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Piezoresistive behavior and multi-directional strain sensing ability of carbon nanotubegraphene nanoplatelet hybrid sheets

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2013 Smart Mater. Struct. 22 015013 (http://iopscience.iop.org/0964-1726/22/1/015013) View the table of contents for this issue, or go to the journal homepage for more

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IOP PUBLISHING Smart Mater. Struct. 22 (2013) 015013 (9pp)

SMART MATERIALS AND STRUCTURES

doi:10.1088/0964-1726/22/1/015013

Piezoresistive behavior and multi-directional strain sensing ability of carbon nanotubegraphene nanoplatelet hybrid sheets
Sang-Ha Hwang, Hyung Wook Park and Young-Bin Park
School of Mechanical and Advanced Materials Engineering and Two-Dimensional Carbon Materials Center, Ulsan National Institute of Science and Technology, UNIST-gil 50, Eonyang-eup, Ulju-gun, Ulsan 689-798, Korea E-mail: ypark@unist.ac.kr

Received 12 August 2012, in nal form 19 November 2012 Published 10 December 2012 Online at stacks.iop.org/SMS/22/015013 Abstract Free-standing carbon nanomaterial hybrid sheets, consisting of multi-walled carbon nanotubes (MWCNTs), exfoliated graphite nanoplatelets (xGnPs) and nanographene platelets (NGPs) of different lengths and lateral dimensions, have been prepared using various material combinations and compositions. When subjected to tensile strains, the carbon nanomaterial sheets showed piezoresistive behavior, characterized by a change in electrical resistance with applied strain. Simultaneous measurement of resistance changes among multiple electrodes placed on the periphery of the hybrid sheets showed the dependence of resistance changes on strain direction, which potentially allows multi-directional strain sensing. Various combinations of MWCNT length, xGnP size and MWCNT-to-xGnP/NGP ratio result in different specic surface areas and nanoparticle interactions, which serve as critical factors for controlling the sensitivity of hybrid sheets. The smaller the nanoplatelet size and the higher the content as compared to MWCNT, the higher the sensitivity. Buckypapers, which are free-standing sheets composed of CNTs, are used as the control materials, and the unique characteristics of hybrid sheets are discussed. (Some gures may appear in colour only in the online journal)

1. Introduction
There has been much research on composite materials containing nanoscale carbon allotropes, including carbon nanobers [1], exfoliated graphite nanoplatelets (xGnPs) [2], fullerenes [3], carbon nanotubes (CNTs) [4] and graphene [5]. These carbon-nanomaterial-lled composites have been intensively studied and reviewed as multifunctional material platforms, owing to their remarkable mechanical, electrical/electronic and thermal properties [6, 7]. Among various smart applications, signicant advances have been achieved from CNT-lled polymeric materials used as strain sensors [813]. There are two main working principles of strain sensing using carbon-nanomaterial-based polymer
0964-1726/13/015013+09$33.00 1

composites. The rst mechanism derives from the relationship between the Raman spectrum shift and mechanical strain, as observed by Frogley et al [14] in CNT composites. The second and more generally applied mechanism is strain-induced change in electrical resistance, known as piezoresistivity, which is observed in both buckypapers, that is, free-standing sheets composed of densely entangled CNT network [14, 15], and CNT-lled polymer composites [8, 9]. In the case of CNT-lled polymer composites, the sensitivity and applicable strain range can be relatively easily controlled by ller content, ller orientation and matrix type. However, it is difcult to fabricate buckypaper-based strain sensors with tailored sensitivity and mechanical properties due to the robust nature of the conductive network formed by densely
c 2013 IOP Publishing Ltd Printed in the UK & the USA

