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Composites: Part A 49 (2013) 51–57 Contents lists available at SciVerse ScienceDirect Composites: Part A journal

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Composites: Part A

A journal homepage: www.elsevier.com/locate/compositesa Thermally reduced graphene oxide acting as a trap for

Thermally reduced graphene oxide acting as a trap for multiwall carbon nanotubes in bi-filler epoxy composites

Swetha Chandrasekaran a, , Gabriella Faiella a , L.A.S.A. Prado a , Folke Tölle b , Rolf Mülhaupt b , Karl Schulte a

a Technische Universität Hamburg-Harburg, Institute of Polymers and Composites, Denickestrasse 15, 21073 Hamburg, Germany b Freiburg Materials Research Center (FMF), Freiburg Institute for Advanced Studies (FRIAS) and Institute for Macromolecular Chemistry of the Albert-Ludwigs University Freiburg, Stefan-Meier-Strasse 31, D-79104 Freiburg, Germany

article info

Article history:

Received 19 July 2012 Received in revised form 11 February 2013 Accepted 15 February 2013 Available online 26 February 2013

Keywords:

A.

Polymer matrix composites (PMCs)

B.

Rheological properties

B.

Electrical properties

abstract

The effect of thermally reduced graphene oxide (TRGO) on the electrical percolation threshold of multi wall carbon nanotube (MWCNT)/epoxy cured composites is studied along with their combined rheolog- ical/electrical behavior in their suspension state. In contrast to MWCNT and carbon black (CB) based epoxy composites, there is no prominent percolation threshold for the bi-filler (TRGO–MWCNT/epoxy) composite. Furthermore, the electrical conductivity of the bi-filler composite is two orders of magnitude lower ( 1 10 5 S/m) than the pristine MWCNT/epoxy composites ( 1 10 3 S/m). This result is pri- marily due to the strong interaction between TRGO and MWCNTs. Optical micrographs of the suspension and scanning electron micrographs of the cured composites indicate trapping of MWCNTs onto TRGO sheets. A morphological model describing this interaction is presented. 2013 Elsevier Ltd. All rights reserved.

1. Introduction

Recent advancements in the field of carbon based composites focuses on the two-dimensional form of carbon sheet called graph- ene [1,2]. Graphene, like carbon nanotubes (CNTs) and fullerenes, is an allotropic form of carbon, which is constituted solely by sp 2 -hybridised carbon atoms. Since its first synthesis, the excep- tional properties of graphene (mechanical properties, electrical and thermal conductivity) became very attractive for the develop- ment of novel polymer composites [3,4]. There are several litera- tures on graphene, production methods of graphene or graphene oxide and their usage as a filler material in composites [5]. One such method is a top-down process where functionalized graphene (FG) is prepared by exfoliation of graphite through the formation of graphite oxide (GO) [6,7]. This layered graphite oxide is exfoliated further to get individual sheets through ultra-sonication in a sol- vent to yield graphene oxide. Graphite oxide which is an insulator by nature due to the oxygen functionalities, can be reduced either thermally or chemically to form an electrically conductive FG [8]. Among the different reduction methods, thermal reduction of GO results in a FG-material called thermally reduced graphite oxide (TRGO). This thermal procedure does not need toxic reducing agents like hydrazine and yields a fine graphene powder that can be used without further purification. Most of the graphene nano- sheets used in the composites are prepared by the reduction of

Corresponding author. Tel./fax: +49 (0) 40 42878 4504. E-mail address: Swetha.chandrasekaran@tuhh.de (S. Chandrasekaran).

1359-835X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.

