Skip to main content

Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils

Abstract

Cellulose nanofibrils (CNF) were isolated from cotton microfibrils (CM) by acid hydrolysis and coated with polyaniline (PANI) by in situ polymerization of aniline onto CNF in the presence of hydrochloride acid and ammonium peroxydisulfate to produce CNF/PANI. Nanocomposites of natural rubber (NR) reinforced with CNF and CNF/PANI were obtained by casting/evaporation method. TG analyses showed that coating CNF with PANI resulted in a material with better thermal stability since PANI acted as a protective barrier against cellulose degradation. Nanocomposites and natural rubber showed the same thermal profiles to 200 °C, partly due to the relatively lower amount of CNF/PANI added as compared to conventional composites. On the other hand, mechanical properties of natural rubber were significantly improved with nanofibrils incorporation, i.e., Young’s modulus and tensile strength were higher for NR/CNF than NR/CNF/PANI nanocomposites. The electrical conductivity of natural rubber increased five orders of magnitude for NR with the addition of 10 mass% CNF/PANI. A partial PANI dedoping might be responsible for the low electrical conductivity of the nanocomposites.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

References

  1. Deepa B, Abraham E, Cherian BM, Bismarck A, Blaker JJ, Pothan LA, Leao AL, Souza SF, Kottaisamy M. Structure, morphology and thermal characteristics of banana nanofibers obtained by steam explosion. Bioresource Technol. 2011;102:1988–97.

    CAS  Article  Google Scholar 

  2. Morán JI, Alvarez VA, Cyras VP, Vázquez A. Extraction of cellulose and preparation of nanocellulose from sisal fibers. Cellulose. 2008;15:149–59.

    Article  Google Scholar 

  3. Fahma F, Iwamoto S, Hori N, Iwata T, Takemura A. Effect of pre-acid-hydrolysis treatment on morphology and properties of cellulose nanowhiskers from coconut husk. Cellulose. 2011;18:443–50.

    CAS  Article  Google Scholar 

  4. Rosa MF, Medeiros ES, Malmonge JA, Gregorski KS, Wood DF, Mattoso LHC, GlennG Orts WJ, Imam SH. Cellulose nanowhiskers from coconut husk fibers: Effect of preparation conditions on their thermal and morphological behavior. Carbohyd Polym. 2010;81:83–92.

    CAS  Article  Google Scholar 

  5. Habibi Y, Lucia LA, Rojas OJ. Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev. 2010;110:3479–500.

    CAS  Article  Google Scholar 

  6. Siró I, Plackett D. Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose. 2010;17:459–94.

    Article  Google Scholar 

  7. Roman M, Winte WT. Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules. 2004;5:1671–7.

    CAS  Article  Google Scholar 

  8. Eichhorn SJ, Baillie CA, Zafeiropoulos N, Mwaikambo LY, Ansell MP, Dufresne A, Entwistle KM, Herrera-Franco PJ, Escamilla GC, Groom LH, Hughes HM, Hill C, Rials TG, Wild PM. Review current international research into cellulosic fibers and composites. J Mater Sci. 2001;36:2107–31.

    CAS  Article  Google Scholar 

  9. Samir MASA, Alloin F, Dufresne A. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules. 2005;6:612–26.

    CAS  Article  Google Scholar 

  10. Mattoso LHC, Medeiros ES, Baker DA, Avloni J, Wood DF, Orts WJ. Electrically conductive nanocomposites made from cellulose nanofibrils and polyaniline. J Nanosci Nanotechnol. 2008;8:1–6.

    Article  Google Scholar 

  11. Hu W, Chen S, Yang Z, Liu L, Wang H. Flexible electrically conductive nanocomposite membrane based on bacterial cellulose and polyaniline. J Phys Chem B. 2011;115:8453–7.

    CAS  Article  Google Scholar 

  12. Müller D, Rambo CR, Recouvreux DOS, Porto LM, Barra GMO. Chemical in situ polymerization of polypyrrole on bacterial cellulose nanofibers. Synthetic Met. 2011;161:106–11.

    Article  Google Scholar 

  13. Visakh PM, Thomas S, Oksman K, Mathew AP. Crosslinked natural rubber nanocomposites reinforced with cellulose whiskers isolated from bamboo waste: processing and mechanical/thermal properties. Compos A. 2012;43:735–41.

    CAS  Article  Google Scholar 

  14. Wang Y, Tian H, Zhang L. Role of starch nanocrystals and cellulose whiskers in synergistic reinforcement of waterborne polyurethane. Carbohyd Polym. 2010;80:665–71.

    CAS  Article  Google Scholar 

  15. Martins MA, Pessoa JDC, Gonçalves PS, Souza FI, Mattos LHC. Thermal and mechanical properties of the açaí fiber/natural rubber composites. J Mater Sci. 2008;43:6531–8.

    CAS  Article  Google Scholar 

  16. Siqueira G, Tapin-Lingua S, Bras J, Perez DS, Dufresne A. Mechanical properties of natural rubber nanocomposites reinforced with cellulosic nanoparticles obtained from combined mechanical shearing, and enzymatic and acid hydrolysis of sisal fibers. Cellulose. 2011;18:57–65.

