Journal Pre-proof

Recent Advances and Future Perspectives for Graphene Oxide

Reinforced Epoxy Resins

Weixin Hou, Ya Gao, John Wang, Daniel John Blackwood, Serena

Teo

PII: S2352-4928(19)31693-9
DOI: https://doi.org/10.1016/j.mtcomm.2019.100883
Reference: MTCOMM 100883

To appear in: Materials Today Communications

Received Date: 15 November 2019

Accepted Date: 28 December 2019

Please cite this article as: Hou W, Gao Y, Wang J, Blackwood DJ, Teo S, Recent Advances
and Future Perspectives for Graphene Oxide Reinforced Epoxy Resins, Materials Today
Communications (2020), doi: https://doi.org/10.1016/j.mtcomm.2019.100883

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 Recent Advances and Future Perspectives for Graphene Oxide

Reinforced Epoxy Resins

Weixin Hou,1 Ya Gao,1 John Wang,1* Daniel John Blackwood,1* Serena Teo2

1. Materials Science & Engineering, Faculty of Engineering, National University of

Singapore

2. St John's Island National Marine Laboratory, Tropical Marine Science Institute (TMSI),

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National University of Singapore

* To whom correspondence: Prof John Wang, Email: msewangj@nus.edu.sg

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Associate Prof Daniel John Blackwood, Email: msedjb@nus.edu.sg
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Abstract: Compared to graphene, graphene oxides (GO) have also been applied in many areas

due to their unique structures and properties, such as tunable and functionalized surfaces, great

processing and competition for scalable production. In this review, GO reinforced epoxy resins

are systematically looked into, where they can be classified into two broad groups: epoxy/GO

nanocomposites and epoxy/GO coatings, depending on the application types. In the epoxy/GO

nanocomposites, the GO reinforcement on the different properties of epoxy matrices are

described in details, like mechanical, toughness, thermal conductivity and so on. As for the

epoxy/GO coatings, the GO effect on the anti-corrosion properties is one of the main concerns.

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For both of them, GO modification methods and dispersing routes in the respective epoxy

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matrices are among the most important considerations. There are some remaining unsolved

issues, which will be highlighted together with the future perspectives of the GO reinforced

epoxy resins.
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Keywords: Graphene oxide, Epoxy, Nanocomposites; Coating and painting
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1. Introduction:

Since the discovery of epoxy in 1936 by Dr Castan of Switzerland and Dr Greenlee of USA

[1], thermosetting resins have been widely used for aerospace [2-3], automotives [4-5],

coatings [6-7], construction structures [8-9], electronic materials [10-11], biomedical devices

[12-13] and adhesives, [14-15] due to their excellent properties, such as outstanding

mechanical properties [16], high adhesion strength [17], superior heat [18] and electrical

resistance [19], impressive thermal stability [20] and solvent resistance [21]. On the other hand,

the epoxy resins are rigid and brittle, because of their crosslink structures, leading to poor

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resistance to crack initiation and growth, which have been limiting their applications in some

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other areas, such as structural materials and high loading applications [8]. Many attempts have

been made to improve their physical and mechanical properties, using various toughening or
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strengthening agents. Moreover, fillers are also introduced into epoxy for improving specific
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properties designed for targeted applications. Inorganic particles/nanoparticles are among the

major fillers, which have been used to reinforce epoxy resins, like silica [22-23], clay [24-25],
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carbon fibre [26-27], carbon nanotube [28-29], graphene [30-31]and so on [32-33].

Graphene is a magical material, which consists of a one-atom-thick planar sheet comprising

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of carbon atoms in a sp2 hexagonal bonding configuration. Since Geim and Novoselov reported

a single layer graphene prepared by a micro-mechanical stripping method from graphite in

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2004 [34], graphene has gained considerable interest in the large field of material science and

engineering. Compared with other nanomaterials, graphene is unique and special, which is
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known as the strongest material ever measured. It exhibits a high thermal conductivity of 5000

W·m-1·S-1 [35], extremely high surface area of 2630 m2/g [36], high Young’s modulus of

around 1 TPa [37], high electron mobility of 200,000 cm2·V-1·s-1 [38] and an electrical

conductivity of up to 1000 S/cm [39]. All these remarkable properties make graphene become

a rising star in many application areas.