GO [9,10]. At present, a chemical procedure for the production of graphene is most suited for the large scale production needed for the preparation of composites. One of the potential areas for this new carbon filler is in the field of polymer nanocomposites, where nanoparticles are incorporated in a polymeric matrix. Dispersion of nanofillers in the polymer ma- trix is a main factor which determines the final properties of the nanocomposites. For example, in CNT/polymer composite, the effectiveness of the filler in terms of strength is achieved only by well dispersed CNTs by preventing slippage of CNTs and their agglomeration [11]. On the other hand, for electrical properties, CNT re-agglomeration during the curing process aids in achieving lower percolation in the composite [12]. When compared with car- bon nanotubes, graphene and FG sheets have less entanglement and large specific surface area making them an ideal candidate for mechanical reinforcement in the matrix. The remnant function- alities in the FG result in better dispersion of this filler in the ma- trix and thereby improve the strength of the nanocomposite [13]. Ramanathan et al. showed 30% increase in T g and in storage mod- ulus for PMMA based composite [14]. The addition of TRGO to polymer matrices (high density polyethelene) provides composites with lower electrical conductivity [15]. Incorporation of 0.125 wt.% of TRGO in epoxy seems to increase the fracture toughness of the epoxy by 115% and also improves the fatigue performance [16,17]. Epoxy based nanocomposites with commercially available graphene nanoplatelets (GNP) are no exception in terms of mechanical properties. Higher filler loadings of 6 wt.% of GNP the modulus increases by 24% [18].

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The need for multi-functional polymer composite led to com- bine several nanoparticles of different geometry, in order to achieve synergetic effects in so-called multi-filler composites [19,20]. Graphene and FG are also utilized in multi-filler based composites and its combination with CNT or carbon black (CB) showed synergy in terms of tensile strength, thermal conductivity and also on super-capacitance [21,22]. The development of multi- filler polymer nano-composites is an effective procedure for the preparation of materials with improved mechanical and thermal properties [23,24]. On the other hand, the filler–filler interactions play also a key role on the final properties of the composite. It was seen that there is a reduction in the CNTs effective aspect ratio due to the formation inter-connects between the tubes which leads to decreasing mechanical properties at higher filler loadings [25]. Partial replacement of mono-dimensional filler like carbon nano- tubes (MWCNT) by carbon black (CB) spherical nanoparticles en- abled the production of highly conducting epoxy/MWCNT/CB. It was proposed by the authors that the CB shortcuts some parts of MWCNT network and thereby increases the electrical conductivity with lower loadings of MWCNT. A conductivity of 5 10 4 S/m at 0.2 wt.% with 50 phr of CB and 50 phr of MWCNT nano-composites was observed at very low CNT concentration [26]. In this study, we describe the properties of a bi-filler epoxy based composite containing nanotubes and thermally reduced graphene oxide, starting from the rheological behavior of the sus- pension until the electrical properties of the cured composites. The results provided by combined rheological/electrical measurements together with the investigation of the percolation behavior of the cured composites, gave a wide range of information on the MWCNT–TRGO interactions and on their effect on the final electri- cal properties.

2. Experimental

2.1. Preparation of nanocomposite

In this study, two different nano-filler suspensions namely TRGO/epoxy and MWCNT/epoxy suspensions were prepared using the three-roll-milling technique. All the composites were produced using diglycidyl ether of bisphenol A epoxy resin (Araldite LY 556) as matrix, cured using an anhydride (Aradur CH917) and an imid- azole accelerator (DY070) (100:90:1 phr) all supplied by Hunts- man. The fillers used were multi walled carbon nanotubes (NC 7000, supplied by Nanocyl S.A.) and thermally reduced graphene oxide (TRGO) from Freiburg University [27]. The TRGO used in this method is prepared from graphite via GO synthesized by Hum- mer’s method [28]. The GO was reduced in a tube furnace at 750 C in a nitrogen atmosphere. The lateral dimensions of the TRGO sheets vary from 1.4 to 4.6 l m with a specific surface area of 413 m 2 /g and have some 12 wt.% of oxide content (elemental analysis). Raman spectra, thermo-gravimetric analysis (TGA) and elemental analysis for the fillers used are provided in Supporting information (Figs. S1 and S2). Composite suspensions were pro- duced using three-roll-mill (EXAKT 120E). Appropriate amounts of nanofiller and epoxy were mixed inside the glove box and were milled using the EXAKT three-roll-mill by varying the distance be- tween the rolls. To this suspension 90 parts of hardener and 1 part of accelerator were added and mixed manually for 10 min. The mixture was then degassed under vacuum at 50 C to remove air bubbles. The final mixture was poured into the curing mold and cured in the oven for 80 C for 4 h and 140 C for 8 h [23]. The weight percentage of TRGO in TRGO/epoxy suspension was fixed to 0.02 wt%, as this suspension was below its electrical percolation threshold. A master batch of 0.1 wt% of MWCNT/epoxy was pre- pared by 3-roll-mill and diluted using epoxy to 0.01 wt%,