    CAS  Article  Google Scholar 

  17. Pasquini D, Teixeira EM, Curvelo AAS, Belgacem MN, Dufresne A. Extraction of cellulose whiskers from cassava bagasse and their applications as reinforcing agent in natural rubber. Ind Crop Prod. 2010;32:486–90.

    CAS  Article  Google Scholar 

  18. Bendahou A, Kaddami H, Dufresne A. Investigation on the effect of cellulosic nanoparticles’ morphology on the properties of natural rubber based nanocomposites. Eur Polym J. 2010;46:609–20.

    CAS  Article  Google Scholar 

  19. Bras J, Hassan ML, Bruzesse C, Hassan EA, El-Wakil NA, Dufresne A. Mechanical, barrier, and biodegradability properties whiskers reinforced natural rubber nanocomposites. Ind Crop Prod. 2010;32:627–33.

    CAS  Article  Google Scholar 

  20. Micusık M, Omastova M, Prokes J, Krupa I. Mechanical and electrical properties of composites based on thermoplastic matrices and conductive cellulose fibers. J Appl Polym Sci. 2006;101:133–42.

    Article  Google Scholar 

  21. Auad ML, Richardson T, Orts WJ, Medeiros ES, Mattoso LHC, Mosiewicki MA, Marcoviche NE, Arangurene MI. Polyaniline-modified cellulose nanofibrils as reinforcement of a smart polyurethane. Polym Int. 2011;60:743–50.

    CAS  Article  Google Scholar 

  22. Araujo JR, Adamo CB, De Paoli MA. Conductive composites of polyamide-6 with polyaniline coated vegetal fiber. Chem Eng J. 2011;174:425–31.

    CAS  Article  Google Scholar 

  23. Malmonge JA, Camilo EC, Moreno RMB, Mattoso LHC, McMahan CM. Comparative study on the technological properties of latex and natural rubber from Hancornia speciosa Gomes and Hevea brasiliensis. J Appl Polym Sci. 2009;111:2986–91.

    CAS  Article  Google Scholar 

  24. Medeiros ES, Mattoso LHC, Filho RB, Wood DF, Orts WJ. Self-assembled films of cellulose nanofibrils and poly(o-ethoxyaniline). Colloid Polym Sci. 2008;286:1265–72.

    CAS  Article  Google Scholar 

  25. Dong XM, Revol J-F, Gray DG. Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose. 1998;5:19–32.

    CAS  Article  Google Scholar 

  26. Martins MA, Teixeira EM, Corrêa AC, Ferreira M, Mattoso LHC. Extraction and characterization of cellulose whiskers from commercial cotton fibers. J Mater Sci. 2011;46:7858–64.

    CAS  Article  Google Scholar 

  27. Julien S, Chornet E, Overend RP. Influence of acid pretreatment (H2SO4, HCl, HNO3) on reaction selectivity in the vacuum pyrolysis of cellulose. J Anal Appl Pyrol. 1993;21:25–43.

    Article  Google Scholar 

  28. Traore MK, Stevenson WTK, McCormick BJ, Dorey RC, Wen S, Meyers D. Thermal analysis of polyaniline Part I Thermal degradation of HCl-doped emeraldine base. Synthetic Met. 1991;40:137–53.

    CAS  Article  Google Scholar 

  29. Rannon P, Nechtschein M. Aging studies on polyaniline: conductivity and thermal stability. Synthetic Met. 1997;84:755–6.

    Article  Google Scholar 

  30. Chen E-C, Lin Y-W, Wu T-M. Fabrication, morphology and thermal degradation behaviors of conductive polyaniline coated monodispersed polystyrene particles. Polymer Degrad Stabil. 2009;94:550–7.

    CAS  Article  Google Scholar 

  31. Oliveira LCS, Rosa DP, Arruda EJ, Costa RB, Gonçalves PS, Delben A. Comparative studies of latex obtained of rubber tree clones (Hevea brasiliensis) – series IAC 328 – Votuporanga – SP. J Therm Anal Cal. 2004;75:495–500.

    Article  Google Scholar 

  32. Medeiros ES, Galiani PD, Moreno RMB, Mattoso LHC, Malmonge JA. A comparative study of the non-isothermal degradation of natural rubber from Mangabeira (Hancornia speciosa Gomes) and Seringueira (Hevea brasiliensis). J Therm Anal Calorim. 2010;100:1045–50.

    CAS  Article  Google Scholar 

  33. Rodriguez NL, Thielemans W, Dufresne A. Sisal cellulose whiskers reinforced polyvinyl acetate nanocomposites. Cellulose. 2006;13:261–70.

    Article  Google Scholar 

Download references

Acknowledgements

The authors acknowledge the Brazilian agencies CNPq, CAPES, and FAPESP for financial support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to J. A. Malmonge.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Silva, M.J., Sanches, A.O., Medeiros, E.S. et al. Nanocomposites of natural rubber and polyaniline-modified cellulose nanofibrils. J Therm Anal Calorim 117, 387–392 (2014). https://doi.org/10.1007/s10973-014-3719-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-014-3719-1

Keywords

  • Cellulose nanofibrils
  • Cotton cellulose
  • Polyaniline
  • Natural rubber