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The physical properties of sulfonated graphene / poly(vinyl alcohol) composites Rama K. Layek, Sanjoy Samanta, Arun K. Nandi PII: DOI: Reference: To appear in: Received Date: Accepted Date: S0008-6223(11)00780-9 10.1016/j.carbon.2011.09.039 CARBON 6845 Carbon 10 May 2011 15 September 2011

Please cite this article as: Layek, R.K., Samanta, S., Nandi, A.K., The physical properties of sulfonated graphene / poly(vinyl alcohol) composites, Carbon (2011), doi: 10.1016/j.carbon.2011.09.039

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The physical properties of sulfonated graphene / poly(vinyl alcohol) composites Rama K. Layek, Sanjoy Samanta , Arun K. Nandi* Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India

*Corresponding author: Tel: 913324734971 (extn. 561), Fax: 913324732805, email address: psuakn@mahendra.iacs.res.in (A. K. Nandi).

Abstract: Composites of poly(vinyl alcohol) (PVA) with sulphonated graphene (SG) show fibrillar, dendritic & rod like structures for SG1, SG3 and SG5 samples, respectively, where the number indicates weight percent of SG. Differential scanning calorimetry shows a new peak in addition to that of PVA arising from the supramolecular organization of the components in SG1 and SG3. 17 and 36% increases of PVA crystalline thickness and 77 and 79% increases in amorphous overlayer thickness for SG1 and SG3 over PVA are evident from small angle X-ray scattering results but SG5 does not show any change. Atomic force microscopy results of SG suggest aggregation at higher concentration and the composites exhibit composition dependent mechanical properties with the highest increase of stress (177%), strain at break (45%) and toughness (657%) in SG3 over PVA. Youngs modulus increases with increasing SG concentration with a maximum 180% increase in the SG5 sample. The storage modulus of SG3 shows the highest increase (1005%) over PVA. A ten orders of magnitude increase of dc conductivity over PVA and a 10 fold increase in the dendritic SG3 to that of other composites are observed. SG1 is semiconducting, SG3 shows an electronic memory and SG5 exhibits a rectification property.

1. Introduction: Graphene/polymer composites are interesting materials for their good electrical and mechanical properties. A major difficulty arises during its preparation because of scarcity of a soluble / dispersible graphene in a common solvent with the polymer. Graphene oxide (GO) provides important routes for its modification [1-13] e.g. (i) amidation of -COOH group [14, 15] (ii) nucleophilic substitution of epoxy group [16] (iii) diazonium salt coupling, [17,18] (iv) polymer grafting via atom transfer radical polymerization (ATRP) [9,10,19] etc. A particular type of modification has its own advantages for making the composites as interfacial interaction between the graphene and polymer varies yielding composites of different properties. The interfacial interaction can also be tuned with the composition of the hybrid. So far GO is mostly used to make the polymer composites and in GO/ poly(vinyl alcohol)(PVA) composite the tensile strength has increased by 35% for 3 wt% GO [20]. Also it has increased by 76% with a 60% decrease of strain at break for 0.7 wt % filler [21]. In a PVA / reduced graphene oxide (RGO) composite a 200% increase of tensile strength with a 75% decrease of elongation at break is reported at 3 vol% graphene concentration [22]. In an electrochemically modified graphene (ECG) / PVA composite the tensile strength has increased by 50% with only 4% increase of elongation at break for the 7 wt % filler but above it the elongation at break decreases [23]. Thus in the graphene/PVA composites an increase in tensile strength is mostly accompanied by a decrease in strain at break, so it would be of great importance if both the above properties can be enhanced simultaneously.

Also in the most graphene / PVA composites conductivity is not reported and only in ECG / PVA composite the reported conductivity is 10-7 S/cm for 6 wt% graphene [23]. This value is rather low compared to the graphene/ polystyrene composite (0.15 S/cm for 1.2wt% graphene) [24]; graphene/ polycarbonate composites (0.5 S/cm for 2.2vol % graphene) [25] and RGO / poly (vinylidene fluoride) (PVDF) composites (10-4 S/cm for 4 wt% RGO) [26]. Here we are interested to increase both the conductivity and mechanical properties of PVA, significantly. For this purpose RGO is obviously a good choice, but it has the difficulty of dispersion in aqueous medium required to mixing with PVA. In order to alleviate the problem the anchoring -SO 3H group on the graphene surface followed by reduction (with hydrazine) may be a promising method to yield a highly conducting and dispersible graphene in aqueous medium [18]. The anchored SO3H group in the sulphonated graphene (SG) is a stronger H-bonding group compared to -COOH / -OH groups present in RGO and it may strongly supramolecularly interact with PVA through H-bond formation with the OH group of PVA. The strong and directional nature of Hbonding interaction may yield new supramolecular structure of the composite. Recently, oriented structure of GO is reported at a high GO concentration in the GO/PVA composite showing significant mechanical property enhancement in the plane of alignment [27]. Actually at lower GO concentration anisotropic oriented structures are not produced but here we can expect an oriented structure even at the low filler concentration due to the anchoring of a strongly interacting SO3H group on the graphene surface. Sulphonation is performed by oxidizing graphite with HNO3 and then reacting with sulphanilic diazonium salt [18]. PVA is then blended with 1, 3 and 5 wt % of SG by