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 As a major derivative of graphene, graphene oxide (GO) is obtained from the chemical

treatment of graphite through oxidation, which is generally produced by the treatment of

graphite using strong mineral acids and oxidizing agents, typically via the Hummers method

[40], Staudenmaier [41] or Brodie methods [42], or some variations of these methods [43-44].

Due to the yield limit of graphene, GO shows great potential as a cost-effective and large-scale

precursor for the production of graphene-based materials [45]. Compared to graphene, the

oxygen groups on the GO can cause various defects in the structure, which can limit the

applications in electrically active materials and devices; on the other hand, these functional

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groups including hydroxyl, epoxy and carboxy, et al, will provide potential advantages for

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using GO, such as excellent dispersibility in many solvents [46] and easy modification with

different functional groups [47]. Furthermore, GO can be applied in many areas. For example,
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GO can be used for the fabrication of field‐effect transistors even without reduction [48]; GO

and GO based materials have an exceptional importance in current sensors science [49]; GO
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based membranes can used for gas separation [50], water purification and desalination [51];
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GO can be also used in catalysis [52] and biomedical applications [53]. In this paper, the recent

progress of GO reinforced epoxy is reviewed with two major application areas: epoxy/GO
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nanocomposites and epoxy/GO coatings. Based on the two areas, the effects of GO to the

different properties of epoxy, like mechanical, thermal, anti-corrosion and so on are described.
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Processing and dispersing methods of GO to epoxy are critically important for both of them.

There are unsolved problems for both of them, which will be given together with the
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perspectives in the near future.

2. GO reinforced epoxy resins

Surface modification of nanoparticles/nanofillers has been a key issue for polymer

nanocomposites. The purpose of surface modification is to improve their interactions and/or

dispersion in the polymer matrix. As for GO reinforced epoxy resins, surface functionalizations

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of GO and interfacial controls are critically important, in order to develop the designed

interface, performance and properties. Ascribed to the existence of hydroxyl, epoxy and

carboxyl groups on GO, chemicals with amine, epoxy and siloxane functional groups have

often been used to modify GO. Scheme 1 illustrates the main GO modification methods that

have been reported so far.

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Scheme 1: GO functionalizations and their applications

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Amino polymers, silanes, amines, ionic liquids and nanoparticles are among the main types of
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chemicals that have been used for GO functionalisation, where the common reactions involved

include those between amine and epoxy, amine and carboxyl or silanization. Most of these
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chemicals contain two or more reactive groups in their chemical structures, in which one or

more groups will be left (usually amines) after GO modification in order to react with epoxy

matrix. Due to the large surface area and strong π-π interaction, GO can easily aggregate

together especially in the dry state. Therefore, the GO functionalization not only help to

improve the interaction between GO and epoxy resins, but hinder the unwanted aggregation

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between different GO sheets. On the other hand, due to the high viscosity of epoxy and

hydrophilic surface of GO, selected solvents are widely used to assist the dispersion of GO in

epoxy matrix, especially those polar solvents, as shown in Scheme 1. Therefore, besides the

surface functionalization of GO, the type and amount of solvent used for GO dispersion in both

epoxy nanocomposites and epoxy coatings are very important as shown in Table 1, which will

be included in the description of both.