0.02 wt%, 0.05 wt%, and 0.07 wt% respectively. To this diluted sus- pension 50 phr of 0.02 wt% of TRGO/epoxy suspension was added and then the bi-filler suspension was milled again using the same condition. A higher concentration of 0.57 wt% MWCNT/epoxy and 0.57 wt% TRGO/epoxy was also prepared and mixed using the three-roll-mill in 1:1 ratio to measure the electrical conductivity. The study at such a concentration of TRGO (0.57 wt%) well above the electrical percolation threshold will give more insight on the electrical conductivity by addition of TRGO to MWCNT/epoxy composite.

2.2. Electro-rheological measurements of nanocomposite suspension

Combined rheological and electrical measurements were car- ried out on the freshly prepared suspensions using a modified stress-controlled rheometer (StressTech HR, Rheological Instru- ments), in order to evaluate the agglomeration behavior of the bi-filler system under shear. It must be noted that the time be- tween measurement and sample preparation was less than 24 h. This ensured that there were no effects on the agglomeration or sedimentation and in turn on the conductivity from the storage time. Optical, electrical and rheological in situ measurements were possible with this test setup [29]. Shear rate step tests were carried out, by shearing at a constant rate for 10 min and simultaneously measuring the electrical conductivity. The shear rates were chan- ged from 100 s 1 to 0.1 s 1 [30,31]. Measurements were carried out at 60 C for better resolution of the data.

2.3. Electrical conductivity of cured nanocomposite

The second part of the experimental work aimed to study the electrical conductivity of the TRGO–MWCNT/epoxy cured compos- ite, in order to make a comparison with MWCNT/epoxy composites properties. This study will give information about the effect of TRGO on MWCNT/epoxy cured composite due to ‘‘temperature in- duced agglomeration’’ [32]. Therefore, the electrical conductivity of the cured composite for both TRGO–MWCNT/epoxy and the MWCNT/epoxy systems were measured using Hewlett Packard impedance analyzer (HP4284A LCR) using two-point contact. Cir- cular shaped samples of diameter 15 mm and thickness of 2 mm coated with silver paint on both sides were used for this test.

3. Results and discussion

3.1. Combined electrical and rheological measurements of suspension

The electrical conductivity of different weight percentage of MWCNTs in epoxy suspension as function of shear rate is shown in (Fig. 1a and b). The electrical conductivity for both mono-filler (MWCNT/epoxy) suspensions and bi-filler (TRGO–MWCNT/epoxy) suspensions are plotted in the same graph for the ease of comparison. It is visible from the above graph, (Fig. 1a and b) that the elec- trical conductivity increases as the shear rate is decreased for both bi-filler and mono-filler suspensions. At higher shear rates (e.g. 100 s 1 ) the filler particles cannot agglomerate, since the energy input by the shearing is enough to separate the particles from each other. As the shear rate is decreased, the filler particles are ex- pected to build up agglomerates and their contact giving rise to an electrically conductive network. However, the electrical conductivity of the TRGO–MWCNT/epoxy suspensions does not increase at low shear rates unlike mono-filler MWCNT/epoxy suspensions. Unlike MWCNT suspensions, the bi-filler (TRGO–MWCNT/ epoxy) suspensions seem to have a less pronounced tendency to