solvent casting method to observe a variation in physical properties. PVA is a biocompatible polymer and it is used in tissue engineering, drug delivery and in other biotechnological devices [28, 29]. So any enhancement in mechanical and electronic properties of PVA with SG would be helpful for fabricating new biotechnological devices. Here we report that both stress (177%) and strain at break (45%) increase till the addition of 3% SG concentration contributing to a 235% increase of toughness but above 3% SG the stress increases with a decrease of strain at break. A new type of morphology (dendritic) is observed at 3% (w/w) SG concentration and 10 orders hike in the magnitude of dc conductivity over PVA is achieved in these new composites. Probable explanation from the supramolecular organization of SG / PVA complex and its variation with composition are discussed.

2. Experimental: 2.1 Materials. Graphite, sodium borohydride, sulfanilic acid (Aldrich, USA) and sodium nitrate, potassium permanganate, 35 % hydrocholoric acid, hydrazine hydrate solution (99%, synthetic grade), (Merck, Mumbai) are used as received. PVA (Aldrich, USA; 99+% hydrolyzed ) has M v = 130,000 which is measured from the intrinsic viscosity in water at 30 oC (Mark- Houwink constants, K=42.8 X10 -5 dl/g & = 0.64) . The PVA is used as received and water is doubly distilled before use. 2.2 Modification of graphene: At first, the starting material graphite oxide(GO) is prepared from graphite powder by oxidizing with KMnO4 / NaNO3 mixture in concentrated H2SO4 using Hummers method [30]. Then, 75 mg GO is dispersed in 75ml water (0.1% w/v) and is sonicated for 1 h in

an ultrasonic bath (60W, frequency 28KHz, Model AVIOC, Eyela). A clear brownish dispersion of GO is formed indicating the exfoliation of GO in the medium. The process of synthesizing SG from GO consists of three steps : (a) pre-reduction of GO with sodium borohydride; (b) sulfonation with the aryl diazonium salt of sulfanilic acid; and (c) post-reduction with hydrazine to remove epoxy (>O) functionality completely (Fig.1). The pre-reduction of GO is essential: (i) to enable the sulphonation reaction by increasing the domain size of sp2 carbon for reaction with aryl diazonium salt and (ii) it also helps to achieve complete reduction during hydrazine treatment after sulphonation. The later reduction is necessary to get more sp2 carbon atoms in the graphene and hence to get extended conjugation in the graphene [18]. The pH of GO dispersion is adjusted between pH 9-10 with the addition of 5% (w/v) sodium carbonate solution. Then 15 ml sodium borohydride solution (4%, w/v) in water is mixed with the GO dispersion and is kept at 80 oC for 1 h under constant stirring. The partially reduced product (reduced graphene oxide, RGO) is washed with water until its pH becomes 7 and it is re-dispersed in water for diazonium coupling. For this purpose 46 mg sulphanillic acid and 10mg sodium nitrate are dissolved in 10 ml water with the addition of 1.15 ml 12 N HCl at ice cooled condition. The mixture is then added to the RGO dispersion at 0 oC and is kept for two hrs with stirring. It is centrifuged, washed repeatedly with water until pH becomes 7. The product is then re-dispersed in 100 ml water for final reduction with 2ml hydrazine hydrate solution under refluxed condition for 24 h at 100 oC. Finally it is washed with water thoroughly and dried in vacuum at 60 oC. The mechanism of sulfonation of RGO by diazonium salt of sulfanilic acid involves the homolytic fission of dinitrogen from the diazonium salt leading to the generation of aryl radical which binds to the graphene

surface via carbon-carbon covalent bond [31, 32]. This is also evident from the absence of nitrogen in the PSG sample (SI Fig.1). In order to obtain an experimental support of the scheme (Fig.1) elemental analysis data of sulfonated graphene (SG) has been performed from the EDXS experiment (SI Fig. 1). The sulphur contents before and after hydrazine hydrate treatment are represented by the S:C atomic ratio showing the values 1:41 and 1:43 for pre-reduced sulfonated graphene (PSG) and SG samples, respectively. This indicates a small (0.28 wt%) loss of sulphur with respect to carbon during hydrazine treatment. These sulphur contents are very close to that reported by Si and Samulski [18] in the SG sample. Graphene oxide after pre-reduction with NaBH4 (i.e.RGO) shows an average thickness of 1.800.07 nm measured from AFM height profile (SI-Fig.2). It increases after sulphonation by diazonium coupling (i.e. PSG) to 2.000.16 which on reduction with N2H4 remains almost unchanged with an average value of 1.99 0.2 nm for SG. Thus due to sulphonation an increase of graphene thickness is observed. The degree of surface modification has also been evaluated from TGA thermograms (SI Fig.3) of the above three samples taking the TGA thermogram of pure graphite as a reference. From the figure it is evident that there is 33% weight loss in RGO indicating the presence of 33% oxygenous functional material. After sulphonation by diazonium treatment there is 10% more loss suggesting 10 wt % sulfanilic acid group is introduced on the RGO surface. On the final reduction with N2H4, H2O the weight loss from the TGA reference is 27.5% indicating a decrease of (43-27,5 =) 15.5% weight loss after reduction by hydrazine hydrate (i.e.SG). This result implies a significant increase of SP2 character of graphene after hydrazine reduction due to removal of oxygenous materials. From the AFM results

