Graphene  Vol.4 No.1 , January 2015
Investigation of the Electro-Mechanical Behavior of Hybrid Polyaniline/Graphene Nanocomposites Fabricated by Dynamic Interfacial Inverse Emulsion Polymerization
This paper describes a study on electrical resistivity under loading of polyaniline (PANI)/graphene nanocomposite powders and compacts. The composites were prepared by an in-situ interfacial dynamic inverse emulsion polymerization technique under sonication of aniline in the presence of graphene sheets in chloroform. During polymerization the graphene nanoplatelets are coated with PANI and are well dispersed both in the polymeric suspension and then in the dried polymer matrix as evidenced by cryogenic transmission electron microscopy (Cryo-TEM) and high resolution scanning microscopy (HRSEM). The presence of graphene nanoplatelets lowers the electrical resistivity of the polyaniline by two orders of magnitude for both the powder and the compact composites as demonstrated by their electrical resistance measurements conducted under loading. The lowest measured electrical resistivity values were 5 Ω·cm for 33% wt. graphene powder and 8 Ω·cm for 41% wt. graphene compacted composites. Cyclic electrical measurements under loading showed a distinct reproducible dependence of the bulk resistivity vs. applied pressure. This repetition is a key component for electro-mechanical sensors. To the authors’ best knowledge, this is the first report on polymerization of aniline in presence of graphene by the in-situ interfacial dynamic inverse emulsion polymerization technique and also the first report on cyclic electrical measurements under pressure of PANI/graphene nanocomposites.

Cite this paper
Regueira, R. , Suckeveriene, R. , Brook, I. , Mechrez, G. , Tchoudakov, R. and Narkis, M. (2015) Investigation of the Electro-Mechanical Behavior of Hybrid Polyaniline/Graphene Nanocomposites Fabricated by Dynamic Interfacial Inverse Emulsion Polymerization. Graphene, 4, 7-19. doi: 10.4236/graphene.2015.41002.
[1]   Mukhopadhyay, P. and Gupta, R.K. (2012) Graphite, Graphene, and Their Polymer Nanocomposites. CRC, Boca Raton.

[2]   Rosen-Kligvasser, J., Suckeveriene, R.Y., Tchoudakov, R. and Narkis, M. (2013) A Novel Methodology for Controlled Migration of Antifog from Thin Polyolefin Films. Polymer Engineering & Science, 54, 2023-2028.

[3]   Peng, R., Wang, Y., Tang, W., Yang, Y. and Xie, X. (2013) Progress in Imidazolium Ionic Liquids Assisted Fabrication of Carbon Nanotube and Graphene Polymer Composites. Polymers, 5, 847-872.

[4]   Fakirov, S. (2013) Nano- and Microfibrillar Single-Polymer Composites: A Review. Macromolecular Materials and Engineering, 298, 9-32.

[5]   Byrne, M.T. and Gun’ko, Y.K. (2010) Recent Advances in Research on Carbon Nanotube-Polymer Composites. Advanced Materials, 22, 1672-1688.

[6]   Paul, D.R. and Robeson, L.M. (2008) Polymer Nanotechnology: Nanocomposites. Polymer, 49, 3187-3204.

[7]   Suckeveriene, R.Y., Mechrez, G., Filiba, H.O., Mosheev, S. and Narkis, M. (2012) Synthesis of Hybrid Polyaniline/ Carbon Nanotubes Nanocomposites in Toluene by Dynamic Interfacial Inverse Emulsion Polymerization under Sonication. Journal of Applied Polymer Science, 128, 2129-2135.

[8]   Geim, A.K. and Novoselov, K.S. (2007) The Rise of Graphene. Nature Materials, 6, 183-191.

[9]   Novoselov, K.S., Geim, A.K, Morozov, S.V., Jiang, D., Zhang, Y., Dubonos, S.V., Grigorieva, I.V. and Firsov, A.A. (2004) Electric Field Effect in Atomically Thin Carbon Films. Science, 306, 666-669.

[10]   Novoselov, K.S., Geim, A.K, Morozov, S.V., Jiang, D., Katsnelson, M.I., Grigorieva, I.V., Dubonos, S.V. and Firsov, A.A. (2005) Two-Dimensional Gas of Massless Dirac Fermions in Graphene. Nature, 438, 197-200.

[11]   Kuila, T., Bose, S., Mishra, A.K., Khanra, P., Kim, N.H. and Lee, J.H. (2012) Chemical Functionalization of Graphene and Its Applications. Progress in Materials Science, 57, 1061-1105.

[12]   Ebrahimi, F. (2012) Nanocomposites—New Trends and Developments. InTech, Rijeka.