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et al. / Composites: Part A 49 (2013) 51–57 53 Fig. 1. Electrical conductivity at different

Fig. 1. Electrical conductivity at different shear rates for the MWCNT/epoxy and TRGO–MWCNT/epoxy suspensions (a) at lower concentration of filler and (b) at very high filler concentration respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

form agglomerates under shear. The first agglomerates of MWCNT start to connect already at 0.02 MWCNT wt.%, whereas the first agglomerates form only at 0.07 wt% of MWCNT for bi-filler suspen- sion (0.02 TRGO–0.07 MWCNT wt.%/epoxy). The suspension con- taining 0.02 TRGO–0.05 MWCNT wt.%/epoxy also shows the formation of the conducting agglomerates at 0.1 s 1 shear rate, but these agglomerates are not stable under shear. Only at 0.02 TRGO–0.07 MWCNT wt.%/epoxy, stable agglomerates can be formed at a shear rate of 0.1 s 1 . At this percentage of the nano- tubes (0.07 wt%), the electrical conductivity of the mono-filler epoxy suspension is at least two orders of magnitude higher than the corresponding suspension containing TRGO and MWCNT. A similar trend is also observed at 0.57 TRGO–0.57 MWCNT wt.%/ epoxy suspensions (Fig. 1b) which indicates that the effect of TRGO on MWCNT/epoxy suspension is same irrespective of the filler con- tent. The conductivity decreases by 1 order of magnitude at low shear rates (0.1 s 1 ) and by three orders for higher shear rate (100 s 1 ) in the case of 0.57 TRGO–0.57 MWCNT wt.%/epoxy sus- pension (Fig. 1b). Adding high content of TRGO also seems to re- duce the electrical conductivity of MWCNT/epoxy system. An in situ optical microscopy analysis of the filler structure formed under shearing at lower concentration is shown in (Fig. 2). It is evident from the optical micrographs (Fig. 2) that the size of the agglomerates of MWCNT/epoxy suspension is bigger than that of the TRGO–MWCNT/epoxy suspension. In fact, the suspension at 0.02 MWCNT wt.% forms already connected agglomerates (Fig. 2i) at 0.1 s 1 , the corresponding one containing TRGO does not show any connected network (Fig. 2c), which is in line with the insulat- ing behavior of the suspension all over the range of applied shear rates. A clearly visible agglomerated network can be observed for the 0.05 MWCNT wt.%/epoxy suspension (Fig. 2m and n), while a less connected structure is present in the corresponding suspen- sion containing TRGO (Fig. 2e and f). The shear induced agglomer- ation behavior of the suspension containing only 0.02 TRGO wt.%/ epoxy was investigated as well, and no network formation during shear was appreciated both by electrical measurements and mor- phological observations. Findings are in Supporting information (Figs. S3 and S4). The electrical conductivity measured for bi-filler suspension of 0.02 TRGO–0.07 MWCNT wt.%/epoxy suspension is

mainly due to the presence of MWCNTs at high content, which is sufficient enough to form connected network of agglomerates. The filler agglomeration observed in TRGO–MWCNT/epoxy sus- pension is mostly due to tendency of MWCNTs to form percolated network structure. Graphene oxide flakes confine the MWCNT in finite and restricted regions within the resin, hindering their agglomeration and consequent contact and thereby reducing the electrical conductivity. These first results on the study of the ‘‘shear induced agglomeration behavior’’ of TRGO–MWCNT suspensions show that addition of TRGO lowers the conductivity of MWCNT/ epoxy suspension by hindering the formation of shear induced per- colated network.