0-5 oC

Figure 1. A schematic presentation of SG preparation from graphite powder (GO = graphene oxide; RGO reduced graphene oxide, PSG = pre-reduced sulphonated graphene and SG= sulphonated graphene after reduction by hydrazine.

we have observed the average thickness of the SG sheets =1.990.20nm, average length =35293 nm and average breadth = 21971.nm (from ~20 measurements) for 1% (w/w) SG concentration. 2.3 Composite preparation: 250mg PVA is dissolved in 5ml water by heating at 90 oC and is cooled to room temperature (30 oC). SG solution is prepared in 5ml water by sonication for 30 minutes and is then mixed with the PVA solution in different proportions. The mixture is sonicated for another 30 minutes for homogeneous mixing. Finally slow evaporation of the solvent in a petri-dish yields films of the composites which are dried at 60 oC for three days in vacuum. The composites are designated as SG0.5, SG1, SG3, and SG5, respectively, the numbers indicate the weight percent of SG in the composites. In a similar fashion the composites of PSG are prepared for comparison in properties and are designated as PSG3 and PSG5 for 3 and 5 % (w/w) PSG samples. 2.4 Characterization: 2.4.1 Microscopy: The field emission scanning electron microscopy (FESEM) is conducted by casting the films from the composite solution in a fresh silicon wafer via slow evaporation of the solvent on a hot plate. They are dried at 60 oC in a vacuum for three days and the morphology is studied using a FESEM instrument (Jeol GSM-5800). The transmission electron microscopy (TEM) is conducted from a thin film on carbon coated copper grid produced by dispersing SG in water and by taking a drop of it on the grid. It is dried slowly at 30 oC for a week. The atomic force microscopy (AFM) is conducted in the non contact mode at a resonance frequency of 250 KHz of the tip using

an AFM instrument (Veeco, model AP 0100). The films are cast on mica surface from a drop of the SG dispersion (without PVA) in water. 2.4.2 Spectral characterization: Raman spectra are studied by casting films of the composite solutions on quartz plate and slow evaporation of water on a hot plate at ~50
o

C followed by vacuum drying at 60 oC for three days. Raman studies were performed

using a micro Raman spectrometer (Agitron) with spot size of 1m2 using 785 nm laser. FTIR study of the samples are performed using a FTIR instrument (model 8400S Shimadzu). The films are cast from aqueous solutions (2% w/v) by spreading over the silicon wafer surface. The films are dried on a hot plate (60 oC) in air and finally in vacuum at 60 oC for three days. The FTIR peaks at 1042 and 1250 cm-1 of PSG and those at 1042, 1125 and 1170 cm-1 in the SG (SI Fig.4) correspond to the presence of SO3H group [18]. 2.4.3 Thermal study: A Perkin Elmer differential scanning calorimeter (DSC 7, Diamond) working under nitrogen atmosphere is used to measure the thermal properties. It is calibrated with indium before use. 4-5 mg samples are taken in aluminum pans and are crimped using a universal crimper. They are scanned from -20 oC at the heating rate of 20 oC / min to 242 oC. The crystallinity (c) values of PVA and of the composites are calculated from the equation:

c =
where

H H 0u

H is the measured enthalpy of fusion (from DSC) and H 0 u is the enthalpy

of fusion of pure PVA crystal (138.6 J g-1) [33].

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2.4.4 X-ray scattering: Wide angle X-ray scattering (WAXS) and small angle X-ray scattering (SAXS) patterns are obtained by fixing the composite films on an aluminum holder and using a Bruker AXS diffractometer (model D8) fitted with a Lynx Eye detector. The instrument is operated at 40 kV and 40 mA current. For WAXS, the samples are scanned from 2=5 to 35 o at the scan rate 0.5 sec per step and for SAXS, the instrument is scanned from 2=0.2 to 5 o at the scan rate of 2 sec per step with a step size of 0.02 o. The crystalline thickness is calculated by multiplying crystallinity with the long distance and the interlamellar amorphous overlayer thickness is measured from the difference between long distance and crystalline thickness. 2.4.5 Mechanical properties: The storage modulus (G'), loss modulus (G'') and tan values of the composites are measured using a dynamic mechanical analyzer (DMA) (model Q-800, TA instruments). Sample films (25mm 5mm 0.15mm) are prepared by pouring the aqueous solution on a die, slow evaporation of the solvent on a hot plate and are finally dried in vacuum at 60 oC for three days. The films are installed at the tension clamp of a calibrated instrument. The samples are heated from -50 oC to 100 oC at the heating rate of 10 oC/min. The G', G'' and tan values are measured at a constant frequency of 1 Hz with a static force of 0.02 N. Tensile tests are carried out from water cast films of uniform thickness using a universal testing machine (Zwick Roell, model Z005) at a strain rate of 1 mm/min at 30 oC. Each experiment is repeated for three times to observe reproducibility. 2.4.6 Conductivity measurement: The dc-conductivity of the films is measured by fixing them between two gold electrodes. The electrical connection is made through copper wires using silver paste on the gold electrodes. The area and thickness of the samples are

