- NANO EXPRESS
- Open Access
Investigating the Inter-Tube Conduction Mechanism in Polycarbonate Nanocomposites Prepared with Conductive Polymer-Coated Carbon Nanotubes
© Ventura et al. 2015
Received: 17 September 2015
Accepted: 7 December 2015
Published: 16 December 2015
A well-known strategy to improve the electrical conductivity of polymers is to dope them with high-aspect-ratio and conductive nanoparticles such as carbon nanotubes (CNTs). However, these nanocomposites also exhibit undesirable properties such as damage-sensitive and history-dependent conductivity because their macroscopic electrical conductivity is largely determined by the tunneling effect at the tube/tube interface. To reduce these issues, new nanocomposites have been developed with CNTs that have been coated with a conductive layer of poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT/PSS). It has been posited that the insulating region between the CNTs is replaced by a conductive polymer bridge; this has not been proven up to now. We propose here to investigate in-depth how the macroscopic conductivity of these materials is changing when (1) varying the frequency of the electrical loading (impedance spectroscopy), (2) varying the mechanical hydrostatic pressure, and (3) varying the voltage of the electrical loading. The response is systematically compared to the one of conventional carbon nanotube/polycarbonate (CNT/PC) nanocomposites so we can clarify how efficiently the tunneling effect is suppressed from these composites. The objective is to elucidate further the mechanism for conduction in such material formulations.
A carbon nanotube/polymer nanocomposite can be described as a percolated network of conductive fillers embedded in an insulating matrix. Its macroscopic electrical conductivity is mainly dominated by the inter-particle junction behavior .
In direct current (DC) conditions, the junction behavior has been explained by the tunneling effect  which described how charge carriers travel through the insulating barrier (typically 0.5 to 2 nm thick) from one electrode to another. With this model, the junction can be represented as a resistive element, the resistance of which depends on strain, temperature, and voltage .
However, analysis of nanocomposites in the frequency-dependent domain has revealed that the AC conductivity of conductive particle-filled nanocomposites follows the universal AC behavior of disordered solids [4–6]. In general, this signifies that the real part of the AC complex conductivity increases with frequency following a classical power law [3, 7, 8]. Experimental observation of the AC behavior from dielectric and resistive frameworks have led to the description of an equivalent electrical circuit in which the inter-particle junctions are represented as Voigt elements (combination of a resistive and a capacitive part in parallel configuration) [5, 9]. The frequency dependency of the purely resistive part has been explained in terms of the characteristic percolated network microstructure. While in DC the charge carriers must travel along the percolated path throughout the sample, in AC, they only travel a probed distance which is inversely proportional to the frequency. As the probe distance is smaller with increasing frequency, many charge carriers travel mostly within favorable paths such as low-resistance junctions and nanoparticle bundles while highly resistive junctions are avoided [5, 7–11]. On the other hand, the capacitive element arises from the dielectric properties of the resin separating the conductive electrodes (the carbon nanotubes (CNTs)). Thus, under the influence of an AC, the charges accumulate on the junction and create polarization effects . The frequency dependency of this element has also been described by works measuring the dielectric constant [4, 12, 13].
Recently, we have investigated the electrical and thermal properties and piezoresistive behavior of multiwall carbon nanotubes (MWCNTs)/polycarbonate (PC) nanocomposites in which the MWCNTs have been coated with the conductive polymer poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT/PSS) via a solution method [14, 15]. Our observations suggest that the MWCNTs are responsible for the construction of the percolated network, but the charge carrier transport is done through the PEDOT/PSS coatings.
The objective of this study is to clarify how the charge transfer mechanism is affected by the presence of the PEDOT/PSS coating at the inter-tube junctions. In particular, we observe the frequency dependency of the resistive and capacitive parts by performing a single electrical impedance spectroscopy experiment. We also present the results of the effect of hydrostatic pressure on conductivity and the voltage-current behavior. By comparing the electrical responses of this material with the expected features of classical nanocomposites, we can get some information about the efficiency of the PEDOT/PSS coating in replacing the insulating resin at the tube/tube interface.
Rectangular samples (60 mm ± 0.5 × 10 mm ± 0.5 × 300 μm ± 30) are prepared by casting and hot pressing for E-CNT/PC and CNT/PC nanocomposites  and equipping with silver paint electrodes (gauge length: 25 mm ± 0.5). Thin film samples of EPP (rectangular samples: 30 mm ± 0.5 × 6 mm ± 1 × 40 μm ± 0.5) were also prepared by spin-casting process to investigate the response of the PEDOT/PSS coating itself, which has never been reported. These were also equipped with silver paint electrodes separated by 19 mm.
We systematically investigated the change in electrical conductivity when these formulations are subjected to (1) AC frequency sweep, (2) hydrostatic pressure sweep, and (3) DC voltage sweep.
For the electrical impedance spectroscopy (EIS), the resistance and reactance of the samples were measured simultaneously with an Agilent E4980A Precision LCR meter in a four-probe configuration using Kelvin clips. The frequency range spans from 20 Hz to 2 MHz. The AC electrical conductivity and the tan δ were calculated accordingly.
For hydrostatic pressure testing, the samples were placed inside an air pressurized container in which the pressure could be regulated from 1 to 20 bar while the resistance of the samples was measured using a four-probe technique with an Agilent 1252B multimeter. Finally, the electrical conductivity, σ, with respect to electric field, E, was obtained from V-I curves using a Keithley 4200 semiconductor parameter analyzer and a Cascade probe station.