Dispersing methods References

Solvent assisted: Acetone [54-60]

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Solvent assisted: Ethanol [61-62], [71-72]
Mechanical property Solvent assisted: IPA [63]
Solvent assisted: THF [64]

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Phase transfer agent [67]
Epoxy/GO 3D GO network materials [68-69]
nanocomposites
Solvent assisted: THF [74]
Fracture toughness -p
Directly disperse in curing agent [75-77]
Solvent assisted: Ethanol [78]
Solvent assisted: Ethanol [82]
Thermal conductivity Solvent assisted: Acetone [84-85]
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Ball milling [86]
Tribological property Solvent assisted: Water [87]
Shield property Solvent assisted: Acetone [88]
Water borne epoxy Solvent assisted: Water [85-92]
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coatings Solvent assisted: Ethanol [93-96]

Solvent assisted: Acetone [97-98]
Solvent assisted: Ethanol [99-100]
Solvent assisted: THF [101-103]
Epoxy/GO Solvent assisted: DMF [104-106]
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coatings Solvent borne epoxy Solvent assisted: Water [107-112]

coatings Direct mix with epoxy without solvent [113-121]
Dissolved with xylene [122-125]
Dissolved with n-butyl alcohol [126]
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Dissolved with butyl acetate [127]

Dissolved with toluene [128]
Table 1. The dispersing methods of GO in epoxy
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2.1 Epoxy/GO nanocomposites

2.1.1 GO effects to mechanical property of epoxy

Similar to other nanoparticles/nanofillers, GO is widely used for epoxy resins to improve

their mechanical properties. Compared to use of other nanoparticles, the mechanical property

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shows an obvious enhancement at a lower GO content, because of its high aspect ratio. The

main issue for GO reinforced epoxy is the effective dispersion, and the wet transfer method

was widely used for better GO dispersions as shown in Table 1. Many volatile solvents, like

acetone [54-60], ethanol [61-62], Isopropyl alcohol (IPA) [63] and THF [64] were selected for

GO dispersion. Meanwhile, different chemicals, such as amines [49-50], polymers [58], silanes

[60] and particles [58, 65, 66] and others [54, 57, 61, 62] were used for the GO modification to

increase the interaction with the epoxy matrices. For example, Ferreira et al [56] have reported

the effects of amine-modified graphene oxide on the dispersion and micro-hardness of epoxy-

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based nanocomposites, and the GO was modified with hexamethylenediamine (AGO) and

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dispersed in acetone before being added to the epoxy. The results provide evidence that GO

surface modification improves the dispersion and interactions between the modified graphene
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oxide and the selected epoxy resin (Fig 1), where the hardness showed a 33% increase for the

AGO reinforced epoxy nanocomposites. Surnova et al used IPA to transfer GO to epoxy resin
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at different wt% (0.05%, 0.1%, 0.2%, 0.4% and 0.6%), and the results showed that the addition
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of the GO will increase the viscosity of the composition especially at higher concentrations

(0.4% and 0.6%); moreover, a sharp decrease in Tg (from 170˚C to 137˚C) is observed for

Epoxy/GO (0.6%), which can be explained by the fact that GO reduces the crosslink density of
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the epoxy matrix [57].

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Figure 1. Fracture surface micrograph of (a-b) neat epoxy, (c-d) GO/epoxy and (e-f) AGO/epoxy. Ref [56]
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Qi et al [64] have prepared epoxy nanocomposites reinforced by both graphene oxide (GO)
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and hyperbranched polyamide (HBPA) functionalized GO (HBPA-GO). The as-prepared GO

was dispersed in THF before being introduced to epoxy. The HBPA-GO can effectively
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enhance the curing reactions of epoxy matrix, due to the high density of terminal primary amine

groups, resulting in excellent mechanical properties of the epoxy nanocomposites; Moreover,

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the interfacial properties between HBPA-GO and the epoxy matrix can be tuned by varying the

temperature of the HBPA-GO/epoxy reaction as shown in Fig 2.

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Figure. 2. Tensile properties of epoxy composites at the additive amount of 0.5 wt% and different reaction
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temperatures (25°C, 40°C, 60°C and 80°C). Five test samples were measured for each category and the error

bars represent standard deviation. Ref [64]

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At present, wet transfer method is still the most commonly used route for the transfer of GO to

epoxy. However, organic solvents, vigorous mechanical processes and complicated modification of GO
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are usually required, increasing the overall cost and hindering the development and largescale
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applications of epoxy nanocomposites. To solve this problem, Tang et al [67] reported a green, facile,

and efficient method of preparing epoxy/GO nanocomposites. Triglycidyl para-aminophenol (TGPAP)

was used as both the surface modifier and phase transfer agent of GO. GO can be transferred from

simply by manual stirring at the presence of TGPAP, as shown in Fig 3. A higher TGPAP content in

the epoxy resin gives rise to a faster phase transfer rate, more uniform dispersion, and better exfoliation

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of the GO nanosheets, as well as remarkable improvement in the mechanical properties of the resulting

nanocomposites.