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measured by a screw gauge. The conductivity () of the above films are measured by two probe technique with an electrometer (Keithley, model 617) at 30 oC using the equation: =
1 l R a

(1)

where l is the thickness and a is the area and R is the resistance of the sample. The current-voltage (I-V) studies are performed using the same samples by applying voltage from -5 to +5 V and the current is measured at each applied voltage. 3. Results and discussion: 3.1 Morphology and structure: The FESEM micrographs (Fig.2) of SG3 and SG5 show dendritic and rod like morphology, respectively. SG1 has patches of closely spaced fibrillar morphology (SI Fig-5), but none of these morphologies are present in pure SG and PVA (SI Fig-6). The enlarged FESEM picture of SG1 (SI Fig.5) show closely spaced fibrils in patches widely

2m

2m

Fig. 2 FESEM micrographs of (a) SG3 and (b) SG5 composites 12

separated from each other, that of SG3 shows densely branched fibers producing the dendrites and in SG5 the folded SG sheets produce a rod shaped structure. The evolution of different morphologies with composition is interesting and it may arise due to the variation of interfacial interaction between SG and PVA. The TEM micrographs (Fig.3) indicate sheet morphology of SG and dendritic morphology of SG3. It is interesting to note that the sheet morphology of SG is totally absent in SG3, instead the fibrils constitute the dendrites. The new morphology may arise from the self organization of the supramolecular complex between SG and PVA producing fibrils and hence dendrites. The evidence of supramolecular interaction (H bonding) comes from the absence of infrared absorption bands of OH and SO3H groups (2647, 2890 & 3060 cm-1) [34] of SG in any of the composites (SI Fig.7) and a schematic model of the SG - PVA supramolecular interaction is presented in Fig.4. Both the nature of supramolecular complex and its self-organization may depend on

Fig. 3 TEM images of (a) SG and (b) SG3 sample

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the variation of interfacial interaction with composition and it would be evident from the following discussions. .

Fig. 4 H-bonding interaction between PVA and SG In order to elucidate the cause of different morphologies we have made the DSC (Fig.5), WAXS( Fig.6), SAXS (Fig.7, SI Fig.8) and Raman spectra (SI Fig.9) and the data are summarized in Table-1. In the DSC thermograms (Fig.5), pure PVA and SG5 show only one endothermic peak while SG1 and SG3 have two endothermic peaks corresponding to the two different species present in SG1 and SG3. The higher temperature peak is for the melting of PVA crystal entrapped between the SG nanostructures and the lower temperature broad peak may arise from the supramolecular complex of PVA and SG. At lower SG concentration (1% w/w) a majority of PVA chains supramolecularly organize with SG and finally crystallize to produce fibers. As the SG concentration is increased to

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2 2 9 .7

SG5 Heat Flow(Endo Up) 2 3 4 .6 1 4 1 .6 SG3 2 3 2 .8

1 3 4 .3 SG1 2 2 8 .8 PVA 100 150


0

200

T e m p e ra tu re ( C )

Fig. 5 DSC melting endotherms (scan rate 20 0C/min) of different PVA -SG composites

1 9 .4 0

1 9 .4 8

SG 5 SG3

1 9 .5 8

Intensity (a.u)

1 9 .8 0

SG 1

1 9 .8 0

S G 0 .5

PVA 2 5 .2 4 SG 8 .0 7 5 10 15 20 25 30 35

2 (d e g re e )
Fig. 6 WAXS patterns of SG and different PVA-SG composites.

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3% the supramolecular complex organizes in dendritic form while for SG5 rods are produced. The fibril formation of SG-PVA supramolecular complex may be understood in the following way. DSC and WAXS results (Fig.5 and Fig.6) indicate that PVA is a semi-crystalline polymer and the SAXS result (Fig.7 & SI Fig.8) indicates the presence of a lamellar peak. The long distance (13.2 nm) of PVA have increased by 56 and 64% reflecting 17 and 36% increase in crystalline thickness and 77 and 79% increase in amorphous overlayer thickness for SG1 and SG3 systems, respectively. A probable reason is that SG sheets enter into the inter-lamellar amorphous zone causing an increase of amorphous overlayer thickness of PVA. The small increase in crystalline thickness of PVA may be attributed to the disposition of SG sheet near the crystal amorphous interface enhancing irregular chain folding which increase the crystal / amorphous interface

