin A - Sika 7666	3.3
CF-Resin B - Sika 7666	6.4
CF-Resin A - Sika 7888	6
CF-Resin B - Sika 7888	19
CF-Resin A - Sika 7666 + Gr-NAN	6.1
CF-Resin A - Sika 7666 + Gr-AVA	4.2
CF-Resin A - Sika 7888 + Gr-NAN	21

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