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Figure 3. Schematic of phase transfer of GO from water to DGEBA with TGPAP as the phase transfer agent and

photographs of GO dispersion in water and DGEBA (EP0) or DGEBA with different TGPAP contents (i.e.,
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EP10 and EP20) before and after manual stirring for 5 min under ambient conditions. The top aqueous layer

becomes remarkably lighter with increasing TGPAP content in the DGEBA. Ref [67]
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Another way is to make use of three-dimensional (3D) graphene network materials to

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improve the dispersion and orientation of the graphene sheets [68-69]. Ni et al [69] prepared a

3D graphene oxide skeleton (3DGS) by self-assembly and in situ reduction method, in which
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poly(amidoamine) (PAMAM) dendrimer acted as the reductant and cross-linking agent. By

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filling the porous structure of 3DGS with epoxy, a 3DGS/epoxy nanocomposite was resulted,

which showed a significant increase in the tensile and compressive strengths by 120.9% and

148.3%.

Beside as a main filler for the reinforcement of epoxy, GO can be used as a co-filler with

other nanoparticles, especially fibres [70-73]. By the surface modification of GO, the fibres

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can improve their interaction with epoxy. Zhang et al [70] modified the carbon fibre (CF) with

GO, and further grafted with polyhedral oligomeric silsesquioxane (POSS). The presence of

GO linkage and POSS could significantly enhance both the area and wettability of the fibre

surface, leading to an increase in the interfacial strength between the fibres and resin, as shown

Figure 4. Compared with the desized CF composites, the grafted CF nanocomposites fabricated

by compression molding method exhibited 53.05% enhancement in the inter-laminar shear

strength.

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Figure. 4. SEM images of carbon fibers: (a) desized carbon fiber, (b) CF–GO, (c) CF–GO–POSS. Ref [70]

2.1.2 GO effect to fracture toughness of epoxy

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In addition to increase in the mechanical strength of epoxy, GO has also been employed as

an epoxy toughener in recent years [74-78]. Due to the crosslink structure, epoxy exhibits high
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rigidity and strength, which also make epoxy intrinsically brittle and vulnerable to cracks.

Unlike common tougheners, like liquid rubber [79] and thermoplastic polymers [80], which
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require high content by sacrificing other properties, GO can realise the toughing effect at a low

content while keeping the epoxy strength. There are two main mechanisms for toughening of
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epoxy by graphene/GO related materials as suggested by S. Chandrasekaran et al [81]. One of

the mechanisms includes crack pinning and the other involves crack deflection. Sahu et al [78]

have investigated the mechanical and thermal properties of epoxy nanocomposites by using

poly (allyl amine) (PAA) grafted graphene oxide (GO) as a toughening agent. The modified

GO was dispersed in ethanol before adding to the epoxy. The GO-g-PAA modified epoxy

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nanocomposites showed excellent improvement in the flexural, compression and fracture

properties compared to neat epoxy and GO modified epoxy, and fracture toughness increased

from 0.94 MPa m-1/2 for neat epoxy to 1.75 MPa m-1/2 (87%) for epoxy nanocomposites

modified with 0.7 wt% of GO-g-PAA nanosheets, as shown in Figure 5.