0 .4 1

Intensity

SG3
0

0 .6 7

PVA 1 2 3 2 (d e g re e ) 4 5

Fig. 7 SAXS patterns of PVA and SG3 composite. 16

Table-1. Melting temperature (Tm), enthalphy of fusion (Hf), long distance (L), crystallinity (1-)H, crystalline thickness (lc) and amorphous thickness (la) of PVA-SG composites. Tm (oC) Sample (J/g) PVA 228.8 232.8 SG1 134.3 234.6 SG3 141.6 SG5 229.7 49.4 54.3 13.57 40 5.39 8.14 30.2 41.1 21.52 30 6.46 15.06 49.6 37.7 20.52 27 5.58 14.94 (nm) 13.17 36 4.74 8.43 Hf L (1-)H (%) lc (nm) la (nm)

reflecting an increase in crystalline thickness. Also the specific interaction between SG and PVA at the interface might also contribute to some extent to the increase of crystalline thickness. This PVA lamella and the amorphous layer of SG-PVA complex supramolecularly organize to produce fibrillar morphology and it has been clarified in a schematic model (Fig.8). The longitudinal growth of fibers may be assisted by the supramolecular interaction of SG sheets present at the end of fibrils facilitating the nuclei to grow longitudinally. The presence of SG sheets is confirmed from the Raman spectra (SI fig.9) of the composites where the D and G bands of SG is clearly observed in all the composites, reflecting its concentration is responsible for the morphology change. At the

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inter-fibrillar region some SG and PVA chains (with defect structure e.g entangles, knots etc.) may exist and the population of SG sheets in the inter fibrillar region increases as

PVA:SG = 99:1 Stacked fiber

Growth

= PVA lamella

= SG sheet

PVA:SG = 97:3

Dendritic structure

Cohesive force

PVA:SG = 95:5
Adhesive force

Aggregation induced bended SG sheets coated with PVA


Fig. 8 Suppramolecular organization of PVA and SG for (a) SG1 (b) SG3 and (c) SG5 samples producing different morphology. 18

the SG concentration increases. In SG3 sample the interfibrillar SG concentration is large and the lateral dimensions of SG (length & width ~352 & 219 nm) are also large making a difficulty of diffusion of impurities from the growth font yielding proturbances causing the fibrils to splay in the whole space. The high diffusion constant / growth rate (D/G) ratio causes the branching of fibrils producing dendrites (Fig.8). The dendrites consist of radiating fibrils which share a common crystallographic plane with that of the mother [35, 36]. A decrease of fusion enthalpy (H) of PVA (higher melting peak) in SG1 (Table-1) is probably due to the complexation of a fraction of PVA chains with SG and it is also true for SG3 sample. In both cases a broad peak for melting of SG-PVA supramolecular complex is observed at ~140 oC and it is absent in SG5 sample, where the SG sheets become folded producing a rod like structure. It is evidenced from the almost unchanged Tm and invariant Hf of SG5 with that of pure PVA (Table-1) and a slight increase over PVA may be attributed to the confinement of the chains between the nanorods. At increased SG concentration (5 % w/w) intramolecular attraction between SG sheets causes self-assembly between the sheets which experience an unbalanced force causing bending. The interfacial interaction is of two types: (i) force of adhesion of SG with PVA and (ii) force of cohesion among the SG sheets. Though it is difficult to quantify the magnitude of the above forces, it is likely that the force of adhesion is lower than that of cohesion which increases with SG concentration because at higher concentration SGs are not dispersed rather they are aggregated. In the aggregated SG sheets the upper sheet is in

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an unbalanced state of tension for the inequality of the two forces causing it to bend giving the shape of rod above which PVA wraps. In the composites studied here the SG concentration is varied from 0.5 to 5 wt%. At the lower concentration SG remain exfoliated within the PVA matrix and with the gradual increase of SG aggregated structure may result. Interfacial interaction is dependent on the surface area, so in aggregated state a decrease in interfacial interaction is expected. Here PVA concentration is large and in excess, so the variation of interfacial interaction only results from the variation of SG concentration; as a consequence, the self organization of the system changes. The aggregation of SG sheets with increasing SG concentration may be evidenced from a blank experiment where the SG samples (designated as BSG1, BSG3, and BSG5 analogous to those of the composites) are dispersed in water under similar condition of making the composite without adding any PVA. The absence of PVA avoids any coating of the polymer on SG in the dried state. The thicknesses of the films are measured from AFM (Fig.9). In BSG1 the graphene sheets are widely separated from each other and from the height profiles of 25 particles the histogram of thickness of SG sheets are made. The thickness varies from 1.1 to 2.4 nm having an average value of 1.99 nm. In BSG3 the number density of SG sheets is high but they are homogenously dispersed. On the other hand, in BSG5 the graphene sheets are aggregated and density is lower than SG3. The average thickness of BSG3 and BSG5 are 2.89 and 21.67 nm, respectively. These results suggest that SG thickness increases due to aggregation at higher concentration. In the PVA matrix the environment of SG sheets may not be exactly identical and the state of aggregation may decrease to some extent. PVA chains have pendent OH group similar to water molecules, so the chemical force on SG would