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entangled CNT bundles. Despite several disadvantages, a densely entangled CNT bundle is expected to achieve higher sensitivity in a local area and direction-dependent piezoresistivity due to its isotropic structure [14]. In recent years, free-standing graphene and graphene oxide lms or papers have been processed and characterized [1618]. However, the primary focus has been placed on uniform dispersion of graphene or graphene oxide nanosheets in an aqueous or organic solution and controlled assembly into high-strength, high-stiffness free-standing lms or papers. Their electromechanical properties are yet to be investigated. Recently, the graphitic nanostructured particles were hybridized with CNTs and were mainly studied as functional materials for particular applications, such as supercapacitors [19], transparent electrodes [20], catalyst supports [21], eld emission devices [22], gas sensors [23] and photonic applications [24]. Knowledge about the synergistic effect was obtained from a recent electrochemical study of hybrid lms while their effects on electromechanical properties are still elusive. We report the fabrication and characterization of multiwalled carbon nanotube (MWCNT) buckypapers hybridized with xGnPs and nanographene platelets (NGPs). Various combinations of MWCNT length, xGnP size, NGP size and MWCNT:xGnP or MWCNT:NGP content ratio were used to process carbon nanomaterial hybrid sheets through ltration, and their mechanical, electrical, piezoresistive and microstructural properties were characterized. xGnPs and NGPs consist of sp2 carbon atoms, which allow them to have strong interactions as well as van der Waals interactions. Thus, CNTs combined with xGnPs or NGPs in sheet form are expected to have a whole new range of interesting properties, especially a change in electrical behavior when subjected to an external loading, due to nanobernanoplatelet interactions. Only a few research groups have reported their work on hybrid sheets consisting of CNTs and graphitically structured nanomaterials, and their electromechanical properties are yet to be studied. In order to capture the unique properties of MWCNTxGnP and MWCNTNGP hybrid sheets, the study was focused on two aspects: (1) investigating the effects of the hybridized nanostructure on piezoresistivity and understanding the underlying physics; and (2) exploring the potential for wide-area strain sensing by demonstrating proof-of-concept of a two-dimensional strain sensing ability under exure.

2.1%, and surface area of 400800 m2 g1 was purchased from Angstron Materials. The carbon nanomaterials were used without any further chemical modication. 2.2. Preparation of MWCNTxGnP and MWCNTNGP hybrid sheets Surfactants, sodium lauryl sulfate (SLS) and Triton X-100, were purchased from Sigma-Aldrich and Daejung Chemicals, respectively, and solutions were prepared with a concentration of 0.05 wt% in methyl alcohol. 120 mg of MWCNTxGnP or MWCNTNGP mixture with various proportions of xGnP or NGP versus MWCNTs and various MWCNT and xGnP types was dispersed in 2 l of SLS/Triton X-100 solution. After 1 h of stirring and 3 h of sonication in a bath-type sonicator, the solutions were further treated for 2 h using a horn-type sonicator. A nylon ltering membrane (0.45 m pore size, Millipore) was used for making hybrid sheets by vacuum ltration. Two liters of suspension was ltered to yield one 78-mm diameter paper. The paper was then washed using methanol and acetone to remove residual surfactants and then placed in an oven and dried at 60 C overnight before being peeled off the membrane. 2.3. Microstructure characterization The morphologies and microstructures of as-received MWCNTs, xGnPs and NGPs were observed using a scanning electron microscope (SEM, FEI Nanonova 230) and a transmission electron microscope (TEM, JEOL JEM-2100). A confocal Raman microscope (WITec alpha300 R) was used to assess the nature of carbon atom bonding in the basal plane and the degree of defects in xGnPs and NGP. Hybrid sheets with various carbon nanomaterial compositions were analyzed at the micro- and nanoscale using the SEM operated at 15 kV to observe the interaction between MWCNTs and xGnPs/NGPs as well as the sheet morphologies. For selected sheet samples, SEM images were taken after stretching the sheet in tension to observe the MWCNTxGnP/NGP interaction after undergoing tensile deformation. Buckypapers and hybrid sheets are inherent porous media, as they are formed by entangled, inter-connected MWCNTs, xGnPs and GNPs. In order to understand the effects of various material combinations on the porosity of the hybrid sheets, their surface areas were measured using a BrunauerEmmettTeller (BET) surface area analyzer (Micromeritics ASAP 2020) using N2 adsorption at 77 K. 2.4. Mechanical property characterization Specimens of size 5 mm 15 mm were cut from each hybrid sheet using a 25 W laser cutter (Universal Laser Systems VersaLaser 2.30) for tension tests. A dynamic mechanical analyzer (DMA, TA Instruments Q800) was used in static mode to measure the tensile properties. After being installed in the DMA, the specimens were subjected to quasi-static tension to failure at a constant strain rate of 1 min1 . A total of seven specimens were tested for each sample, and ve intermediate measurement data were selected to obtain the average tensile modulus, tensile strength and % elongation to failure.
2

