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Licensed Unlicensed Requires Authentication Published by De Gruyter June 30, 2014

Dispersion Enhancement of Multi-Walled Carbon Nanotubes in Nitrile Rubber

  • A. Boonbumrung , P. Sae-oui and C. Sirisinha


A study of reinforcement mechanism of multi-walled carbon nanotubes (MWCNT) in nitrile rubber (NBR) matrix was carried out. Attempts to enhance the dispersion degree of MWCNT and the NBR-MWCNT interaction were conducted using numerous approaches, namely, sonication and chemical treatments of MWCNT with nitric acid (HNO3), nitric-sulfuric acid mixture (HNO3/H2SO4) and potassium permanganate (KMnO4). Rheological behavior, dynamic properties and electrical properties of MWCNT/NBR vulcanizates were monitored. Results gained reveal the magnitude of Payne effect increases with MWCNT content and mixing time. The expanded MWCNT and continuous-network formation are observed with an increase in mixing time, yielding enhanced mechanical properties and electrical properties. With MWCNT modification, a significant reduction in the state-of-mix of MWCNT composites is exhibited. SEM results demonstrate the highest magnitude of MWCNT dispersion in the system with HNO3, but relatively poor interaction with NBR. The HNO3/H2SO4 or KMnO4 system demonstrates poor MWCNT dispersion after treatment which is probably due to the compaction of MWCNT during the drying stage after the chemical treatment process, giving the detrimental effect to mechanical and electrical properties of vulcanizates.

* Mail address: Chakrit Sirisinha, Department of Chemistry, Faculty of Science, Mahidol University, Bangkok 10400, Thailand, E-mail:


Baughman, R. H., Zakhidov, A. A. and De Heer, W. A., “Carbon Nanotubes – The Route Toward Applications”, Science, 297, 787792 (2002) 10.1126/science.1060928Search in Google Scholar PubMed

Bhattacharyya, S., Sinturel, C., Bahloul, O., Saboungi, M.-L., Thomas, S. and Salvetat, J.-P., “Improving Reinforcement of Natural Rubber by Networking of Activated Carbon Nanotubes”, Carbon, 46, 10371045 (2008) 10.1016/j.carbon.2008.03.011Search in Google Scholar

Chang, C., Liu, Y., “Functionalization of Multi-Walled Carbon Nanotubes with Furan and Maleimide Compounds through Diels-Alder Cycloaddition”, Carbon, 47, 30413049 (2009) 10.1016/j.carbon.2009.06.058Search in Google Scholar

Chakrapani, N., Wei, B., Carrillo, A., Ajayan, P. M. and Kane, R. S., “Capillarity-Driven Assembly of Two-Dimensional Cellular Carbon Nanotube Foams”, PNAS, 101, 40094012 (2004) 10.1073/pnas.0400734101Search in Google Scholar PubMed PubMed Central

Chen, J., Rao, A. M., Lyuksyutov, S., Itkis, M. E., Hamon, M. A. and Hu, H., “Dissolution of Full-Length Single-Walled Carbon Nanotubes”, Journal of Physical Chemistry B, 105, 25252528 (2001) 10.1021/jp002596iSearch in Google Scholar

Chen, L., Xie, H., Li, Y. and Yu, W., “Surface Chemical Modification of Multiwalled Carbon Nanotubes by a Wet-Mechanochemical Reaction”, Journal of Nanomaterials, 2008 (2008)10.1155/2008/783981Search in Google Scholar

Coleman, J. N., Khan, U., Blau, W. J. and Gun'ko, Y. K., “Small But Strong: A Review Of The Mechanical Properties Of Carbon Nanotube-Polymer Composites”, Carbon, 44, 16241652 (2006) 10.1016/j.carbon.2006.02.038Search in Google Scholar

Das, A., Stockelhuber, K. W., Jurk, R., Saphiannikova, M., Fritzsche, J. and Lorenz, H., “Modified and Unmodified Multiwalled Carbon Nanotubes in High Performance Solution-Styrene-Butadiene and Butadiene Rubber Blends”, Polymer, 49, 52765283 (2008) 10.1016/j.polymer.2008.09.031Search in Google Scholar