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be of same nature when it is dispersed either in aqueous medium or in PVA. But the high viscosity of high molecular weight PVA may decrease the aggregation of SG sheets to some extent. The highly dense but homogenously dispersed state of SG in SG3 is interesting and it supports the cause of dendrite formation discussed above. From WAXS patterns (Fig.6) it is evident that PVA exhibits a sharp diffraction peak at 2=19.80 (dhkl=4.48 A0) which progressively shifts to lower 2 value and finally reaches at 19.40 (dhkl= 4.57A0) for SG5. Though unusual, the specific interaction between SG and PVA may expand the unit cell dimensions of PVA to some extent (2%) in the composites. In SG5 the increase of d-spacing is somewhat lower than that of SG1 & SG3 (cf; relative decrease of 2 values) and the increase of dhkl indicates an interaction also exists between PVA and the SO3H groups at the outer surface of SG rods. In literature [20-23, 37] there are some reports on WAXS of PVA/GO or PVA/graphene composites. GO has a diffraction peak at 110 corresponding to its interlayer spacing (7.8 A0). This diffraction peak disappears when mixed with PVA indicating exfoliation of GO sheets [37]. The PVA peak intensity at 2 = 200 decreases in all the composites with increase in graphene / GO concentration indicating a decrease of PVA crystallinity, however, the peak position remains unchanged. But in the present system the decrease in 2 value is unique due to the presence of strongly interacting -SO3H group. The fillers in the blends / composites may present in the intercrystalline region which includes interlameller, interfibriliar and interspherulitic zones [38]. The distribution of the filler in the three zones depends on the dimension of the filler, concentration of the filler and its interaction with the polymer. If the filler is within the interlamellar amorphous region as shown in Fig.7, the interlamellar amorphous overlayer thickness would increase

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and it is reflected in the present SAXS data (Table-1) for SG1 and SG3 due to their lower thickness value. An enlarged long spacing in the two is observed over PVA, but in SG5 the long spacing value is almost the same. The large increase of interlamellar amorphous overlayer thickness than

a
No of particle

7 6 5 4 3 2 1 0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 Thickness (nm)

b
No of particle
No of particle

8 7 6 5 4 3 2 1 0 2.1 2.4 2.7 3.0 3.3 3.6 Thickness (nm)

10 8 6 4 2 0 5 10 15 20 25 30 35 40 Thickness (nm)

Fig. 9 AFM image of SG at (a) 0.01 (w/v) (b) 0.03 (w/v) and (c) 0.05 (w/v) 22

crystalline thickness indicates that the supramolecular complex is produced both in the crystal amorphous interface and more preferably within the amorphous overlayer region of PVA crystals. Considering the average thickness of SG sheets (1.99 & 2.89 nm in BSG1 and BSG3 from AFM analysis) it is evident that a maximum of 3 SG sheets can enter into the interlamellar amorphous layer of PVA to increase the amorphous overlayer thickness by ~8 nm. In SG5 the aggregated SG sheet (av. thickness. 21.7nm) can not enter into the amorphous overlayer region making an almost unchanged value in the crystal and amorphous overlayer thickness with that in PVA. Hence it may be concluded that in SG5 the SGs are not inter-lamellar whereas in SG1 and in SG3 samples SGs are not only inter-lamellar but also inter fibrillar. 3.2 Mechanical properties:

Young's Modulus (GPa)

200 180

8 6

Tensile Stress (M Pa)

160 140 120 100 80 60 40 20 0 0

SG3
4 2

1 2 3 SG % (w/w)

SG5 SG1 PVA

SG0.5 200 250 300

50

100

150

Strain (%)
Fig. 10 Mechanical property of PVA and its composites with sulphonated graphene at indicated compositions. 23

The mechanical properties of different SG composites (Fig.10 and Table-2) are interesting. Both stress and strain at break gradually increase with increasing SG concentration except for SG5 where an increase of stress (157%) occurs though strain at break decreases abruptly (even lower than that of pure PVA). Among the three composites the highest increase of both stress (177%) and strain at break (45%) is observed in the dendritic SG3. Consequently, the toughness of the material has the value of 657 Nmm, with a 235 % increase over PVA. To our knowledge, it is the highest increase of toughness yet reported in the literature for the PVA-graphene composite.

Table-2. Stress at break, Strain at break, Youngs modulus, Toughness of PVA and PVASG composites at 30 oC.

Sample

Strain

% increase

Stress (MPa)

% increase

Modulus (GPa)

% Increase

Toughness (Nmm)

% Increase

PVA SG1 SG3 SG5 PSG3 PSG5

187 266 272 84 256 101

42 45 -55 36.8 -45

48 97 133 101 130 104

102 177 111 170 116.7

2.9 3.9 5.3 8.0 5.5 7.8

36 86 180 89.7 169

196 526 657 222 645 227

169 235 13.5 229 15.8

Due to nano-confinement the PVA chains experience lesser flexibility for the large cohesive force of the SG nanosheets. On application of stress, the alignment of SG sheets