2. Experimental details
2.1. Materials MWCNTs, grown by chemical vapor deposition, with a purity rating of >95%, 510 nm inner diameter, 60100 nm outer diameter, and two different lengths100 m (CM-100) and 250 m (CM-250)were purchased from Hanwha Nanotech. Two types of xGnP with average lateral dimensions of 5 m (M-5) and 15 m (M-15) were purchased from XG Sciences. NGP with a documented average lateral dimension of 10 m, average thickness of <1 nm, oxygen content of

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Figure 1. Inter-probe resistance and piezoresistivity measurement setup. (a) Multi-electrode measurement scheme. (b) Piezoresistivity measurement setup. (c) Loading conguration during piezoresistivity measurement. (d) Bottom view showing the quasi-uniaxial strain eld in the longitudinal direction.

2.5. Electrical property and piezoresistivity characterization The surface and volume resistivities of hybrid sheets were measured using a four-point probe measurement system (Advanced Instrument Technology CMT-SR1000N). Five measurements were made at different locations per sample, and the average values were recorded. In addition, resistance measurements were made to indirectly assess the degree of carbon nanomaterial dispersion. Hybrid sheets were cut into 50 mm 50 mm squares and were bonded to 10 mm-thick polymethylmethacrylate (PMMA) plates using an epoxy glue, as shown in gure 1(a). Eight electrodes were attached on the periphery of the square lm using a silver paste, which were connected to the electrical signal acquisition system consisting of a Keithley 2002 multimeter and 7001/7012-S switching system, operated by the manufacturer-programmed data acquisition software. A set of inter-probe resistances per unit length from all electrode pairs was obtained, and the averages and standard deviations were compared among various inter-probe distance groups. The hybrid-sheet-bonded PMMA plates were subjected to three-point bending using a universal materials testing system (Instron 5982), as shown in gures 1(b)(d), and piezoresistivity was measured. The upper exural strain limits to ensure linear, elastic deformations of hybrid sheets were determined through preliminary experiments, and accordingly 2 and 1% of exural strains were applied at a strain rate of 4% min1 for MWCNTxGnP and MWCNTNGP hybrid sheets, respectively.