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Figure 5. (a) Typical load vs. displacement curves of fracture toughness test and (b) KIC as a function of GO

and GO-g-PAA content of epoxy nanocomposites. Ref [78]

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GO has also been used as a co-filler with other materials, where GO can strength while
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another one can toughen the epoxies. For example, Xu et al [74] reinforced the epoxy with both

graphene oxide and sulfonated polystyrene-block-poly(ethylene-co-butylene)-block-

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polystyrene (SSEBS). In order to disperse GO and dissolve epoxy and SSEBS, THF was used

as the main solvent. The as-prepared epoxy nanocomposites showed a dramatic increase in the
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fracture energy (GIC) by almost 200% and the uniaxial tensile strength by nearly 50%, as

shown in Figure 6. The SSEBS in the nanocomposites servicing as a bridge between epoxy
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matrix and GO, improves the dispersion of GO in epoxy matrix and enhances their interaction.

The presence of GO sheets and SSEBS block ionomer simultaneously and significantly

increases the tensile strength and fracture energy of epoxy resin.

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 Figure. 6 (a) Tensile stress-strain curves of epoxy resin composites; (b) The critical stress intensity factor

(fracture toughness) KIC and critical strain energy release rate (fracture energy) GIC versus graphene oxide

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content of epoxy/SSEBS composites. Ref [74]

2.1.3 GO effect to thermal conductivity of epoxy

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Epoxy resins are widely used as adhesives in various electronic products [10], whereas the
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heat dissipation affects the service life of the products and user experience. Therefore, the

thermal conductivity of epoxy is also an interesting topic for the nanocomposites research [84-
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86]. Zhang et al [84] prepared polyhedral oligomeric silsesquioxanegraphene oxide (POSS-
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GO), by using 1,6-Hexanediamine (HDM) as a bridge. The POSS-GO was dispersed in ethanol

before adding to the epoxy. The introduction of HDM-POSS molecular chains can not only

improve the dispersion of GO in epoxy, but also as the “stent” prevent the accumulation of GO.
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Figure 7 shows that, at the incorporation of GO and POSS-GO at 1%, the thermal conductivity

of the nanocomposite was improved by 26.32 and 63.16%, respectively, as compared with neat
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epoxy.
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 Figure 7. Thermal conductivity of GO/EP and POSS-GO/EP composites. Each sample was tested three times

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at 25, 50, and 75˚C, respectively. Ref [84]

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Besides the solvent-assisted dispersing method, the GO can also be dispersed in epoxy by

mechanical mixing methods [83, 86]; however, the desired thermal conductivity can be
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obtained at higher GO content, which may well be due to the GO aggregation. For example,

Huang et al [86] have reported an epoxy-based nanocomposite with increased thermal

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conductivity by using graphene oxide-encapsulated boron nitride (h-BN@GO) hybrids as
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fillers. The h-BN@GO was mixed with epoxy by a sealed ball-milling tank. The thermal

conductivity of the obtained nanocomposites showed a maximum value of 2.23 W·m-1·K-1

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when the loading was controlled at 40 wt%, which doubled that of the composites filled with

h-BN, as shown in Figure 8. This increase is attributed to the presence of GO, which improved
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the compatibility of h-BN with epoxy resin, along with the reduced interfacial thermal

resistance between h-BN and epoxy resin.

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 Figure 8. Thermal conductivity of (a) GO/epoxy composites and (b) h-BN@GO/epoxy and h-BN/epoxy

composites with different mass fractions. Ref [86]

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2.1.4 GO effect to other properties of epoxy

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Besides above-mentioned properties, GO was also reported to reinforce epoxy for some

other applications. For example, tribological phenomenon is the most common behaviour in
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modern life., which will cost additional energy, broken the component parts and reduce the
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lifetime of instruments. Therefore, by modifying the surface of components to reduce friction

and increasing wear resistance is important in improving fuel economy, reducing CO2
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emissions and meeting those tough legislative targets. GO can be used to reduce the friction

and wear of epoxy by the modification of ionic liquid (IL) [87], and the modified GO showed
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significantly improved dispersibility in epoxy matrix by a two-phase extraction route with

water. It has been discovered that the addition of GO-IL significantly reduced the friction and
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wear of EP in a wide range of lubrication regimes, as shown in Figure 9, which was due to the

formation of a nanostructured tribofilm comprising GO-IL nanosheets and other tribological

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products.