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changes relaxing the PVA chains, hence causing an increase of strain at break. In SG5 as the rods are randomly oriented having lower surface area than that of sheets the strain at break has decreased and the stress at break has increased to 111% over PVA. The Youngs modulus increases progressively with increasing SG concentration in the composite and the highest value (8GPa) is achieved for SG5 (Table-2). The reported enhancements of Youngs modulus are 62% for 0.7 wt% GO [9], 100% for 1.8 vol% RGO [10] and 128% for 3wt% GO [8]. However, in the present system 180% increase of Youngs modulus, is a maximum yet reported in the literature for the PVA/ graphene composites. It is to be noted here that GO/ PVA composites causes a decrease of percent strain with increase of stress on addition of GO [9,10, 20], but in the present system both strain and stress increase till 3 wt % addition of SG. So the SO3H group of SG is influencing the mechanical property of PVA much more effectively than that of COOH group of GO. The mechanical properties of SG composites are compared by making composites with PSG samples at two compositions identical to SG3 and SG5 composites. Youngs modulus, strain at break and toughness are comparable to those for SG

coposites (Table- 2) suggesting that hydrazine treatment used for reduction of PSG does not affect the mechanical property almost unchanged. The storage modulus (G) vs temperature plot (Fig.11), show a significantly large increase in the composites and it is very large in SG3 (Table-3). The highest (1005%) increase of SG3 over PVA is observed at 30 oC enabling it to behave as a promising reinforced plastic at ambient condition. The loss modulus (G) vs temperature plot has also similar trend and SG3 exhibits the highest value compared to the other composites (SI Fig.10). This indicates that the cause of increase G and G is the same and the

25

reinforcement of dendrites is the highest due to the very large surface area of the dendrites. Recently Brinson & coworkers have reported 650% and 1019 % increases of G for 44% and 60% (w/w) GO, respectively, in GO / PVA composites [27]. We have found 1005% increase in storage modulus for 3% (w/w) SG content only. So in the present system

20000 4 Stortage modulus 16000 3 2 5 1. PVA 2. SG 0.5 3. SG 1 4. SG 3 5. SG 5

12000 1

8000

4000

0 -40 -20 0 20 40
0

60

80

100

Temperature ( C)

Fig.11 Storage modulus -temperature plots of different PVA-SG composites.

addition of a very small amount of SG is very much effective in increasing G and it is due to the formation of supramolecular organized structure. The peak temperature of Tan vs temperature plot (SI Fig-10) indicates glass transition temperature (Tg ) of PVA in the composites. It has decreased in the composites and the lowest Tg in SG3 (Table-3) compared to those of the others is for its dendritic morphology. The densely spaced and widely distributed fibrils decrease the interaction amongst the PVA segments. This

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causes an increase of free volume of PVA in the system facilitating the onset of segmental motion at lower temperature [39,40]. So in the present system addition of a very small amount of SG is very much effective in increasing the segmental motion of PVA chains hence decreasing the Tg .

Table-3. Storage modulus (G') and Glass transition temperature (Tg) from Tan plots and values of PVA-SG composites.

Sample

Tg ( C)

G' (MPa) at -30 oC 11265 13995 17463 16946

% increase

G' (MPa) at 0 oC

% increase

G' G' % (MPa) (MPa) increase at 30 oC o at 10 C

% increase

PVA SG1 SG3 SG5

32.2 24.8 21.8 29.2

24.2 55 50

3507 10885 14426 7417

210 311 112

3496 10874 14341 7332

211 310 109

749 6946 8274 1708

827 1005 128

3.3 Conductivity: Graphene is a good conductor of electricity [41, 42] and PVA is an insulator, ( =5.31014

S/cm), but SG0.5, SG1, SG3 and SG5 have conductivity 6.110-10, 1.2 10-5, 0.9 10-4,

and 1.5 10-5 S/cm at 30 oC. Thus compared to pure PVA there is 10 orders increase in the magnitude of dc-conductivity in SG3 which also shows a 10 fold higher conductivity than that of other composites. This is due to the easier hopping of charge carriers through the closely spaced fibrils of SG3 dendrites. Also the planar structure of dendrites causes

27

an easier charge movement contributing to the highest conductivity. We have plotted conductivity vs. SG concentration (Fig.12) and it shows a percolation threshold at a SG concentration of 0.37 wt%. This low percolation threshold is

-4 -6 log() -8

-10 -12 -14 0 0.37 1 2 3 4 5

S G % (w /w )

Fig. 12 Conductivity log() vs SG% (w/w) plot

indicative of good dispersion of SG in the composite at lower concentration and at a 1 wt% SG the system shows a saturation in the conductivity value. It is true that in some graphene polymer composites the conductivity is very high e.g in graphene/ polystyrene composite it has the highest conductivity (0.15 S/cm) for 1.2 wt% graphene [24]; 0.5 S/cm for 2.2 vol % graphene in graphene / polycarbonate composites [25]; 0.01 S/cm for 2.5 vol% graphene in PS / graphene composites [43] etc. But there are also reports where modified graphene composites has much lower conductivity e.g. 10-5 S/cm for PVDF/grahene-PMMA [10] for 5 wt% filler, 10-4 S/cm for RGO /PVDF composite at 4wt% filler [26]. In a surfactant wrapped graphene / PVC composites the

