A Review of Conductivity of Conductive Polymers; Polyaniline (Pani) and its Nanocomposites

Authors

  • Humphrey Darkeh Assem Department of Physics Kwame Nkrumah University Science and Technology Kumasi-Ghana (West Africa)
  • Mensah Samuel Agyei Department of Physics Kwame Nkrumah University Science and Technology Kumasi-Ghana (West Africa)
  • Reuben Yao Tamakloe Department of Physics Kwame Nkrumah University Science and Technology Kumasi-Ghana (West Africa)
  • Robert K. Nkum Department of Physics Kwame Nkrumah University Science and Technology Kumasi-Ghana (West Africa)

DOI:

https://doi.org/10.14738/aivp.122.16704

Keywords:

conducting polymers, four-point probe, electrical conductivity, nanocomposites, polyaniline, water-soluble polyaniline

Abstract

Doped and non-doped conducting polymers represent two distinct categories within the realm of conductive polymers. The conductivity observed in non-doped conjugated polymers is attributed to the presence of a conductivity band resembling that of metals. This conductivity arises from a specific molecular configuration, wherein three out of four valence electrons undergo localized sp2 hybridization, forming robust sigma bonds. The remaining unpaired electron of each carbon atom occupies a Pz orbital, which, upon overlap with adjacent Pz orbitals, creates a pi bond. The resulting delocalization of pi electrons facilitates conductivity, albeit at a relatively modest level. The demand for high-performance materials is particularly pronounced in mobile structural applications and the energy storage sector, encompassing aerospace and space exploration vehicles, unmanned aerial vehicles (UAVs), energy-efficient air and ground vehicles, satellites, smartphones, photovoltaic cells, and flexible electronics. Notably, advancements in electrochemical energy storage materials have been directed toward enhancing ion-storage capacity and cycle life. This review delves into the intricacies of electrical conductivity within conducting polymers, with a specific focus on polyaniline (PANI) and its emeraldine-based composites. The investigation encompasses various experimental configurations, culminating in the assertion that the electrical conductivity of conducting polymers is intricately linked to their intrinsic properties, doping mechanisms, and preparation techniques, including considerations of concentration and molecular weight. The utility of conducting polymers, particularly exemplified by polyaniline, extends to a wide array of technical applications, underscoring the ongoing research interest in optimizing their conductivity. Polyaniline's conductivity can be modulated through doping or reduction processes, while the incorporation of nanoparticles offers avenues for achieving enhanced conductivity. Moreover, the exploration of thermoelectric energy conversion holds promise for harnessing waste heat, thus further amplifying the relevance of conducting polymers in contemporary technological landscapes.

References

Aashis. S. Roy, Koppalkar.R.Anilkumar and M.V.N.Ambika Prasad; J.(2011) Appl. Poly. Sci, 121 pg. 67

Abbas Z.K. (2009) Ph.D. Thesis. Kingston University; London, UK: Intrinsically Conducting Polyaniline Blends.

Ahmed Al-Dulaimi A., Hashim S., Abdulrazak L. F., Husham M. (2018) Electrically conductive polyaniline in various nanostructures for corrosion inhibition of carbon steel. Journal of Mechanical Engineering and Sciences ISSN (Print): 2289-4659; e-ISSN: 2231-8380 Volume 12, Issue 2, pp. 3738-3749 DOI: https://doi.org/10.15282/jmes.12.2.2018.18.0330

Alig, I.; Lellinger, D.; Dudkin, S.M.; Pötschke, P. (2007) Conductivity spectroscopy on melt processed polypropylene-multiwalled carbon nanotube composites: Recovery after shear and crystallization. Polymer 2007, 48, 1020–1029.

Anbarasan R., Yelil A., Jeyakumari J. J. L., Sundaresan B. and Dhanalakshmi V. (2009) FTIR Spectroscopy: A Useful Tool for Structural Determination of Polyaniline and its Nanocomposites, Smithers Rapra Technology Polymers & Polymer Composites, Vol. 17, No. 7.