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Figure 9. (a) Friction coefficient tendencies as functions of sliding time and speed; (b) Stribeck curves

depicted based on average friction coefficients at various stages; (c) specific wear rates and (d, e) mean friction

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coefficients and wear rates of EP, GO-EP and GO-IL-EP obtained from sliding for 3 h at constant speeds of 0.2

and 0.05 m/s. Applied load: 400 N. (A colour version of this figure can be viewed online). Ref [87]
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Moreover, combined with certain functional particles, GO can also improve some special
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properties for epoxy [88-89]. For example, Hashemi et al [88] prepared lead oxide-decorated

graphene oxide. The as-prepared GO-Pb3O4 particle was dispersed in acetone before being
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mixed with epoxy, and X-ray attenuation examination revealed that reinforcement of epoxy-

based composites with GO-Pb3O4 led to a significant improvement in the overall attenuation
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rate of X-ray beam; this is because the GO can boost the charge migration and extend photo-

generated charges lifetime, which increases the optoelectrical activity of Pb3O4-decorated GO

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nanoparticles leading to increase in the atomic weight the X-ray attenuation rate.
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2.2 Epoxy/GO coatings

Metals such as iron, aluminium, copper and magnesium and their alloys are widely used in

different areas, including buildings, vehicles, marine, pipes, and home appliances etc However,

corrosion can occur when metals are exposed to the environment along with reactions to water,

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acids, salts, and other chemicals, which is always the major reason of energy and material loss.

Due to the crosslink structures, high adhesion and excellent chemical resistance, epoxy resins

are widely applied as anti-corrosive coatings. With the large surface area and different tunable

functional groups, GO can effectively block the penetration of corrosion species and be easy

to be modified; therefore, it has been employed as an effective filler to improve the anti-

corrosion properties of epoxy in recent years. Furthermore, comparing with epoxy/GO

nanocomposites, the solvent used for epoxy/GO coatings also included some low-polar

solvents (Table 1), which are commonly used in painting industry.

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2.2.1 GO reinforced waterborne epoxy coatings

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Waterborne epoxy resins have been steadily replacing solvent-borne epoxy resins in coating

formulations due to their environmental considerations. However, the residual hydrophilic

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groups or surfactants in the epoxy after curing could decrease the water-resistance of the
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coatings, as well as the corrosion protection properties [90]. Therefore, inorganic fillers, like

GO, was used to reinforce the anti-corrosion property. Water exhibited high solubility and
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dispersibility to the waterborne epoxy and GO, which was selected by most researchers as a

solvent to disperse GO in the waterborne epoxy. Moreover, different chemicals, including ionic
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liquids [91], silica [92], lysine [93], oligoanilines [94-95] and polyaniline [96] et al [97-98],

were employed to modify GO, in order to improve the interactions with epoxy, or decrease the
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agglomeration of GO sheets in the epoxy system. Liu et al [91] synthesized an ionic liquid–

graphene oxide hybrid nanomaterial via a grafting reaction between an imidazole ionic liquid
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(IL) and the graphene oxide. The electrochemical impedance spectroscopy revealed that ionic

liquid–graphene oxide hybrids effectively improved the anticorrosion performance of epoxy-

based waterborne coatings, as shown in Figure 10, which is due to the ionic liquid facilitated

the dispersion of graphene in a polymer matrix and endowed the graphene sheets with a

corrosion inhibition effect. Figure 11 showed the IL-GO0.5%/epoxy coating obtained the

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highest adhesion strength (3.55 MPa) as compared to the pure (2.21 MPa) and rGO0.5% (2.82

MPa) epoxy coatings, which is due to the well-dispersed IL-GO reduced void spacing in the

coating matrix and enhanced the coating density.