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conductivity is 10-4 S/cm at 5.5 vol % filler [44] and in ECG / PVA composite the conductivity is 10-7 S/cm for 6 wt% filler [23]. So different conductivity is reported and particularly for composites with the modified graphene conductivity is lower. In the present system the conductivity is in the lower group and no definite reason can be afforded for this lower conductivity. One probable reason is that the nonconducting PVA becomes supramolecularly linked with SG from all sides of its surface decreasing its conducting paths. This supramolecularly interacted SG / PVA complex organizes into fibrils, dendrites or rods. So SG is not dispersed as sheets as graphene in the first group of composites but its supramolecularly organized structure with decreased conducting path become dispersed throughout the matrix yielding lower conductivity. Also during sulphonation some sp
2

hybridized bonds being converted into sp

hybridized bonds,

which are not totally recovered to sp 2 hybridized bonds during reduction by hydrazine, and destroys the conjugation to some extent. Due to the above reasons conductivity of SG/PVA composites is lower than other graphene/polymer (polystyrene or

polycarbonate) composites We have compared the conductivity of PSG/PVA composites at two identical compositions with those of SG/PVA composites. The conductivity of PSG3 is 1.110-7 S/cm which is three orders lower over SG3 composite (0.910-4 S/cm). In PSG5 composite the conductivity is found to be 1.2 x 10-7 S/cm which is also 2 orders lower over SG5 sample (1.5 x10-5 S/cm). Thus a 2- 3 orders increase in magnitude of conductivity is observed in the hydrazine reduced SG3 samples. As discussed in the mechanical property section the percentage increases of stress, Youngs modulus and toughness of PSG composites are comparable with SG composites (Table- 2) suggesting

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that hydrazine treatment increases the conductivity keeping the mechanical property almost unchanged. The current-voltage (I-V) characteristic curves of SG3 and SG5 composites are presented in Fig.13, clearly indicating a significant variation of I-V properties with composition. SG1 shows a typical semi-conducting behavior, SG3 shows an electronic memory and SG5 shows a rectification behavior. The increased graphene concentration

80 40 0 -40 300 SG5

Current ( amp)

150 0 -150 -300 70 35 0 -35 -70 -6 -4 -2 0 2 Voltage (V) 4 6 SG1 SG3

Fig. 13 Current-voltage (I-V) characteristic curves of different SG-PVA composite at indicted compositions.

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has generated different morphology which may be attributed to the different I-V behavior. The semiconducting nature of SG1 may be attributed to the patches of fibrils with a gap between them (SI Fig.5) causing a hindrance to the charge transport. The memory effect in SG3 is due to its dendritic morphology. In the forward bias it shows an inflection voltage at 3.01 V where the charge carrier reaches the conduction band but on decreasing voltage in the backward bias the charges are retained at the junction points of fibrils in the dendrites. At a much lower voltage (threshold voltage= 0.6 V) the charge becomes annihilated. The SG5 sample has rod like morphology showing a rectification property (rectification ratio=3.5). Like carbon nanotubes the graphene ring is a good acceptor of electrons and here electrons become stabilized by resonance between the graphene rings [45] and can act as a p-type semiconductor. PVA acts as a n-type semiconductor due to the presence of lone pair of electrons on the oxygen atom of OH group. Hence the uniform distribution of rods makes the system an effective p-n junction suitable for rectification. It is to be noted that in the positive bias it also exhibits memory effect (inflection voltage 3.4 V) due to the charge trapping by the graphene rods and it requires a lower voltage for annihilation (threshold voltage 2 V). 4. Conclusions: PVA/SG composite exhibits different morphology at different compositions of the hybrids due to supramolecular organization. SG1 has fibrillar morphology, SG3 shows dendritic morphology and SG5 exhibits rod like morphology. The supramolecular interaction (H-bonding) is evident from Fourier transform infrared spectroscopy (FTIR). DSC study shows a new peak in addition to that of PVA arising from supramolecular organization of the components in SG1 and SG3 samples but this is absent in SG5 sample. SAXS results indicate 17 and 36% expansion of PVA crystalline

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thickness and 77 and 79% increase in amorphous overlayer thickness for SG1 and SG3 systems but SG5 do not show any appreciable change from that of PVA. AFM results indicate aggregation of SG sheets with increasing concentration and a maximum of three SG sheets can enter into the interlamellar amorphous zone of PVA crystal during composite formation. The composites exhibit a dramatic change in mechanical property which is also dependent on composition, hence morphology of the system. The highest increase of stress (177%), strain at break (45%) and toughness (235%) over PVA is observed in the dendritic SG3. Youngs modulus increases progressively with increasing SG concentration in the composites showing the highest increase (180%) over PVA for SG5 system. The storage modulus of SG3 shows the highest (1005%) increase over PVA at 30 oC. Also a 10 orders increase in the magnitude of dc conductivity over PVA and 10 fold increase in dc conductivity in the dendritic SG3 than any other morphology are achieved. In the I-V characteristic curves, SG1 exhibit typical semiconducting nature, SG3 shows an electronic memory and SG5 exhibit a rectification behavior. Similar dendritic type morphology may be achieved in other systems also by proper modification of graphene, suitable for supramolecular interaction with the polymer of interest. Acknowledgment: We gratefully acknowledge DST, New Delhi (grant No.SR/SI/PC26/2009) and DST funded Unit of Nano Science at IACS for financial assistance. RKL acknowledges CSIR new Delhi for granting fellowship. We also acknowledge Dr. Nikhil Jana of IACS for helping in micro Raman spectra.

Supporting Information Available: EDXS, AFM, TGA, Raman spectra, FESEM, SAXS, FTIR, Loss Modulus and Tan plots are available at the web free of charge.

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