Results and Discussion
Finally, Fig. 3 b shows the change in conductivity of PC nanocomposites with respect to the applied DC electric field. Polymer nanocomposites usually display a non-ohmic behavior [16, 17] which is a consequence of the non-linear effective resistance of the tunneling junctions . As expected, this effect is noticeable in our CNT/PC samples in which inter-tube tunneling is the driving effect. This effect gets very attenuated in E-CNT composites. This is a first indication that tunneling is replaced by less voltage-dependant mechanisms in this new formulation.
The results of the presented characterization techniques indicated that the presence of the EPP coating on the MWCNTs changes dramatically the electrical behavior of the percolated network of CNTs at the level of the inter-tube junctions. In CNT/PC samples, the junction behavior is dependant on the distance between fillers. It can be represented by a Voigt element (a combination between a resistive and a capacitive element), albeit the resistance and the capacitance are themselves frequency dependent as the probing distance becomes smaller with increasing frequency. On the other hand, in E-CNT/PC samples, the junctions are replaced by a conductive polymer bridge with a purely resistive behavior. The existence of this bridge is here fully demonstrated by its impact of the macroscopic response to voltage sweep, frequency sweep, and pressure sweep.
Funding for this work was provided from King Abdullah University of Science and Technology (KAUST) baseline funds. The authors are grateful to KAUST for its financial support.
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- Bao W, Meguid S, Zhu Z, Weng G (2012) Tunneling resistance and its effect on the electrical conductivity of carbon nanotube nanocomposites. J Appl Phys 111(9): 093726.View ArticleGoogle Scholar
- Simmons JG (1963) Generalized formula for the electric tunnel effect between similar electrodes separated by a thin insulating film. J Appl Phys 34(6): 1793–1803.View ArticleGoogle Scholar
- Barrau S, Demont P, Peigney A, Laurent C, Lacabanne C (2003) DC and AC conductivity of carbon nanotubes-polyepoxy composites. Macromolecules 36(14): 5187–5194.View ArticleGoogle Scholar
- Jonscher AK (1977) The ’universal’ dielectric response. Nat 267(5613): 673–679.View ArticleGoogle Scholar
- Dyre JC, Schrøder TB (2000) Universality of AC conduction in disordered solids. Rev Mod Phys 72: 873–892.View ArticleGoogle Scholar
- Dyre JC (1988) The random free-energy barrier model for ac conduction in disordered solids. J Appl Phys 64(5): 2456–2468.View ArticleGoogle Scholar
- Curran SA, Talla J, Dias S, Zhang D, Carroll D, Birx D (2009) Electrical transport measurements of highly conductive carbon nanotube/poly(bisphenol a carbonate) composite. J Appl Phys 105(7): 073711.View ArticleGoogle Scholar
- Kilbride BE, Coleman JN, Fraysse J, Fournet P, Cadek M, Drury A, Hutzler S, Roth S, Blau WJ (2002) Experimental observation of scaling laws for alternating current and direct current conductivity in polymer-carbon nanotube composite thin films. J Appl Phys 92(7): 4024–4030.View ArticleGoogle Scholar
- Garrett MP, Ivanov IN, Gerhardt RA, Puretzky AA, Geohegan DB (2010) Separation of junction and bundle resistance in single wall carbon nanotube percolation networks by impedance spectroscopy. Appl Phys Lett 97(16): 163105.View ArticleGoogle Scholar
- Psarras GC (2006) Hopping conductivity in polymer matrix-metal particles composites. Compos Part A: Appl Sci Manuf 37(10): 1545–1553.View ArticleGoogle Scholar
- Masenelli-Varlot K, Chazeau L, Gauthier C, Bogner A, Cavaille JY (2009) The relationship between the electrical and mechanical properties of polymer-nanotube nanocomposites and their microstructure. Compos Sci Technol 69(10): 1533–1539.View ArticleGoogle Scholar
- Risi CLS, Hattenhauer I, Ramos A, Coelho LAF, Pezzin SH (2015) A contribution from dielectric analysis to the study of the formation of multi-wall carbon nanotubes percolated networks in epoxy resin under an electric field. Mater Chem Phys 160(0): 289–295.View ArticleGoogle Scholar
- Panteny S, Stevens R, Bowen C (2005) The frequency dependent permittivity and AC conductivity of random electrical networks. Ferroelectr 319(1): 199–208.View ArticleGoogle Scholar
- Zhou J, Lubineau G (2013) Improving the electrical conductivity in polycarbonate nanocomposites using highly conductive PEDOT/PSS coated MWCNTs. ACS Appl Mater Interfaces 5: 6189–6200.View ArticleGoogle Scholar
- Zhou J, Aguilar Ventura I, Lubineau G (2014) Probing the role of poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonate)-coated multiwalled carbon nanotubes in the thermal and mechanical properties of polycarbonate nanocomposites. Ind Eng Chem Res 53(9): 3539–3549.View ArticleGoogle Scholar
- Wichmann MHG, Buschhorn ST, Gehrmann J, Schulte K (2009) Piezoresistive response of epoxy composites with carbon nanoparticles under tensile load. Phys Rev B 80: 245437.View ArticleGoogle Scholar
- Benoit J, Corraze B, Chauvet O (2002) Localization, coulomb interactions and electrical heating in single-wall carbon nanotubes/polymer composites. Phys Rev B 65: 241405.View ArticleGoogle Scholar