3.2. Electrical conductivity of cured nanocomposite

It must be noted that the amount of the filler used in rheological experiments are with respect to LY556 epoxy (i.e., prior to the addition of anhydride and imidazole components), whereas, for the cured composite the weight percentage of the filler is halved due to the addition of hardener and accelerator. For better under- standing, electrical conductivity of pristine TRGO/epoxy cured composite and bi-filler TRGO–MWCNT/epoxy cured composite as a function of weight percentage of the filler are summarized in (Fig. 3a and b). In Fig. 3a the electrical conductivity of TRGO/epoxy composites as a function of weight percentage is shown. Comparing Fig. 3a with b (denoted by circle and line symbol), it can be concluded that TRGO/epoxy composites are less conductive than MWCNT/epoxy composites. When the two fillers are combined, the bi-filler com- posites exhibit neither synergy nor obey the rule of mixtures but instead an opposite of the synergetic effect is observed. Essentially, addition of TRGO decreases the electrical conductivity of MWCNT/ epoxy composite. The same was measured for higher concentra- tion of filler and the electrical conductivity of 0.57 TRGO– 0.57 MWCNT wt.%/epoxy cured composite is 3 10 3 S/m which is one order of magnitude lesser than the mono-filler 0.57 wt% MWCNT/epoxy cured composite (7.8 10 2 S/m). On comparing the conductivity of the bi-filler (TRGO–MWCNT/ epoxy) cured composite to that of MWCNT/epoxy cured composite,

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Chandrasekaran et al. / Composites: Part A 49 (2013) 51–57 Fig. 2. Optical micrographs of 0.02

Fig. 2. Optical micrographs of 0.02 TRGO–0.02 MWCNT wt.%/epoxy (a–c), 0.02 TRGO–0.05 MWCNT wt.%/epoxy (d–f), 0.02 MWCNT wt.%/epoxy (g–i) and 0.05 MWCNT wt.%/ epoxy (l–n).

MWCNT wt.%/epoxy (g–i) and 0.05 MWCNT wt.%/ epoxy (l–n). Fig. 3. (a) Electrical conductivity of TRGO/epoxy

Fig. 3. (a) Electrical conductivity of TRGO/epoxy cured composite at different weight percentage and (b) comparison of the electrical conductivity between bi-filler TRGO– MWCNT/epoxy and pristine MWCNT/epoxy cured composites respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

there seems to be a decrease in the conductivity of the composite due to the addition of TRGO. This decrease in conductivity of the bi-filler cured composite is about two orders of magnitude for low- er concentration of filler content (0.01 TRGO–0.01 MWCNT wt.%/ epoxy) and is about one order of magnitude for higher filler con- tent (0.01 TRGO–0.035 MWCNT wt.%/epoxy). The addition of TRGO affects more the conductivity of MWCNT/epoxy cured composite at lower concentrations of MWCNT. As the filler content increases, agglomeration of the tubes due to high concentration dominates the electrical transport behavior, which does not depend much on the type of filler added, but rather only on an increase of con- ductive fillers coming in contact. When a steep increase in electri- cal conductivity is observed for the cured MWCNT/epoxy composites, a less significant change in the conductivity is found in the TRGO–MWCNT epoxy composites, thus a steep increase in

electrical conductivity cannot be appreciated at any filler concen- tration. Clearly, the minimum optimal amount of MWCNT for per- colation threshold requires not a homogenous dispersion but an adequate dispersion, sufficient enough to form conduction pattern along the matrix. This is possible in MWCNTs in epoxy at even low- er loadings due to the high dispersive surface energy which pro- duces spontaneous re-agglomeration. The same phenomenon is also observed in carbon black filled epoxy systems where the network formation depends on particle– particle interaction which in turn is controlled by the shear forces or ionic interaction of the resin [33]. From these findings it is very clear that TRGO reduces the electrical conductivity of CNT compos- ites by hindering the agglomeration of the carbon nanotubes. This effect seems to be independent whether the agglomeration of MWCNT is by shear (Fig. 1a and b) or by temperature (Fig. 3b).