Frogley, M. D., Ravich, D. and Wagner, H. D., “Mechanical Properties of Carbon Nanoparticle-Reinforced Elastomers”, Compos. Sci. Technol., 63, 16471654 (2003) 10.1016/S0266-3538(03)00066-6Search in Google Scholar

Gojny, F. H, Wichmann, M. H. G., Kopke, U., Fiedler, B. and Schulte, K., “Carbon Nanotube-Reinforced Epoxy-Composites: Enhanced Stiffness and Fracture Toughness at Low Nanotube Content”, Compos. Sci. Technol., 64, 23632371 (2004) 10.1016/j.compscitech.2004.04.002Search in Google Scholar

Lu, L, Zhou, Z., Zhang, Y., Wang, S. and Zhang, Y., “Reinforcement of Styrene-Butadiene-Styrene Tri-Block Copolymer by Multi-Walled Carbon Nanotubes via Melt Mixing”, Carbon, 45, 26212627 (2007) 10.1016/j.carbon.2007.08.025Search in Google Scholar

Kim, M., Hong, C. K., Choe, S. and Shim, S. E., “Synthesis of Polystyrene Brush on Multiwalled Carbon Nanotubes Treated with KMNO4 in the Presence of a Phase-Transfer Catalyst”, J. Polym. Sci., Part A: Polym. Chem., 45, 44134420 (2007) 10.1002/pola.22190Search in Google Scholar

Krause, B., Villmow, T., Boldt, R., Mende, M., Petzold, G. and Pötschke, P., “Influence of Dry Grinding in a Ball Mill on the Length of Multiwalled Carbon Nanotubes and their Dispersion and Percolation Behaviour in Melt Mixed Polycarbonate Composites”, Compos. Sci. Technol., 71, 11451153 (2011) 10.1016/j.compscitech.2011.04.004Search in Google Scholar

Leblanc, J. L., “Rubber-Filler Interactions and Rheological Properties in Filled Compounds”, Prog. Polym. Sci., 27, 627687 (2002) 10.1016/S0079-6700(01)00040-5Search in Google Scholar

Liu, P., Wang, T., “Ultrasonic-Assisted Chemical Oxidative Cutting of Multiwalled Carbon Nanotubes with Ammonium Persulfate in Neutral Media”, Appl. Phys. A, 97, 771775 (2009) 10.1007/s00339-009-5314-zSearch in Google Scholar

López-Manchado, M. A., Biagiotti, J., Valentini, L. and Kenny, J. M., “Dynamic Mechanical and Raman Spectroscopy Studies on Interaction between Single-Walled Carbon Nanotubes and Natural Rubber”, J. Appl. Polym. Sci., 92, 33943400 (2004) 10.1002/app.20358Search in Google Scholar

López-Manchado, M. A., Valentini, L., Biagiotti, J. and Kenny, J. M., “Thermal and Mechanical Properties of Single-Walled Carbon Nanotubes-Polypropylene Composites Prepared by Melt Processing”, Carbon, 43, 14991505 (2005) 10.1016/j.carbon.2005.01.031Search in Google Scholar

Ma, P. C., Siddiqui, N. A., Marom, G., Kim, J. K., “Dispersion and Functionalization of Carbon Nanotubes for Polymer-Based Nanocomposites: A Review”, Composites Part A, 41, 13451367 (2010) 10.1016/j.compositesa.2010.07.003Search in Google Scholar

Perez, L. D., Zuluaga, M. A., Kyu, T., Mark, J. E. and Lopez, B. L., “Preparation, Characterization, and Physical Properties of Multiwall Carbon Nanotube/Elastomer Composites”, Polym. Eng. Sci., 49, 866874 (2009) 10.1002/pen.21247Search in Google Scholar

Pötschke, P., Fornes, T. D. and Paul, D. R., “Rheological Behavior of Multiwalled Carbon Nanotube/Polycarbonate Composites”, Polymer, 43, 32473255 (2002) 10.1016/S0032-3861(02)00151-9Search in Google Scholar

Li, Q., Depaula, R., Zhang, X., Zheng, L., Arendt, P. N. and Mueller, F. M., “Drying Induced Upright Sliding and Reorganization of Carbon Nanotube Arrays”, Nanotechnol., 17, 45334536 (2006) 10.1088/0957-4484/17/18/001Search in Google Scholar PubMed

