Abstract
The present study introduces a systematic approach to disperse graphene oxide (GO) during emulsion polymerization (EP) of Polyaniline (PANI) to form nanocomposites with improved electrical conductivities. PANI/GO samples were fabricated by loading different weight percents (wt%) of GO through modified in situ EP of the aniline monomer. The polymerization process was carried out in the presence of a functionalized protonic acid such as dodecyl benzene sulfonic acid, which acts both as an emulsifier and protonating agent. The microstructure of the PANI/GO nanocomposites was studied by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV–Vis spectrometry, Fourier transform infrared, differential thermal, and thermogravimetric analyses. The formed nanocomposites exhibited superior morphology and thermal stability. Meanwhile, the electrical conductivities of the nanocomposite pellets pressed at different applied pressures were determined using the four-probe analyzer. It was observed that the addition of GO was an essential component to improving the thermal stability and electrical conductivities of the PANI/GO nanocomposites. The electrical conductivities of the nanocomposites were considerably enhanced as compared to those of the individual PANI samples pressed at the same pressures. An enhanced conductivity of 474 S/m was observed at 5 wt% GO loading and an applied pressure of 6 t. Therefore, PANI/GO composites with desirable properties for various semiconductor applications can be obtained by in situ addition of GO during the polymerization process.
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Han D, Chu Y, Yang L, Liu Y, Lv Z (2005) Reversed micelle polymerization: a new route for the synthesis of DBSA–polyaniline nanoparticles. Colloids Surf A 259(1–3):179–187. doi:10.1016/j.colsurfa.2005.02.017
Liu N, Luo F, Wu H, Liu Y, Zhang C, Chen J (2008) One-step ionic-liquid-assisted electrochemical synthesis of ionic-liquid-functionalized graphene sheets directly from graphite. Adv Funct Mater 18(10):1518–1525
Cassagneau T, Guérin F, Fendler JH (2000) Preparation and characterization of ultrathin films layer-by-layer self-assembled from graphite oxide nanoplatelets and polymers. Langmuir 16(18):7318–7324. doi:10.1021/la000442o
Wilson NR, Pandey PA, Beanland R, Young RJ, Kinloch IA, Gong L, Liu Z, Suenaga K, Rourke JP, York SJ, Sloan J (2009) Graphene oxide: structural analysis and application as a highly transparent support for electron microscopy. ACS Nano 3(9):2547–2556. doi:10.1021/nn900694t
Rourke JP, Pandey PA, Moore JJ, Bates M, Kinloch IA, Young RJ, Wilson NR (2011) The real graphene oxide revealed: stripping the oxidative debris from the graphene-like sheets. Angew Chem Int Ed 50(14):3173–3177. doi:10.1002/anie.201007520
Thomas HR, Valles C, Young RJ, Kinloch IA, Wilson NR, Rourke JP (2013) Identifying the fluorescence of graphene oxide. J Mater Chem C 1(2):338–342. doi:10.1039/c2tc00234e
Bora C, Dolui SK (2012) Fabrication of polypyrrole/graphene oxide nanocomposites by liquid/liquid interfacial polymerization and evaluation of their optical, electrical and electrochemical properties. Polymer 53(4):923–932. doi:10.1016/j.polymer.2011.12.054
Jiang X, Drzal LT (2011) Improving electrical conductivity and mechanical properties of high density polyethylene through incorporation of paraffin wax coated exfoliated graphene nanoplatelets and multi-wall carbon nano-tubes. Compos Part A 42(11):1840–1849. doi:10.1016/j.compositesa.2011.08.011
Yang N, Zhai J, Wan M, Wang D, Jiang L (2010) Layered nanostructures of polyaniline with graphene oxide as the dopant and template. Synth Met 160(15–16):1617–1622. doi:10.1016/j.synthmet.2010.05.029
Kumar NA, Choi H-J, Shin YR, Chang DW, Dai L, Baek J-B (2012) Polyaniline-grafted reduced graphene oxide for efficient electrochemical supercapacitors. ACS Nano 6(2):1715–1723. doi:10.1021/nn204688c
Kuilla T, Bhadra S, Yao D, Kim NH, Bose S, Lee JH (2010) Recent advances in graphene based polymer composites. Prog Polym Sci 35(11):1350–1375. doi:10.1016/j.progpolymsci.2010.07.005
Yu L, Zhang Y, Tong W, Shang J, Lv F, Chu PK, Guo W (2012) Hierarchical composites of conductivity controllable polyaniline layers on the exfoliated graphite for dielectric application. Compos Part A 43(11):2039–2045. doi:10.1016/j.compositesa.2012.06.001
Zhao Y, Tang G-S, Yu Z–Z, Qi J-S (2012) The effect of graphite oxide on the thermoelectric properties of polyaniline. Carbon 50(8):3064–3073. doi:10.1016/j.carbon.2012.03.001
Xu LQ, Liu YL, Neoh K-G, Kang E-T, Fu GD (2011) Reduction of graphene oxide by aniline with its concomitant oxidative polymerization. Macromol Rapid Commun 32(8):684–688. doi:10.1002/marc.201000765