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3.3. Morphological characterization of the cured composite

To better understand this finding scanning electron micro- graphs of cured composite containing 0.035 MWCNT wt.%/epoxy and 0.01 TRGO–0.035 MWCNT wt.%/epoxy are shown in (Fig. 4). The distribution of the MWCNT agglomerate and dense MWCNT agglomerates can be seen in (Fig. 4a) and the formation of perco- lated conducting network by connecting two MWCNT agglomer- ates are additionally confirmed in (Fig. 4b). When TRGO is added to the MWCNT/epoxy system, the distribution of MWCNT agglom- erates is affected to a great extent. First, the agglomerates are spar- sely distributed and appear to be less dense when compared to mono-filler MWCNT/epoxy composite. The question is where do the rest of the CNTs disappear? (Fig. 4c) shows an agglomerate of TRGO with MWCNT (0.01 TRGO–0.035 MWCNT wt.%/epoxy). A clo- ser examination on this figure shows some MWCNT in the vicinity of the TRGO sheets and the agglomerate of TRGO is more three- dimensional. More micrographs as in (Fig. 4d and e) show the hin- drance of CNT network by a TRGO sheet both parallel and in per- pendicular to the CNT network. This morphology of the TRGO–MWCNT bi-filler composite ex- plains the lower conductivity when compared to mono-filler MWCNT/epoxy composite. The TRGO sheets attract the carbon nanotubes and thereby hinders the formation of percolated con- ductive networks. The MWCNT within or on the TRGO can be entangled within these walls or disentangled. The remaining MWCNTs that are not affected by the presence of TRGO sheets form percolated networks which give rise to an increase of the

electrical conductivity. However, the MWCNTs that are trapped by the TRGO sheets do not contribute to the conductive path; hence a higher amount of tubes is needed to reach appreciable levels of conduction. Scanning electron micrographs of 0.01 TRGO wt.%/epoxy (Fig. S5) given in Supporting information shows the agglomeration of only TRGO sheets in epoxy. From the images, the depth of agglomerates of TRGO sheets is lesser when compared to TRGO–MWCNT agglomerate in epoxy. This may be due to the presence of MWCNT agglomerates in-between the TRGO sheets.

3.4. Proposed theory for reduced conductivity of bi-filler nanocomposite

Based on this a hypothesis a morphological model is proposed to explain the experimental results as shown in the schematic in (Fig. 5). The schematic shows both the cross-sectional view of this TRGO–MWCNT agglomeration and their top view. The SEM of pris- tine TRGO sheets which is provided in Supporting information (Fig. S6) show a much wrinkled surface (top view) which arises from the thermal reduction and exfoliation of the sheets by the re- lease of gases. The cross-sectional view of the TRGO sheets have an accordion like structure and from the image the gap between the sheets are more than 1 l m. This gap is sufficient enough for MWCNT to accommodate themselves in. This morphology was very clearly seen at higher concentration of bi-filler composites

seen at higher concentration of bi-filler composites Fig. 4. Scanning electron micrographs of 500 nm thin

Fig. 4. Scanning electron micrographs of 500 nm thin slices of composite deposited on Si substrate. (a and b) SEM of mono-filler MWCNT/epoxy (0.035 MWCNT wt.%/epoxy) cured composite; (c–e) SEM of bi-filler TRGO–MWCNT/epoxy (0.01 TRGO–0.035 MWCNT wt.%/epoxy) cured composite.

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Chandrasekaran et al. / Composites: Part A 49 (2013) 51–57 Fig. 5. Morphological model for TRGO–MWCNT/epoxy

Fig. 5. Morphological model for TRGO–MWCNT/epoxy cured composite; (a) cross-sectional view and (b) top-view respectively. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