[13]   Nicolais, L., Borzacchiello, A. and Lee, S.M. (2012) Wiley Encyclopedia of Composites. 2nd Edition, John Wiley & Sons, Inc., Hoboken.

[14]   Ciric-Marjanovic, G. (2013) Recent Advances in Polyaniline Research: Polymerization Mechanisms, Structural Aspects, Properties and Applications. Synthetic Metals, 177, 1-47.

[15]   Sapurina, I. and Stejskal, J. (2008) The Mechanism of the Oxidative Polymerization of Aniline and the Formation of Supramolecular Polyaniline Structures. Polymer International, 57, 1295-1325.

[16]   Leea, H.Y., Rwei, S.P., Wang, L. and Chen, P.H. (2008) Preparation and Characterization of Core-Shell Polyaniline- Polystyrene Sulfonate@Fe3O4 Nanoparticles. Materials Chemistry and Physics, 112, 805-809.

[17]   Li, Z.H. and Wang, Y.W. (2010) Characterization of Polyaniline/Ag Nanocomposites Using H2O2 and Ultrasound Radiation for Enhancing Rate. Polymer Composites, 31, 1662-1668.

[18]   Jeon, I.Y., Tan, L.S. and Baek, J.B. (2010) Synthesis and Electrical Properties of Polyaniline/Polyaniline Grafted Multiwalled Carbon Nanotube Mixture via in Situ Static Interfacial Polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 48, 1962-1972.

[19]   Li, S., Gan, M., Ma, L., Yan, J., Tang, J., Fu, D., Li, Z. and Bai, Y. (2013) Preparation and Microwave Absorbing Properties of Polyaniline-Modified Silicon Carbide Composites. High Performance Polymers, 25, 901-906.

[20]   Suckeveriene, R.Y., Zelikman, E., Mechrez, G., Tzur, A., Frisman, I., Cohen, Y. and Narkis, M. (2011) Synthesis of Hybrid Polyaniline/Carbon Nanotube Nanocomposites by Dynamic Interfacial Inverse Emulsion Polymerization under Sonication. Journal of Applied Polymer Science, 120, 676-682.

[21]   Wang, H., Hao, Q., Yang, X., Lu, L. and Wang, X. (2010) A Nanostructured Graphene/Polyaniline Hybrid Material for Supercapacitors. Nanoscale, 2, 2164-2170.

[22]   Fan, Y., Liu, J.H., Yang, C.P., Yu, M. and Liu, P. (2011) Graphene-Polyaniline Composite Film Modi?ed Electrode for Voltammetric Determination of 4-Aminophenol. Sensors and Actuators B, 157, 669-674.

[23]   Radhapyari, K., Kotoky, P., Das, M.R. and Khan, R. (2013) Graphene-Polyaniline Nanocomposite Based Biosensor for Detection of Antimalarial Drug Artesunate in Pharmaceutical Formulation and Biological Fluids. Talanta, 111, 47-53.

[24]   Salavagione, H.J., Martinez, G. and Ellis, G. (2011) Recent Advances in the Covalent Modification of Graphene with Polymer. Macromolecular Rapid Communications, 32, 1771-1789.

[25]   Bai, H., Xu, Y., Zhao, L., Li, C. and Shi, G. (2009) Non-Covalent Functionalization of Graphene Sheets by Sulfonated Polyaniline. Chemical Communications, 13, 1667-1669.

[26]   Tkalya, E.E., Ghislandi, M., de With, G. and Koning, C.E. (2012) The Use of Surfactants for Dispersing Carbon Nanotubes and Graphene to Make Conductive Nanocomposites. Current Opinion in Colloid & Interface Science, 17, 225- 232.

[27]   Shan, C., Yang, H., Han, D., Zhang, Q., Ivaska, A. and Niu, L. (2009) Water-Soluble Graphene Covalently Functionalized by Biocompatible Poly-L-Lysine. Langmuir, 25, 12030-12033.

[28]   Odian, G. (2004) Principles of Polymerization. 4th Edition, John Wiley & Sons, Inc., Hoboken.

[29]   Bovey, F.A., Kolthoff, I.M., Medalia, A.I. and Meehan, E.J. (1955) Emulsion Polymerization. Interscience Publishers, Inc., New York.

[30]   Zelikman, E., Suckeveriene, R.Y., Mechrez, G. and Narkis, M. (2010) Fabrication of Composite Polyaniline/CNT Nano?bers Using an Ultrasonically Assisted Dynamic Inverse Emulsion Polymerization Technique. Polymers for Advanced Technologies, 21, 150-152.

[31]   Nordstrom, J., Klevan, I. and Alderborn, G. (2012) A Protocol for the Classification of Powder Compression Characteristics. European Journal of Pharmaceutics and Biopharmaceutics, 80, 209-216.