Armes S.P. (1987) Optimum reaction conditions for the polymerization of pyrrole by iron (III) chloride in aqueous solution. Synth. Mat. 20, 365–371.

Athawale A.A., Kulkarni M.V., Chabukswar V.V. (2002) Studies on chemically synthesized soluble acrylic acid doped polyaniline. Mater. Chem. Phys.73:106–110. doi: 10.1016/S0254-0584(01)00338-8.

Bailey, R.A., Persaud & K.C. (2000) ‘Sensing Volatile Chemicals Using Conducting Polymer Arrays’ in Polymer Sensors and Actuators, Osada, Y., De Rossi, D.E., Eds., Springer, Germany, vol. 5, pp. 419

Ban Â.G., Saniger Â.M., Hu H. (1999) Thin ® lms of polyaniline ± polyacrylic acid composite by chemical bath deposition. Thin Solid Films. 347:241–247.

Barros, R. A., Azevedo, W. M., & Aguiar, F. M. (2003). Photo-induced polymerization of polyaniline. Materials Characterization, 50, 131-134.

Bhadra, S., Khastgir, D., Singha, N. K., & Lee, J. H. (2009). Progress in preparation, processing and applications of polyaniline. Progress in polymer science, 34(8), 783-810.

Bordes R., Holmberg K. (2014) Amino acid-based surfactants-Do they deserve more attention? Adv. Colloid Interface Sci. 2015; 222:79–91. doi: 10.1016/j.cis.2014.10.013.

Bredas, J. L., & Street, G. B. (1985). Polarons, bipolarons, and solitons in conducting polymers. Accounts of chemical research, 18(10), 309-315.

Brycki B., Szulc A., Babkova M. (2020) Synthesis of silver nanoparticles with gemini surfactants as efficient capping and stabilizing agents. Appl. Sci. 11:154. doi: 10.3390/app11010154.

Casado U.M., Quintanilla R.M., Aranguren M.I., and Marcovich N.E. (2012). Composite films based on shape memory polyurethanes and nanostructured polyaniline or cellulose-polyaniline particles. Synthetic Metals 162, 1654-1664

Chattopadhyay D., and Bain M.K. (2008). Electrically conductive nanocomposites of polyaniline with poly (vinyl alcohol) and methylcellulose. Journal of Applied Polymer Science, 110, 2849-2853.

Chauhan, S. M., Mahida, J., & Chakrabarty, B. S. (2016). Dielectric property and conductivity study of polyaniline–CaF2 nanocomposites. J. Nano. Adv. Mater, 4, 9-17.

Chen P. Y., Hung H. L, Han C. C. and Chiu H. C. (2020) Langmuir, 36, 4153 —4164

Chiang C.K., Fincher Jr C.R., Park Y.W., Heeger A.J., Shirakawa H., Louis E.J., Gau S.C., (1997) MacDiarmid A.G.

Electrical conductivity in doped polyacetylene. Phys. Rev. Lett. 1977; 39:1098. doi: 10.1103/PhysRevLett.39.1098.

Damen M., Cristóbal-Lecina E., Sanmartí G. C., Van Dongen S. F. M., García C. L., (2014) Multifunctional Gemini Surfactants: Structure, Synthesis, Properties and Applications. doi: 10.5772/intechopen.68755

De Topologie I., Dynamique D., Paris U., Diderot D. (1999) Adsorption of human serum albumin onto polypyrrole powder and polypyrrole-silica nanocomposites. Synth. Met. 102:1419–1420. 113.

Detsri, E. and Thierry D. S. (2009) Interfacial Polymerization of Water-Soluble Polyaniline and Its Assembly Using the Layer-By-Layer Technique. Journal of Metals, Materials and Minerals. Vol.19 No.1 pp.39-44.