Ramier, J., Gauthier, C., Chazeau, L., Stelandre, L. and Guy, L., “Payne Effect in Silica-Filled Styrene-Butadiene Rubber: Influence of Surface Treatment”, J. Polym. Sci., Part B: Polymer Physics, 45, 286298 (2007) 10.1002/polb.21033Search in Google Scholar

Rasheed, A., Howe, J. Y., Dadmun, M. D. and Britt, P. F., “The Efficiency of the Oxidation of Carbon Nanofibers with Various Oxidizing Agents”, Carbon, 45, 10721080 (2007) 10.1016/j.carbon.2006.12.010Search in Google Scholar

Santangelo, S., Messina, G., Faggio, G., Abdul Rahimb, S. H. and Miloneb, C., “Effect of Sulphuric-Nitric Acid Mixture Composition on Surface Chemistry and Structural Evolution of Liquid-Phase Oxidized Carbon Nanotubes”, J. Raman Spectrosc., 43, 14321442 (2012) 10.1002/jrs.4097Search in Google Scholar

Schulz, S. C., Faiella, G., Buschhorn, S. T., Prado, L. A. S. A., Giordano, M. and Schulte, K., “Combined Electrical and Rheological Properties of Shear Induced Multiwall Carbon Nanotube Agglomerates in Epoxy Suspensions”, Eur. Polym. J., 47, 20692077 (2011) 10.1016/j.eurpolymj.2011.07.022Search in Google Scholar

Shaffer, M. S. P., Fan, X. and Windle, A. H., “Dispersion and Packing of Carbon Nanotubes”, Carbon, 36, 16031612 (1998) 10.1016/S0008-6223(98)00130-4Search in Google Scholar

Shanmugharaj, A. M., Bae, J. H., Lee, K. Y., Noh, W. H., Lee, S. H. and Ryu, S. H., “Physical and Chemical Characteristics of Multiwalled Carbon Nanotubes Functionalized with Aminosilane and its Influence on the Properties of Natural Rubber Composites”, Compos. Sci. Technol., 67, 18131822 (2007) 10.1016/j.compscitech.2006.10.021Search in Google Scholar

Vaisman, L., Wachtel, E., Wagner, H. D. and Marom, G., “Polymer-Nanoinclusion Interactions in Carbon Nanotube Based Polyacrylonitrile Extruded and Electrospun Fibers”, Polymer, 48, 68436854 (2007) 10.1016/j.polymer.2007.09.032Search in Google Scholar

Verge, P., Peeterbroeck, S., Bonnaud, L. and Dubois, P., “Investigation on the Dispersion of Carbon Nanotubes in Nitrile Butadiene Rubber: Role of Polymer-To-Filler Grafting Reaction”, Compos. Sci. Technol., 70, 14531459 (2010) 10.1016/j.compscitech.2010.04.022Search in Google Scholar

Wang, Y., Wu, J. and Wei, F., “A Treatment Method to Give Separated Multi-Walled Carbon Nanotubes with High Purity, High Crystallization and a Large Aspect Ratio”, Carbon, 41, 29392948 (2003) 10.1016/S0008-6223(03)00390-7Search in Google Scholar

Wepasnick, K., Smith, B., Bitter, J. and Howard Fairbrother, D., “Chemical and Structural Characterization of Carbon Nanotube Surfaces”, Anal. Bioanal. Chem., 396, 10031014 (2010) 10.1007/s00216-009-3332-5Search in Google Scholar PubMed

Yue, D., Liu, Y. and Shen, Z., “Study on Preparation and Properties of Carbon Nanotubes/Rubber Composites”, J. Mater. Sci., 41, 25412544 (2006) 10.1007/s10853-006-5331-7Search in Google Scholar

Zhang, J., Zou, H., Qing, Q, Yang, Y, Li, Q. and Liu, Z., “Effect of Chemical Oxidation on the Structure of Single-Walled Carbon Nanotubes”, The Journal of Physical Chemistry B, 107, 37123718 (2003) 10.1021/jp027500uSearch in Google Scholar

Received: 2014-01-17
Accepted: 2014-01-30
Published Online: 2014-06-30
Published in Print: 2014-07-30

© 2014, Carl Hanser Verlag, Munich

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