3. Results and discussion

3.1. Microstructure Typical TEM and SEM images of both surfaces and cross-sections of xGnPs (M-5, M-15) and NGP particles are shown in gures 2(a)(c), respectively. The high aspect ratio of xGnP is evidenced by the large lateral dimension of the particle as compared to the thickness, which is 18 and 9 nm for M-5 and M-15, respectively. Figure 2(c) shows
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the lateral dimension and thickness of NGP are <2 m and 5 nm, respectively, which would result in much greater surface area than xGnP. The Raman spectra of both xGnP and NGP particles are shown in gure 2(d). The low D band intensity and sharp G band conrm the sp2 -type bonding of the carbon atoms in the basal plane. It is thus believed that the acid intercalation and subsequent pulverization involved during the xGnP manufacturing process did not oxidize the surface of the xGnP, which may degrade the electrical and mechanical properties of an individual platelet. However, a much larger ID /IG ratio was observed from NGP, which may be due to more destructive intercalation and pulverization processes compared to xGnP. It is noted in gures 3(a) and (d) that both xGnP and NGP hybrid sheets are macroscopically robust under exural stress, as they can be almost folded without failure. Figures 3(b), (c), (e) and (f) show the basal plane morphologies of the CM-250/M-5 and CM-250/NGP hybrid sheets before and after stretching. In gures 3(c) and (f), the MWCNT bridging suggests that the surface adhesion between MWCNT and xGnP or NGP is very strong because of the van der Waals interactions and interactions of sp2 carbon atoms. Table 1 summarizes the eight different sets of buckypapers and hybrid sheets prepared for this study. The sample sets and names are based on the combination of MWCNT and xGnP or NGP types and the MWCNT:xGnP or MWCNT:NGP ratio in hybrid sheets. The specic surface areas of buckypapers and selected hybrid sheets, denoted as ABET , are also shown in table 1. The reported specic surface area of MWCNT buckypaper is around 200 m2 g1 , and our measurement showed similar values for the buckypapers of both CNT lengths. From the BET measurement, it is evident that buckypapers have much higher surface areas than MWCNTxGnP hybrid sheets because of the one-dimensional structure, unique morphology and nanoscale size of CNTs. The measured ABET of xGnP M-5 and M-15 was around 90 and 70 m2 g1 , respectively. The measured ABET of NGP was around 400 m2 g1 , and therefore, the ABET

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Figure 2. Typical SEM and TEM micrographs of the surface and the cross sectional view of xGnPs and NGP ((a) M-5, (b) M-15, (c) NGP, respectively). (d) Raman spectra of as-received carbon nanomaterials.

Figure 3. Digital photographs and SEM images of CM-250/M-5 (5:5) hybrid sheet ((a)(c)) and CM-250/NGP (5:5) hybrid sheet ((d)(f)). (a), (c) Digital photographs upon folding. (b), (e) SEM images of hybrid sheet surface. (c), (f) SEM images of crack morphology in hybrid sheets with in-plane tension.

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Table 1. Specic surface areas (ABET s) of buckypapers and hybrid sheets. Material type CM-250 CM-250 and M-5a CM-250 and M-15a CM-250 and NGPc Sample name CM-250 CM-250/M-5 (8:2) CM-250/M-5 (5:5) CM-250/M-5 (3:7) CM-250/M-15 (8:2) CM-250/M-15 (5:5) CM-250/M-15 (3:7) CM-250/NGP (8:2) CM-250/NGP (7:3) CM-250/NGP (6:4) CM-250/NGP (5:5) CM-100 CM-100/M-5 (8:2) CM-100/M-5 (5:5) CM-100/M-5 (3:7) CM-100/M-15 (8:2) CM-100/M-15 (5:5) CM-100/M-15 (3:7) CM-100/NGP (8:2) CM-100/NGP (7:3) CM-100/NGP (6:4) CM-100/NGP (5:5) xGnP or NGP content (wt%) 0 20 50 70 20 50 70 20 30 40 50 0 20 50 70 20 50 70 20 30 40 50 ABET (m2 g1 ) 210.0 197.2 157.2 121.3 109.4b 273.8 324.2 349.8 375.3 197.2 147.8b 101.6b 381.3b