Detsri, E., & Dubas, S. T. (2009). Interfacial polymerization of water-soluble polyaniline and its assembly using the layer-by-layer technique. Journal of Metals, Materials and Minerals, 19(1).

Domingues S. H., Salvatierra R.V., Olveira M. M., Aldo J.G. Zarbin A. J.G., (2011). Transparent and conductive thin films of graphene/polyaniline nanocomposites prepared through interfacial polymerization, Chemical communication, 47,2592- 2594

Duchet J, Legras R& Demoustier-Champagne S. (1998) Chemical synthesis of polypyrrole: structure-properties relationship. Synth. Met. 98, 113–122.

Feast, W.J.; Tsibouklis, J.; Pouwer, K.L.; Groenendaal, L.; Meijer, E.W. (1996). "Synthesis, processing and material properties of conjugated polymers". Polymer 37 (22): 5017.

Fisal Alesary H., Khalil Ismail H., Fadhil Khudhair A., Qasim Mohammed M. (2018) Effects of Dopant Ions on the Properties of Polyaniline Conducting Polymer. Orient. J. Chem. 34:2525–2533. doi: 10.13005/ojc/340539.

Gorman, C. B. Ginsburg, E. J.; Grubbs, R. H. (1993) "Soluble, Highly Conjugated Derivatives of Polyacetylene from the Ring-Opening Metathesis Polymerization of Monosubstituted Cyclooctatetraenes: Synthesis and the Relationship Between Polymer Structure and Physical Properties" Journal of the American Chemical Society, (115) 1397-1409. doi:10.1021/ja00057a024

Guo X, Baumgarten M, Müllen K (2013) Designing π-conjugated polymers for organic electronics. Prog Poly Sci 38:1832–1908

Guo, K., Xi, B., Wei, R., Li, H., Feng, J., Xiong, S (2020) Hierarchical Microcables Constructed by CoP @ C ⊂ Carbon Framework Intertwined with Carbon Nanotubes for Efficient Lithium Storage. 1902913, 1–9. https://doi.org/10.1002/aenm.201902913

Haberko J., Raczkowska J., Bernasik A Rysz., J. Nocun´ M. Nizioł J., Łuzny W. (2008) Conductivity of Thin Polymer Films Containing Polyaniline molecular crystals and liquid crystals Volume 485-Issue 1 doi.org/10.1080/15421400801918112

Ho, K. S., Hsieh, K. H., Huang, S. K., & Hsieh, T. H. (1999). Polyurethane-based conducting polymer blends: I. Effect of chain extender. Synthetic Metals, 107(1), 65-73.

Huang, J., & Kaner, R. B. (2006). Handbook of conducting polymers: Processing and applications (3rd ed.).

Huegun, A.; Fernandez, M.; Muñoz, M.E.; Santamaria, A. (2012) Rheological properties and electrical conductivity of irradiated MWCNT/PP nanocomposites. Compos. Sci. Technol, 72, 1602–1607.

Hussin, Hazira & Gan, Seng Neon & Mohamad, Sutrisno & Phang, Sook. (2017). Synthesis of Water-soluble Polyaniline by Using Different Types of Cellulose Derivatives. Polymers and Polymer Composites. 25. 515-520. 10.1177/096739111702500702.

Inácio ÂS.; Mesquita K. A.; Baptista M.; Ramalho-Santos J.; Vaz W. L. C.; Vieira O. V. (2011) In Vitro Surfactant Structure-Toxicity Relationships: Implications for Surfactant Use in Sexually Transmitted Infection Prophylaxis and Contraception. PLoS One, 6, e19850 10.1371/journal.pone.0019850.

Inzelt G, Pineri M, Schultze J.W& Vorotyntsev M.A. (2000) Electron and proton conducting polymers: recent developments and prospects. Electrochim. Acta. 45, 2403–2421.

Jeevananda, T. (2003). Synthesis and characterization of polyaniline filled PU/PMMA interpenetrating polymer networks. European Polymer Journal, 39(3), 569-578.