Wang D-W, Li F, Zhao J, Ren W, Chen Z-G, Tan J, Wu Z-S, Gentle I, Lu GQ, Cheng H-M (2009) Fabrication of graphene/polyaniline composite paper via in situ anodic electropolymerization for high-performance flexible electrode. ACS Nano 3(7):1745–1752. doi:10.1021/nn900297m
Murugan AV, Muraliganth T, Manthiram A (2009) Rapid, facile microwave-solvothermal synthesis of graphene nanosheets and their polyaniline nanocomposites for energy strorage. Chem Mater 21(21):5004–5006. doi:10.1021/cm902413c
Chiang J-C, MacDiarmid AG (1986) ‘Polyaniline’: protonic acid doping of the emeraldine form to the metallic regime. Synth Met 13(1–3):193–205. doi:10.1016/0379-6779(86)90070-6
Österholm J-E, Cao Y, Klavetter F, Smith P (1994) Emulsion polymerization of aniline. Polymer 35(13):2902–2906. doi:10.1016/0032-3861(94)90329-8
Zhang D (2007) On the conductivity measurement of polyaniline pellets. Polym Test 26(1):9–13. doi:10.1016/j.polymertesting.2006.07.010
Xia Y, Wiesinger JM, MacDiarmid AG, Epstein AJ (1995) Camphorsulfonic acid fully doped polyaniline emeraldine salt: conformations in different solvents studied by an ultraviolet/visible/near-infrared spectroscopic method. Chem Mater 7(3):443–445. doi:10.1021/cm00051a002
Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80(6):1339. doi:10.1021/ja01539a017
Barkade SS, Naik JB, Sonawane SH (2011) Ultrasound assisted miniemulsion synthesis of polyaniline/Ag nanocomposite and its application for ethanol vapor sensing. Colloids Surf A 378(1–3):94–98. doi:10.1016/j.colsurfa.2011.02.002
Jeevananda T, Siddaramaiah, Kim NH, Heo S-B, Lee JH (2008) Synthesis and characterization of polyaniline-multiwalled carbon nanotube nanocomposites in the presence of sodium dodecyl sulfate. Polym Adv Technol 19(12):1754–1762. doi:10.1002/pat.1191
Basavaraja C, Kim WJ, Kim DG, Huh DS (2012) Behavior of polyaniline–dodecylbenzene sulfonic acid/reduced graphene oxide nanocomposite films. Polym Compos 33(3):388–396. doi:10.1002/pc.22160
Lu X, Dou H, Yang S, Hao L, Zhang L, Shen L, Zhang F, Zhang X (2011) Fabrication and electrochemical capacitance of hierarchical graphene/polyaniline/carbon nanotube ternary composite film. Electrochim Acta 56(25):9224–9232. doi:10.1016/j.electacta.2011.07.142
Yuan NY, Ma FF, Fan Y, Liu YB, Ding JN (2012) High conductive ethylene vinyl acetate composites filled with reduced graphene oxide and polyaniline. Nanocompos Part A 43(12):2183–2188. doi:10.1016/j.compositesa.2012.06.003
Šeděnková I, Trchov M, Stejskal J, Bok J (2007) Polymerization of aniline in the solutions of strong and weak acids: the evolution of infrared spectra and their interpretation using factor analysis. Appl Spectrosc 61(11):1153–1162. doi:10.1366/000370207782597058
Huang YF, Lin CW (2012) Polyaniline-intercalated graphene oxide sheet and its transition to a nanotube through a self-curling process. Polymer 53(5):1079–1085. doi:10.1016/j.polymer.2012.01.025
Wang H, Hao Q, Yang X, Lu L, Wang X (2009) Graphene oxide doped polyaniline for supercapacitors. Electrochem Commun 11(6):1158–1161. doi:10.1016/j.elecom.2009.03.036
Venugopal G, Krishnamoorthy K, Mohan R, Kim S-J (2012) An investigation of the electrical transport properties of graphene-oxide thin films. Mater Chem Phys 132(1):29–33. doi:10.1016/j.matchemphys.2011.10.040
Huang YF, Lin CW (2012) Facile synthesis and morphology control of graphene oxide/polyaniline nanocomposites via in situ polymerization process. Polymer 53(13):2574–2582. doi:10.1016/j.polymer.2012.04.022
Hussain M, Choa Y-H, Niihara K (2001) Fabrication process and electrical behavior of novel pressure-sensitive composites. Compos Part A 32(12):1689–1696. doi:10.1016/S1359-835X(01)00035-5
Prokes J, Varga M, Krivka I, Rudajevova A, Stejskal J (2011) The influence of compression pressure on transport properties of polyaniline. J Mater Chem 21(13):5038–5045. doi:10.1039/c0jm03087b
Zhang Z, Han M (2003) One-step preparation of size-selected and well-dispersed silver nanocrystals in polyacrylonitrile by simultaneous reduction and polymerization. J Mater Chem 13(4):641–643
Zhang K, Zhang LL, Zhao XS, Wu J (2010) Graphene/polyaniline nanofiber composites as supercapacitor electrodes. Chem Mater 22(4):1392–1401. doi:10.1021/cm902876u
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This work was supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) from the Ministry of Trade, Industry and Energy of the Republic of Korea through the Human Resources Development Program (Grant No. 20124030200130).
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Imran, S.M., Kim, Y., Shao, G.N. et al. Enhancement of electroconductivity of polyaniline/graphene oxide nanocomposites through in situ emulsion polymerization. J Mater Sci 49, 1328–1335 (2014). https://doi.org/10.1007/s10853-013-7816-5
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DOI: https://doi.org/10.1007/s10853-013-7816-5