[32]   Montes, J.M., Cuevas, F.G., Cintas, J. and Urban, P. (2011) Electrical Conductivity of Metal Powders under Pressure. Applied Physics A, 105, 935-947.

[33]   Han, B.G., Han, B.Z. and Ou, J.P. (2009) Experimental Study on Use of Nickel Powder-Filled Portland Cement-Based Composite for Fabrication of Piezoresistive Sensors with High Sensitivity. Sensors and Actuators A: Physical, 149, 51-55.

[34]   Han, B.G., Yu, Y., Han, B.Z. and Ou, J.P. (2008) Development of a Wireless Stress/Strain Measurement System Integrated with Pressure-Sensitive Nickel Powder-Filled Cement-Based Sensors. Sensors and Actuators A: Physical, 147, 536-543.

[35]   Kawakita, K. and Tsutsmui, Y. (1966) A Comparison of Equations for Powder Compression. Bulletin of the Chemical Society of Japan, 39, 1364-1368.

[36]   Hauptmann, P. (1993) Sensors Principles and Applications. Carl Hanser Verlag, Munich.

[37]   Costa, P., Ferreira, A., Sencadas, V., Viana, J.C. and Lanceros-Mendez, S. (2013) Electro-Mechanical Properties of Triblock Copolymer Styrene-Butadiene-Styrene/Carbon Nanotube Composites for Large Deformation Sensor Applications. Sensors and Actuators A, 201, 458-467.

[38]   Hwang, S.H., Park, H.W. and Park, Y.B. (2013) Piezoresistive Behavior and Multi-Directional Strain Sensing Ability of Carbon Nanotube-Graphene Nanoplatelet Hybrid Sheets. Smart Materials and Structures, 22, Article ID: 015013.

[39]   Li, W., He, D. and Bai, J. (2014) The Influence of Nano/Micro Hybrid Structure on the Mechanical and Self-Sensing Properties of Carbon Nanotube-Microparticle Reinforced Epoxy Matrix Composite. Composites Part A, 54, 28-36.

[40]   Ku-Herrera, J.J., Aviles, F. and Seidel, G.D. (2013) Self-Sensing of Elastic Strain, Matrix Yielding and Plasticity in Multiwall Carbon Nanotube/Vinyl Ester Composites. Smart Materials and Structures, 22, Article ID: 085003.

[41]   Talmon, Y. (1999) Cryogenic Temperature Transmission Electron Microscopy in the Study of Surfactant Systems. Surfactant Science Series, 83, 147-178.

[42]   Kim, D.K., Oh, K.W. and Kim, S.H. (2008) Synthesis of Polyaniline/Multiwall Carbon Nanotube Composite via Inverse Emulsion Polymerization. Journal of Polymer Science Part B: Polymer Physics, 46, 2255-2266.

[43]   Haba, Y., Segal, E., Narkis, M., Titelman, G.I. and Siegmann, A. (1999) Polymerization of Aniline in the Presence of DBSA in an Aqueous Dispersion. Synthetic Metals, 106, 59-66.

[44]   Oyefusia, A., Olanipekuna, O., Neelgund, G.M., Peterson, D., Stone, J.M., Williams, E., Carson, L., Regisfor, G. and Oki, A. (2014) Hydroxyapatite Grafted Carbon Nanotubes and Graphene Nanosheets: Promising Bone Implant Materials. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 132, 410-416.

[45]   Ran, S., Chen, C., Guo, Z. and Fang, Z. (2014) Char Barrier Effect of Graphene Nanoplatelets on the Flame Retardancy and Thermal Stability of High-Density Polyethylene Flame-Retarded by Brominated Polystyrene. Journal of Applied Polymer Science, 131, 40520.

[46]   Xu, J., Liu, J. and Li, K. (2014) Application of Functionalized Graphene Oxide in Flame Retardant Polypropylene. Journal of Vinyl and Additive Technology, Early View.

[47]   Marinho, B., Ghislandi, M., Tkalya, E., Koning, C.E. and de With, G. (2012) Electrical Conductivity of Compacts of Graphene, Multi-Wall Carbon Nanotubes, Carbon Black, and Graphite Powder. Powder Technology, 221, 351-358.

[48]   Wang, D.W., Li, F., Zhao, J., Ren, W., Chen, Z.G., Tan, J., Wu, Z.S., Gentle, I., Lu, G.Q. and Cheng, H.M. (2009) Fabrication of Graphene/Polyaniline Composite Paper via in Situ Anodic Electro Polymerization for High-Performance Flexible Electrode. ASC Nano, 3, 1745-1752.

[49]   Valentova, H. and Stejskal, J. (2010) Mechanical Properties of Polyaniline. Synthetic Metals, 160, 832-834.