Jeevananda, T., & Begum, M. (2001). Studies on polyaniline filled PU/PMA interpenetrating polymer networks. European polymer journal, 37(6), 1213-1218.

Jozefiak, T. H.; Ginsburg, E. J.; Gorman, C. B.; Grubbs, R. H.; Lewis, N. S. (1993)"Voltammetric Characterization of Soluble Polyacetylene Derivatives Obtained from the Ring-Opening Metathesis Polymerization (ROMP) of Substituted Cyclooctatetraenes" Journal of the American Chemical Society; volume 115, pages 4705-4713. doi:10.1021/ja00064a035

Kaynak, Akif and Foitzik, Richard. (2010). Synthesis and Characterization of Soluble Conducting Polymers. Resarch Journal of Textile and Apparel. 14. 10.1108/RJTA-14-02--B005.

Kumar D& Sharma R.C. (1998) Advances in conductive polymers. Eur. Polym. J. 34, 1053–1060.

Langsdorf, Brandi, L.; Zhou, Xin; Lonergan, Mark C. (2001), "Kinetic Study of the Ring-Opening Metathesis Polymerization of Ionically Functionalized Cyclooctatetraenes" Macromolecules, volume 34, pages 2450-2458. doi:10.1021/ma0020685

Laska J. (2004). Conformations of polyaniline in polymer blends. Journal of Molecular Structure 701, 13-18

Li J., Liu L., Zhang D., Yang d., Guo J. and Wei J. (2014) Fabrication of polyaniline/silver nanoparticles/multiwalled carbon nanotubes composites for flexible microelectronic circuits Science Direct Synthetic Metals (192),

Long, Y., Chen, Z., Wang, N., Li, J., & Wan, M. (2004). Electrical transport in POLYANILINE – CSA/POLYANILINE –DBSA polyblends. Physica B: Condensed Matter, 344, 82-87.

Lui, W., Kumar, J., & Tripathy, S. (1999). Enzymatically synthesized conducting polyaniline. Journal of the American Chemical Society, 121, 71-78.

MacDiarmid, A. G., Mammone, R. J., Kaner, R. B., & Porter, L. (1985). The concept of ‘doping’of conducting polymers: The role of reduction potentials. Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences, 314(1528), 3-15.

Maeda S., Ames S.P. (1995) Preparation and characterization of polypyrrole-tin (IV) oxide nanocomposite colloids. Chem. Mater.7:171–178. doi:10.1021/cm00049a026.

Mahnoush B., Suraya A. R., Suhaidi S., Amir Reza S., and Hong N. L. (2021) Preparations, Properties, and Applications of Polyaniline and Polyaniline Thin Films A Review Published online 2021 Jun 18. http://doi.org/10.3390/polym13122003

Manaf, Azwar & Hafizah, Mas & Riyadi, Ahmad & Andreas, (2019). Electrical conductivity of polyaniline (PANI) assisted by anionic surfactant through emulsion polymerization technique. Journal of Physics: Conference Series. 1153. 012067. 10.1088/1742-6596/1153/1/012067.

Modaka P., Kondawara S. B. and Nandanwarb D. V. (2014) Synthesis and characterization of conducting polyaniline/graphene nanocomposites for electromagnetic interference shielding. 2nd International Conference on Nanomaterials and Technologies Procedia Materials Science 10 (2015) 588 – 594

Mzenda V. M., Goodman S. A. and Auret F. D. (2002) Synth. Met., 127, 285 —289

Nagarajan R. (2018) Self-Assembly: From Surfactants to Nanoparticles; Nagarajan R., Ed.; Wiley & Sons Inc.: Hoboken, NJ, USA.