CM-100 CM-100 and M-5a CM-100 and M-15a CM-100 and NGPc

70 wt% was the highest xGnP content achievable. Selected hybrid sheets (MWCNT:xGnP/NGP = 5:5) for ABET comparison purposes. c 50 wt% was the highest NGP content achievable.
b

of MWCNTNGP hybrid sheets was much higher than that of buckypapers. The ABET of xGnP and NGP hybrid sheets as functions of xGnP and NGP contents were in good agreement with the values calculated using the rule-of-mixtures. At 50 wt% xGnP or NGP, which is the highest achievable NGP loading from the point of view of hybrid sheet manufacture, regardless of the type of MWCNT, CM-100/NGP showed the highest ABET while CM-100/M-15 and CM-250/M-15 showed the lowest. This suggests that the length of CNTs does not have a signicant effect on the specic surface areas of hybrid sheets, while the lateral dimension of xGnP or NGP has a signicant inuence; that is, the smaller the lateral dimension, the larger the specic surface area. 3.2. Mechanical properties The tensile properties of MWCNT/xGnP and MWCNT/NGP hybrid sheets at 5:5 content ratio are shown in gure 4. The tensile modulus of the CM-250 buckypaper was increased by 21% from 513 to 609 MPa with the addition of xGnP-M-5, while its tensile strength and elongation were decreased from 21.3 MPa and 6.3% to 14.3 MPa and 3.5%, respectively. Despite the fact that the aspect ratio of xGnP-M-15 is much higher than xGnP-M-5, the stiffening efciency of xGnP in CM-250/M-15 hybrid sheet (only 2.5% improvement in tensile modulus as compared to CM-250 buckypaper) was lower than that in the CM-250/M-5 hybrid sheet. A similar trend is observed in CM-100/xGnP hybrid sheets. This suggests that the size effect, which can be
5

Figure 4. Tensile properties of MWCNT/xGnP and MWCNT/NGP hybrid sheets with various material types at 50 wt% of xGnP or NGP content.

translated into the specic surface area, is more dominant than the aspect ratio, for enhancement of tensile modulus, as the smaller size increases the volume of the interphase between xGnPs and the domain. The tensile moduli of the porous sheets studied are indicative of the packing densities of the carbon nanosheets, and the sheet strengths and elongations are governed by the interactions of carbon nanoparticles or domains. We can infer from the SEM images and BET results that

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Table 2. Average normalized inter-electrode resistances of hybrid sheets and their standard deviations. Average inter-probe resistance ( cm1 ) CM-250 CM-250/M-5 (5:5) CM-250/M-15 (5:5) CM-250/NGP (5:5) CM-100 CM-100/M-5 (5:5) Figure 5. Effect of M-5 and NGP on the normalized inter-electrode resistance of hybrid sheets with each distance group at 50 wt% of xGnP and NGP loading. 2.24 2.63 2.85 3.37 2.34 2.63 Standard deviation ( cm1 ) 0.17 0.20 0.22 0.51 0.15 0.24

electrode pairs (a total of C2 8 = 28 pairs) in sequence. In order to eliminate the inter-electrode distance dependence of the raw resistances measured, each resistance was divided by the distance between the corresponding electrodes as follows: r i,j = Ri,j Li,j (1)

the MWCNT bundles exhibit not only strong van der Waals and interactions but also mechanical interlocking through entanglements. This results in the higher strength and elongation of buckypapers as compared to hybrid sheets. Although it is clear that xGnPs interfere with the interactions between MWCNTs, the small xGnP particles from sonication-induced damage ll the buckypaper pores, thus increasing the occupied volume and modulus. Comparison of MWCNT/xGnP and MWCNT/NGP hybrid sheets at a 5:5 ratio revealed that inclusion of NGPs in buckypaper signicantly decreases its modulus by 57.4% from 513.1 to 218.3 MPa, its ultimate tensile strength by 71.9% from 21.3 to 6.0 MPa, and its maximum elongation by 95% from 6.3 to 0.3%. A similar trend is observed from the CM-100/NGP (5:5) hybrid sheet. This is attributed not only to weak interactions between CNTs and NGP particles, but also to the low packing density of the MWCNT/NGP hybrid sheet. It is elaborated by the combined results from the microstructure and degree of defects of as-received NGPs (gures 2(c) and (d)) and the microstructure of the mechanically stretched MWCNT/NGP hybrid sheet (gure 3(f)). Few-atom-thin NGP nanosheets are thermodynamically unstable, and their high specic surface area maximizes the van der Waals interactions, which results in re-aggregation of MWCNTs and NGPs in suspension, leading to a wrinkled morphology of the hybrid sheet. These pre-agglomerated domains are barely inter-connected for a robust free-standing hybrid sheet, as can be observed from gure 3(f), which leads to deteriorated mechanical properties. In addition, we can easily imagine that the interactions between CNT and NGP particles are weaker than those between CNT and xGnP particles, due to the low crystallinity of NGPs, as conrmed from the Raman spectrum in gure 2(d). 3.3. Electrical properties