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Figure 10. Images of the salt spray-
tested steel substratescovered with (a)
pure epoxy, (b) rGO0.5% and (c) IL-
GO0.5% coatings. Ref [91]
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specimens obtained from the pull-off
test. Ref [91]
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Besides water, ethanol has also been employed as a solvent to disperse GO in water borne
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epoxy, which was mainly used for polymer modified GO [99-100], or some comparative

experiments between different materials [101-102]. For example, Cui et al [99] prepared
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polydopamine coated graphene oxide by the π-π interactions between the GO and self-

polymerized polydopamine (PDA) as well as the covalent bonding between DA and GO, and
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the GO-PDA nanosheets showed well dispersion in the ethanol and superior compatibility with

waterborne epoxy matrix, which leads to a remarkable improvement in the corrosion protection
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performance of the water-borne EP coating, as shown in Figure 12.

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Figure 12. EIS plots of different coating/steel systems under 3.5% NaCl solution at various time intervals, (a)
0.5 h, (b) 20 days and (c) 40 days. Scatters are experimental data and black lines are fitting results. Ref [99]
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2.2.2 GO reinforced solvent borne epoxy coatings

Although the water borne epoxy system is a trend for coating development, the solvent borne
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epoxy still show their superior anti-corrosion properties for protection applications. GO has
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been widely employed to enhance the anti-corrosion properties of these epoxy systems.

Different polar solvents are normally used to disperse GO before mixing with epoxy, such as

acetone [103-104], ethanol [105-106], THF [107-108], DMF [110-112] and even water by the

wet transfer migration (WTM) process [113-118]. However, unlike with water borne epoxy,

these solvents need to be fully evaporated for avoiding the adverse effect on coating property.

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For example, Pourhashem et al [104] have prepared GO via (3-Aminopropyl)triethoxysilane

(APTES) silane functionalization (A-GO). The as-prepared GO was dispersed in acetone

before adding to epoxy and then evaporated thoroughly before application of coatings. The

results showed that the adhesion strength of samples is measured by pull-off adhesion test and

the results show that the adhesion strength of pure epoxy, epoxy/0.1GO, and epoxy/0.1A-GO

coatings on mild steel substrate is 8.5 ± 0.5, 11 ± 1, and 17.7 ± 0.5 MPa, respectively. The

results show that epoxy/A-GO coatings can provided superior corrosion protection

performance and maximum corrosion resistance is achieved via adding 0.1 wt% A-GO. By

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increasing the loading of A-GO, the barrier properties decrease due to agglomeration of

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nanosheets in polymer matrix as shown in Figure 13.

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Figure 13. Visual performance of samples after 300 h of salt spray test: (a) pure epoxy, (b) epoxy/0.05GO,
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(c) epoxy/0.1GO, (d) epoxy/0.3GO, (e) epoxy/0.5GO, (f) epoxy/0.05A-GO, (g) epoxy/0.1A-GO, (h)

epoxy/0.3A-GO, (i) epoxy/0.5A-GO. Ref [104]

Several researchers have tried to add GO into epoxy without solvent to assist, the GO are

usually modified with different nanoparticles, like SiO2 [119], TiO2 [120], Al2O3 [121], Fe3O4

[122], CaCO3 [123], nanotube [124], montmorillonite [125], hydroxyapatite [126] and so on

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[127], which also can give rose to enhanced anti-corrosion property. The introduction of

appropriate nanoparticles will reduce the GO aggregation so as to improve its dispersion in

epoxy, which helps significantly increase the tortuosity for electrolyte diffusion pathway

(lower diffusion length), facilitating the prevention of the underlying metals from corrosion

attack, as shown in Figure 14 [119].

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Figure 14. Schematic representation of the corrosion inhibition properties of SiO2–GO (1:5)/epoxy. Ref [119]
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For the solvent borne epoxy coatings, several investigations have focused on the solvent free

systems, which means the solvent will be evaporated before coating. However, organic solvents
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are commonly added in the industry products in order to adjust the viscosity for the coating

system. Considering the solubility to the epoxy and evaporation rate, low organic solvents, like
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xylene [128-131], n-butyl alcohol [132], butyl acetate [133], toluene [134] are mostly selected

in the industry products. Due to low polar solvent and the hydrophilicity of GO, the dispersion
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issue in these systems would require additional considerations, and necessary modification is

inevitable in these epoxy coatings.