Nagarajan R. (2002) Molecular Packing Parameter and Surfactant Self-Assembly: The Neglected Role of the Surfactant Tail. Langmuir, 18, 31–38. 10.1021/la010831y

Naseem, S., Sajid, I., Irfan, M. S., Saeed, F., Manzoor, M., Qaiser, A., & Shehzad, M. A. (2015). Effect of Dopant Type on the Properties of Polyaniline Filled PU/PMMA Conducting Interpenetrating Polymer Networks. Progress in Rubber Plastics Recycling Technology, 32. https://doi.org/10.1177/147776061603200305

Patial P., Shaheen A., Ahmad I. Synthesis, (2014) characterization and evaluation of the surface-active properties of movel cationic imidazolium gemini surfactants. J. Surfactants Deterg. 17:253–260. doi: 10.1007/s11743-013-1472-2.

Patist A., Bhagwat S. S., Penfield K. W., Aikens P., and Shah D. O (2000) On the Measurement of Critical Concentrations of Pure and Technical-Grade Nonionic Surfactants. Center for Surface Science and Engineering, Department of Chemical and Anesthesiology, University of Florida, Gainesville, Florida 32611

Pei, J., Yu, W. L., Huang, W. & Heeger, A. J. (2000) A Novel Series of Efficient Thiophene-Based Light Emitting Conjugated Polymers and Application in Polymer Light Emitting Diodes’, Macromolecules, vol. 33, No. 7. Pp.

Pötschke, P.; Abdel-Goad, M.; Alig, I.; Dudkin, S.; Lellinger, D. (2004) Rheological and dielectrical characterization of melt mixed polycarbonate-multi walled carbon nanotube composites. Polymer 45, 8863–8870.

Riede A., Helmstedt M., Riede V., Zemek J., Stejskal J. (2000) In situ polymerized polyaniline films. 2. Dispersion polymerization of aniline in the presence of colloidal silica. Langmuir. 2000; 16:6240–6244. doi: 10.1021/la991414c.

Root S. E., Savagatrup S., Printz A. D., Rodriquez D. and Lipomi D. J. (2017) Chem. Rev., 117, 6467 —6499 Rose, Aleena & Prasad, Guru & Sakthivel, Thangavel & Venugopal, Gunasekaran & Maiyalagan, T & Srm

University, T.Vijayakumar. (2018). Electrochemical Analysis of Graphene Oxide/Polyaniline/Polyvinyl Alcohol Composite Nanofibers for Supercapacitor Applications. Applied Surface Science. 449. 10.1016/j.apsusc.02.224.

Sangroniz, A.; Gonzalez, A.; Martin, L.; Irusta, L.; Iriarte, M.; Etxeberria, A. (2019) Miscibility and degradation of polymer blends based on biodegradable poly (butylene adipate-co-terephthalate). Polym. Degrad. Stab., 151, 25–

Schwendeman, I., Hickman, R., Sonmez G., Scotland P., Song K., Welish, D. M. (2002) Electrochromism and Electrochromic Devices Dokumen. Cambridge University Press

Shao L., Qiu J., Liu M., Feng H., Lei L., Zhang G., Zhao Y., Gao C., and Qin L. (2011). Synthesis and characterization of water-soluble polyaniline films. Synthetic Metals 161, 806-811.

Sinha, S., Bhadra, S., & Khastgir, D. (2009). Effect of dopant type on the properties of polyaniline. Journal of Applied Polymer Science, 112(5), 3135-3140.

Stafstrom, S., & Chao, K. (1984). Polaron-bipolaron―soliton doping in polyacetylene. Physical review. B, Condensed matter, 30(4), 2098-2103.

Stafström, S.; Chao, K.A. (1984) Polaron-bipolaron–soliton doping in polyacetylene. Phys. 30, 2098–2103.

Stejskal J., Kratochvíl P., Jenkins A.D. (1996) The formation of polyaniline and the nature of its structures.

Polymer. 1996; 37:367–369. doi: 10.1016/0032-3861(96)81113-X.

Stejskal, J., & Gilbert, R. G. (2002). Polyaniline: The in-depth exploration of its properties and applications. Pure and Applied Chemistry, 74, 857.