where r i,j denotes the normalized resistance measured between electrodes i and j (i, j = 1, 2, 3, . . . , 8), Ri,j is the corresponding raw resistance measured and Li,j is the distance between electrodes i and j. The normalized inter-electrode resistances were categorized into ve distance groups, and selected values are plotted in gure 5. The averages and standard deviations of the normalized resistances of various material combinations are summarized in table 2. Among all carbon nanomaterial sheet types, the CM-250 buckypaper shows the lowest average normalized inter-electrode resistance of 2.24 cm1 and 1 standard deviation of 0.17 cm , indicative of isotropic and homogeneous electrical properties. It can also be inferred that both xGnP-M-5 and M-15 were well dispersed in CM-250/M-5 and CM-250/M-15 hybrid sheets, suggested by low standard deviations of 0.20 and 0.22 cm1 , respectively. However, the CM-250/NGP hybrid sheet shows a relatively high standard deviation of 0.51 cm1 , suggesting less uniform dispersion of NGPs in the hybrid sheet. 3.4. Electromechanical behavior of buckypapers and hybrid sheets Electromechanical tests were performed with buckypapers and hybrid sheets with various material combinations and xGnP or NGP contents under cyclic exural loading. For each electrode pair, the change in resistance was computed by comparing the resistances obtained from two consecutive measurement rounds, and was normalized by dividing it by the initial resistance and the physical distance between the electrodes as follows: ri,j = Ri,j 1 Li,j (R0 )i,j (2)

For the experimental study on piezoresistivity of hybrid sheets, eight electrodes were attached to the periphery of a hybrid sheet bonded to a PMMA plate as previously shown in gure 1(a). The resistances were measured from all possible
6

where ri,j denotes the normalized change in resistance measured between electrodes i and j (i, j = 1, 2, 3, . . . , 8), Ri,j is the corresponding change in resistance, (R0 )i,j is the

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Figure 6. Resistance change in: (a) CM-250 buckypaper; (b) CM-250/M-5 (5:5) hybrid sheet; (c) CM-250/NGP (5:5) hybrid sheet under cyclic exural strain. (R45 denotes resistance between electrodes 4 and 5, and so forth.)

initial resistance and Li,j is the distance between electrodes i and j. As the PMMA plate undergoes three-point bending, the carbon nanomaterial sheet undergoes the same quasi-uniaxial tensile strain as the bottom surface of the plate, as shown in gure 1(d). The normalized resistance change in each pair of electrodes shows orientation-dependent piezoresistive behavior led by the exural-strain-induced stretching and disrupted conductive network (gure 3). Figure 6 shows the

