Improving reinforcement of natural rubber by networking of activated carbon nanotubes Sanjib Bhattacharyya a , Christophe Sinturel a , Ouziyine Bahloul a , Marie-Louise Saboungi a , Sabu Thomas b , Jean-Paul Salvetat a, * a Centre de Recherche sur la Matie `re Divise ´e, CNRS Universite ´ d’Orle ´ans, UMR6619, 1B rue de la Fe ´rollerie, 45071 Orle ´ans cedex 2, France b School of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills P.O. Kottayam, Kerala 686 560, India ARTICLE INFO Article history: Received 31 January 2008 Accepted 14 March 2008 Available online 19 March 2008 ABSTRACT Reinforcement of natural rubber was achieved using carboxylated multiwalled carbon nanotubes (c-MWCNT) dispersed with sodium dodecyl sulfate. The structure of the rein- forced latex films was investigated by TEM and AFM. The tensile and dynamic-mechanical tests demonstrated a strong enhancement in the Young’s modulus (10-fold), tensile strength (2-fold) and storage modulus (60-fold) at low-strain in the rubbery state with up to 8.3 wt% of MWCNTs, with a small reduction in elongation at break. Dielectric mea- surement at room temperature revealed a low percolation threshold (<1 wt%) associated with the formation of an interconnected nanotube network. Latex film formation plays a critical role in the network formation due to the segregation effect at the surface of latex beads. We observed large Payne and Mullins effects due to the mechanical behavior of the nanotube network. The disruption of the network during stretching induces both an increase of electrical resistivity and mechanical stress-softening. Ó 2008 Elsevier Ltd. All rights reserved. 1. Introduction Polymer/nano-filler composites have received intense atten- tion and research in the past decade, driven by the unique properties of nanostructures and potential to create new materials with superior properties. The goal of polymer/ nano-filler composite sciences is not only to fill a matrix with nanometer sized particles, but also to modify the matrix tex- ture by interaction with nano-fillers during processing, in or- der to make new functional materials, especially with improved mechanical properties. In the case of reinforced polymer composites, it is important to distinguish two ther- modynamic regimes (glassy and rubbery regions) related to the viscoelastic behavior of polymer matrices. This because of the different reinforcing mechanisms involved in the glassy and rubbery regimes of polymeric matrices. In the glassy state of the polymer matrix (T < T g the glass transition temperature), reinforcement is achieved with high aspect ra- tio fibers having modulus at least one order of magnitude higher than that of the matrix. The high specific surface area of the nano-fillers is expected to provide enhanced interphase effects and tensile strength. Reinforcement depends essen- tially on the efficiency of load transfer to the fibers and is influenced by the dispersion state and aspect ratio of the fill- ers, and as well as on the quality of the interphase. High levels of reinforcement are achieved when all factors are carefully controlled. However, in the rubbery state of the matrix (T > T g ), elasticity is dominated by the entropy effects rather than elemental bond stiffness [1–3]. In this regime a first level of reinforcement is ‘‘hydrodynamical’’ in origin and can be achieved with dispersed nanoparticles [4–8]. In the second le- vel of reinforcement filler–matrix and filler–filler interactions 0008-6223/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2008.03.011 * Corresponding author: Fax: +33 2 38255376. E-mail address: [email protected](J.-P. Salvetat). CARBON 46 (2008) 1037 – 1045 available at www.sciencedirect.com journal homepage: www.elsevier.com/locate/carbon
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Improving Reinforcement of Natural Rubber by Networking of Activated Carbon Nanotubes
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aCentre de Recherche sur la Matiere Divisee, CNRS Universite d’Orleans, UMR6619, 1B rue de la Ferollerie, 45071 Orleans cedex 2, FrancebSchool of Chemical Sciences, Mahatma Gandhi University, Priyadarshini Hills P.O. Kottayam, Kerala 686 560, India
A R T I C L E I N F O
Article history:
Received 31 January 2008
Accepted 14 March 2008
Available online 19 March 2008
0008-6223/$ - see front matter � 2008 Elsevidoi:10.1016/j.carbon.2008.03.011
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