Stejskal, J., & Sapurina, I. (2005). Polyaniline: Thin films and colloidal dispersions (IUPAC Technical Report). Pure and Applied Chemistry, 77(5), 815-826.

Stejskal, J., Sapurina, I., Prokeš, J., & Zemek, J. (1999). Synthesis of polyaniline: A conducting polymer with extraordinary properties. Synthetic Metals, 105, 195.

Suthar, B. B. A. U. O. D., Xiao, H. X., Klempner, D. B. A. U. O. D., & Frisch, K. C. (1996). A review of kinetic studies on the formation of interpenetrating polymer networks. Polymers for Advanced Technologies, 7(4), 221-233.

Toshima N., Yan H. (1995) Chemical preparation of polyaniline and its derivatives by using cerium (IV) sulfate. Novel preparation of polyxylidines. Bull. Chem. Soc. Jpn. 68:1056–1063. doi: 10.1246/bcsj.68.1056.

Tsukamoto, J. (1992) Recent advances in highly conductive polyacetylene. Adv. Phys., 41, 509–546.

Tsukamoto, J.; Takahashi, A.; Kawasaki, K. (1990) Structure and electrical properties of polyacetylene yielding a conductivity of 105 S/cm. Jpn. J. Appl. Phys., 29, 125

Valentino, O.; Sarno, M.; Rainone, N.G.; Nobile, M.R.; Ciambelli, P.; Neitzert, H.C.; Simon, G.P. (2008) Influence of the polymer strcture and nanotibe concentration on the conductivity and rheological properties of polyethylene/CNT composites. Physics E, 40, 2440–2445.

Valter B., Carrara S., Ram M.K. and Nicolin C., Langmuir, 20 (2004) FTIR: Spectroscopy: A Useful Tool for Structural Determination of Polyaniline and its Nanocomposites. Sage Journals. doi.org/10.1177/096739110901700703

Vijaykumar B. C., Sharanappa G. and Sangshetty K. (2018) Conductivity Study of Polyaniline/ZnFe2O4 Composites JETIR July 2018, Volume 5, Issue 7. www.jetir.org (ISSN-2349-5162)

Vinarov Z., Dobreva P., Tcholakova S. (2018) Effect of surfactant molecular structure on progesterone solubilization. Journal of drug delivery science and technology, 43 (2018), pp. 44-49

Wan M. (2008) Conducting Polymers with Micro or Nanometer Structure. Springer; Berlin/Heidelberg, Germany

Wang Y. and Levon K. (2012) Macromol. Symp., 317–318, 240 —247.

Wang X. S., Tang H. P., Li X. D and Hua K., Int. J. Mol. Sci., 2009, 10, 5257 —5284

Yenwo, G. M., Sperling, L. H., Pulido, J., Manson, J. A., & Conde, A. (1977). Castor oil-based interpenetrating polymer networks, IV. Mechanical behavior. Polymer Engineering & Science, 17(4), 251-256.

Zheng, X.F.; Liu, C.X.; Yan, Y.Y.; Wang, Q. (2014) A review of thermoelectric research—Recent developments and potentials for sustainable and renewable energy applications. Renew. Sustain. Energy Review, (32) 486–503.

Ziyafaddin H.A., Gulnara A.A., Ravan A.R., Seyid-Zeynab F.H., Yusif A., Etibar H.I., Samira A.S., Nahida Z.A., Jochen A. (2020) Aggregation and antimicrobial properties of gemini surfactants with mono- and di-(2-hydroxypropyl) ammonium head-groups: Effect of the spacer length and computational studies. J. Mol. Liq. 302:112579

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Published

2024-04-13

How to Cite

Assem, H. D., Agyei, M. S., Tamakloe, R. Y., & Nkum, R. K. (2024). A Review of Conductivity of Conductive Polymers; Polyaniline (Pani) and its Nanocomposites. European Journal of Applied Sciences, 12(2), 241–270. https://doi.org/10.14738/aivp.122.16704