orientation-dependent piezoresistive behavior of (a) CM-250 buckypaper, (b) CM-250/M-5 (5:5) hybrid sheet and (c) CM-250/NGP (5:5) hybrid sheet. The buckypaper and hybrid sheets exhibit different percentage changes in resistance in longitudinal (between electrodes 4 and 5), transverse (between electrodes 2 and 7) and diagonal (between electrodes 1 and 8) directions. The percentage change in resistance is greatest in the longitudinal direction, as it is aligned in the direction of maximum tensile strain in the PMMA plate (gure 1(d)). On the contrary, negligible and intermediate percentage changes in resistance are observed in the transverse and diagonal directions, respectively, which is in accordance with the relative in-plane strains generated in the carbon nanomaterial sheets. It can be observed that hybrid sheets show a higher percentage change in resistance than that of buckypaper at the same strain level, which indicates the difference in the strain sensitivity, as hybrid sheets have a relatively loose inter-connected conductive network as compared to buckypapers. In addition, at 1% strain, the CM-250/NGP (5:5) hybrid sheet shows 27% higher percentage change in resistance than the CM-250/M-5 (5:5) hybrid sheet. The effects of M-5 and NGP content on the piezoresistivity of CM-250-based hybrid sheets are shown in gure 7. Both CM-250/M-5 and CM-250/NGP hybrid sheets show increasing percentage changes in resistance with increasing M-5 and NGP content. This is due to the fact that as the xGnP or NGP content increases, the conductive network in the hybrid sheet becomes more loosely bound, thus reducing its robustness and therefore increasing the sensitivity. The differences in the sensitivity of MWCNT buckypaper and MWCNTxGnP and MWCNTNGP hybrid sheets can be further elucidated by the schematic shown in gure 8. At the same MWCNT:xGnP/NGP ratio, the MWCNTxGnP hybrid

Figure 7. Effects of M-5 and NGP content on piezoresistivity in the longitudinal direction (R45) of CM-250-based hybrid sheets: (a) CM-250/M-5 hybrid sheets; (b) CM-250/NGP hybrid sheets.
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Acknowledgments
This work was supported by the National Research Foundation of Korea Grant funded by the Korean Government (project nos 2009-0070548, 2010-0023850).

References
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Figure 8. Schematic representation of microstructural changes in buckypaper and hybrid sheets subjected to mechanical strains.

sheet shows higher sensitivity than the MWCNTNGP hybrid sheet because of the large domains formed by pre-aggregated NGP particles. The larger the particle or domain size, the more easily the conductive network gets disrupted by external strains. On the other hand, ber-type MWCNTs form a much more robust conductive network, which results in lower strain sensitivity.

4. Conclusions
A series of MWCNT buckypapers and MWCNTxGnP/NGP hybrid sheets with varying MWCNT:xGnP and MWCNT:NGP ratios were prepared through vacuum ltration. Tensile loadings were applied to the carbon nanomaterial sheets, and their piezoresistive responses were analyzed. Inclusion of xGnP or NGP in buckypapers as well as the MWCNT:xGnP or MWCNT:NGP ratio is strongly correlated with the specic surface area of carbon nanomaterial sheets and the interactions among their constituents, both of which govern the sensitivity. It was revealed that at the same content ratio, the MWCNT/NGP hybrid sheet shows higher sensitivity than the buckypaper or the MWCNT/xGnP hybrid sheet. Also, sensitivity increases as xGnP or NGP content increases. Another critical nding is that using a multi-electrode scheme, a single buckypaper or hybrid sheet allows multi-directional strain measurement. The breadth of parameter selection combined with multi-directional sensing ability lays the groundwork for the development of self-sensing, smart materials and structures enabled by carbon nanomaterial sheets with great design exibility.

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[22] Lee D H, Lee J A, Lee W J and Kim S O 2011 Flexible eld emission of nitrogen-doped carbon nanotubes/reduced graphene hybrid lms Small 7 95100 [23] Jeong H Y, Lee D S, Choi H K, Lee D H, Kim J E, Lee J Y, Lee W J, Kim S O and Choi S-Y 2010 Flexible room-temperature NO2 gas sensors based on carbon nanotubes/reduced graphene hybrid lms Appl. Phys. Lett. 96 213105 [24] Liu Z B, Xu Y F, Zhang X Y, Zhang X L, Chen Y S and Tian J G 2009 Porphyrin and fullerene covalently functionalized graphene hybrid mterials with large nonlinear optical properties J. Phys. Chem. B 113 96816