(0.57 TRGO–0.57 MWCNT wt.%/epoxy) when the cryo-fractured surface was investigated for filler distribution. The cryo-fractured surface of high concentration bi-filler com- posite exhibits morphology where the MWCNT agglomerates are trapped by the TRGO sheets/agglomerates (Fig. 6a), also the MWCNTs are in the vicinity of the TRGO sheets. This again is an indication of strong filler–filler interaction through p p interaction between the MWCNTs and TRGO sheets. Another interesting morphological feature observed on the cryo-fractured surface is the pinning/trapping of MWCNTs on/between the TRGO sheets (Fig. 6b). Thus, the wavy topography of the sheets also aids to pin the MWCNT to their surface [34]. Also the TRGO sheets have around 12 wt.% of strong oxygen functionalities which was determined from elemental analysis. Recent literatures are available about GO acting as a dispersing agent for MWCNT [35]. We believe that the oxygen functionalities play a vital role in attracting the MWCNT to their surface. The oxygen functionalities are decorating the edges of the graphene sheets and also form oxide rich regions like nano-islands on the basal plane. These oxide rich nano-islands are hydrophilic in nature and the regions in the graphene basal plane free of oxide groups are hydrophobic in nature as in (Fig. 7). The MWCNT are attracted through p p interaction by those areas in the GO sheets where there are no oxygen groups in the basal plane [36]. Hence the path of electron mobility on

basal plane [36] . Hence the path of electron mobility on Fig. 7. Schematic representation of

Fig. 7. Schematic representation of graphene oxide (GO) sheets showing both hydro-phobic (blue domain) and hydro-philic (red domain). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

the TRGO sheet is already restricted because of oxygen functional- ities on the basal plane; in addition to this the MWCNT are at- tracted by the p conjugated nano-islands. All these effects make the whole aggregate an insulator; it acts as a barrier for electron transport [35]. Adding to this, the specific surface area of the sheets is 413 m 2 /g which is greater than or equal to that of MWCNT and hence the influence of van der Waals force exerted by the sheets on MWCNTs are much higher. The attraction of carbon particles

MWCNTs are much higher. The attraction of carbon particles Fig. 6. Scanning electron micrograph of cryo-fractured

Fig. 6. Scanning electron micrograph of cryo-fractured surface of bi-filler 0.57 TRGO–0.57 MWCNT wt.%/epoxy cured composite in in-lens mode: (a) MWCNT agglomerates are surrounded by TRGO agglomerates and (b) MWCNTs pinned onto the TRGO sheets respectively.

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by the TRGO sheets was observed not only with MWCNT but also for carbon black particles (not presented here). The presence of functional groups makes the TRGO partially polar which makes it well dispersed in the matrix and their tendency to agglomerate is low. When mixing with MWCNTs, the sheets act as a barrier reducing the mobility of CNT in the matrix. The p p interaction be- tween the TRGO–MWCNT is not the only contributing factor for the observed behavior, the viscosity of the resin along with the dis- persive shear forces could also contribute to this MWCNT–TRGO interaction.

4. Conclusion

The effect of addition of small amounts of TRGO (0.02 wt%) to the MWCNT/epoxy system was investigated under combined rheologi- cal and electrical measurements. The electrical conductivity of the cured composites was also measured, which includes influence of temperature on the agglomeration. The experimental results show that the addition of TRGO reduces the electrical conductivity of MWCNT/epoxy composites by two orders of magnitude. Based on the structural characterization, a morphological model for this bi- filler system is proposed. It can be seen that TRGO sheets hinders the agglomerate formation by trapping the MWCNTs between them.

Author contributions

The

manuscript

was

written

through

contributions

of

all

authors. All authors have given approval to the final version of

the manuscript.

Acknowledgements

The authors would like to acknowledge Adan Hernandéz and Jana Schlutter for their support in sample production and charac- terization. We would like to acknowledge DAAD-SIEMENS A/10/ 71620, German Federation of Materials Science and Engineering (BV MatWerk) and German Research Foundation (DFG) for their financial support.

Appendix A. Supplementary material

The Supporting information consists of the electrical conductiv- ity of pristine 0.02 TRGO wt.%/epoxy suspensions which can be used for comparison with the bi-filler TRGO–MWCNT/epoxy sys- tem. Optical micrographs of the suspension (0.02 TRGO wt.%/ epoxy) at different shear rates are also provided. Scanning electron micrographs of pristine TRGO sheets both top and cross-sectional view is available which helps to visualize better the proposed mor- phological model. Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/

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