3. Summary, unsolved issues and outlook

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 GO, with proper surface modification and functional groups, have been used to reinforce

epoxy nanocomposites and epoxy coatings. For epoxy nanocomposites, GO has been largely

used to improve the mechanical properties, including mechanical strength, modulus and

toughness, given its higher aspect ratio, excellent mechanical properties and easy surface

functionalisation. Moreover, GO has been employed to enhance some other properties of epoxy

resins, such as thermal conductivity, by combining with other functional particles/fillers. For

epoxy coatings, GO can improve the anti-corrosion properties, by effectively blocking the

penetration of corrosion species due to its high surface area. At the present, although water-

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based and some low polar solvents are employed in some epoxy coatings, volatile polar

ro
solvents are still widely used in dispersion of GO into epoxy, given the excellent hydrophilicity

of GO.
-p
Although GO reinforced epoxy resins have been investigated for a rather long period of time,
re
there are still some key unsolved issues. The first one is the GO preparation, considerable

variation in structure and effective dispersion into epoxy in large scale. Compared to graphene,
lP

although GO can be prepared at relatively larger scale and low cost, the surface and functional

groups on GO can cause various defects in the nanocomposite and at the interface, and therefore
na

affect the corresponding properties. Therefore, the oxidation level of GO should be considered

and controlled carefully. Although a high degree of oxidation makes GO easier to be modified
ur

and dispersed, the resulting defects on GO surfaces can significantly deteriorate the

reinforcement to epoxy resins [77], and the GO with different oxidation levels is hard to
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purification after fabrication. The second one is the GO modification. Functionalisation of GO

is a common approach to improve the interaction and dispersion of GO in epoxy resins as has

been discussed above. Most of the chemicals used to modify GO are bifunctional: one side is

anchored on GO, while the other side reacts with epoxy matrices. As both functional groups in

the chemicals can react with GO; therefore, one of the problems is that the modification can

22
form different conformations on GO: loop conformation (both ends of the chemicals attached

to the same single GO sheet), bridge conformation (each end of the chemicals react with

different GO sheets) and tail conformation (one end of the chemicals reacts with GO sheet,

while another one unreacted [135]. They are especially so for chemicals with long chains,

which will inevitably affect the interaction at the interface and dispersion of GO in epoxy. The

third problem is the solvent-assisted GO dispersion. As a result of the rising concern for

environment, green chemistry is a general trend for future research and development. At

present, volatile organic compounds (VOCs) are commonly employed to disperse GO into

of
epoxy, which may restrict the industrial applications of GO in future.

ro
GO preparation at low cost is an important consideration, and the degree of oxidation of GO

should be controlled for the epoxy reinforcement. Therefore, a reproducible GO preparation

-p
route would be essential for different reinforcement purposes of epoxy resins. For GO
re
modification, the tail conformation should dominate, as the other two may decrease the

modifying effect and cause GO aggregation. Accordingly, a proper control in the ratio between
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GO and modifier is very important, especially when one functionalizes GO.

So far, GO reinforced water borne epoxy have received considerable attentions. One reason
na

is the low VOC epoxy meeting the requirements of environment concerns; another is the GO

dispersion in epoxy is controllable due to the presence of water. As for solvent borne epoxy
ur

resins, GO pre-treatment may well be necessary in order to decease the usage of organic

solvents, where one example is the freeze-dried GO after modification, which can develop a
Jo

loosely GO powder and can be dispersed easily in non-polar solvents. Furthermore, the freeze-

dried GO can be directly dispersed in liquid curing agent without the assistance of organic

solvent, which would reduce the usage of solvents in both epoxy nanocomposites, coatings and

paints.

23
Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

Acknowledgment:

This study is supported by the research project “Polymer/Graphene/Fibre nanocomposite

Coating for Next Generation Offshore Structure Protection” and funded by the Singapore

Maritime Institute (Project ID: SMI-2016-OF-03).

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