Interfacial characteristics of a carbon nanotubepolystyrene composite system

Kin Liao and Sean Li Citation: Applied Physics Letters 79, 4225 (2001); doi: 10.1063/1.1428116 View online: http://dx.doi.org/10.1063/1.1428116 View Table of Contents: http://scitation.aip.org/content/aip/journal/apl/79/25?ver=pdfcov Published by the AIP Publishing

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APPLIED PHYSICS LETTERS

VOLUME 79, NUMBER 25

17 DECEMBER 2001

Interfacial characteristics of a carbon nanotubepolystyrene composite system

Kin Liaoa) and Sean Li
School of Materials Engineering, Nanyang Technological University, Singapore

Received 6 August 2001; accepted for publication 13 October 2001 The performance of a composite material system is critically controlled by the interfacial characteristics of the reinforcement and the matrix material. Here we report a study on the interfacial characteristics of a carbon nanotube CNT-reinforced polystyrene PS composite system through molecular mechanics simulations and elasticity calculations. In the absence of atomic bonding between the reinforcement and the matrix material, it is found that the nonbond interactions consists of electrostatic and van der Waals interaction, deformation induced by these forces, as well as stress/deformation arising from mismatch in the coefcients of thermal expansion. All of these contribute to the interfacial stress transfer ability, the critical parameter controlling material performance. Results of a CNT pullout simulation suggests that the interfacial shear stress of the CNTPS system is about 160 MPa, signicantly higher than most carbon ber reinforced polymer composite systems. 2001 American Institute of Physics. DOI: 10.1063/1.1428116

One of the anticipated applications of a carbon nanotube CNT is ultrastrong reinforcement for high performance composite materials.1,2 It has been well established that the performance of a ber reinforced composite depends critically on the interfacial characteristics between the reinforcement and the matrix material. Optimized ber/matrix interfacial adhesion results in enhanced strength, toughness, as well as long-term behavior. Due to the difculties in devising experiments to study the CNT-polymer interface, molecular modeling may serve to elucidate the importance of various factors constituting the interfacial characteristics of CNTreinforced polymer composites. Here we report a study on the interfacial characteristics of a CNT-reinforced polystyrene PS composite system through molecular mechanics simulations and elasticity calculations. Previous studies on a number of CNT-reinforced polymer systems showed that chemical bonding may or may not exist between CNT and the polymer matrix. Wagner et al.3 suggested that the high interfacial shear stress determined from a CNT/polyurethane composite system is attributed to a 2 2 cycloaddition reaction between the reinforcement and the polymer. From infrared transmission spectra, Jia et al.4 concluded that CC bonding exists between a CNT/ polymethylmethacrylate system. However, using Raman scattering and x-ray diffraction, Chang et al.5 showed that there is no chemical bonding between CNT and the polypyrrole matrix. Based on these results, assuming that there is no chemical bonding between CNT and PS after mixing, the composite system is ideal for studying the inuences of nonbond interactions on the interfacial stress transfer characteristics. Previous studies by Wagner and coworkers on CNT/ polymer systems suggested strong CNTpolymer adhesion.3,6,7 However, in a study on load transfer behavior of CNT/epoxy using Raman spectroscopy, Schadler and
a

Author to whom correspondence should be addressed; electronic mail: askliao@ntu.edu.sg

Ajayan concluded that there is only poor interfacial load transfer in tension.8 Adhesion strength between a PS molecule and graphene was studied using a molecular mechanics model with the Hyperchem employing an empirical MM force eld.9 Random coils of PS ( CH2CHC6H6 ) n molecules with n 2, 4, 10, 20, 40, and 80 were constructed and placed near a single layer of graphene sheet of much larger dimension. The PS chain was then pushed towards and pulled away from the graphene sheet, and the energy of the graphene polymer system at a specied distance between the two was calculated. Results for n 2, 4, 10, and 20 are shown in Fig. 1 where the energy of the PSgraphene system was plotted against the distance between the PS chain and the graphene sheet. The adhesion energy, or the depth of the energy well, is calculated as the difference between the minimum energy and the energy at innite separation. On a per PS monomer basis, the adhesion energy is showing a decreasing trend, from 0.41 eV for a dimer to 0.22 eV for an 80-monomer chain, as shown in Fig. 2, and it seems that it has stabilized at longer PS chains. The nature of this adhesion energy comes from electrostatic and van der Waals force. Note that in this kind of simulation no physical constraint was imposed on the graphene sheet from the surrounding while in a composite, CNT is embedded inside the polymer matrix, and such physical constraint will introduce additional CNT polymer interaction. Deformation of the CNT induced by atomic interactions with the polymer matrix contributes to the adhesion characteristics. A model composite system with more than 4000 atoms, shown in Fig. 3, with either a single-wall or a doublewall armchair carbon nanotube outer diameter 13.34 , obtained from the CNT model embedded in a nearly cylindrical block of random PS chains was constructed. After carrying out optimization procedures, the outer diameters of the single-wall and double-wall CNT were reduced by about 0.6%, compared to a free standing CNT. Although this radial deformation may contribute considerably to the local me-

This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: 0003-6951/2001/79(25)/4225/3/$18.00 4225 2001 American Institute of Physics 138.38.63.144 On: Thu, 07 Nov 2013 21:43:52

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FIG. 3. A molecular model of a double-wall CNT in a PS matrix: top view and section view.

10 6 /K. 12 From concentric cylinder model of elasticity, the radial stress on the CNT is estimated to be about 40 MPa/K. 13,14 Hence CTE mismatch is a signicant factor contributing to the mechanical interlocking mechanism. chanical interlocking mechanism for single wall or double Fiber-matrix interfacial shear stress is a critical paramCNT, it may not be signicant for multiwall carbon nanoeter controlling the efciency of stress transfer and hence tubes because of their better resistance to radial some of the important mechanical properties of the composdeformation.10 ite such as elastic modulus, tensile strength, and fracture Mismatch in the coefcient of thermal expansion CTE toughness. Fiber pullout simulations were performed for between CNT and polymer results in thermal residual radial both single-wall and double-wall armchair CNT using the stress and deformation along the tube when the polymer is system shown in Fig. 3, where a fully embedded, 20 long cooled from its melt. To the authors knowledge there is no CNT was being pulled out of the PS matrix. The energy of measured CTE data currently available for CNT. Since CNT the CNT/PS system, plotted against the displacement of the has a similar hexagonal arrangement of carbon atoms as the CNT from the matrix, is shown in Fig. 4. The energy differgraphite crystal, the CTE of graphite crystal, such as c of 6 ence between the fully embedded tube and the complete pull25 10 /K (15 800 C) in the c axis and a of 1.5 11 6 out conguration is the work required for ber pullout. Pull 10 /K (0 150 C) in the a axis, were used as CTE of out energies for single-wall and double-wall tubes are 158.7 CNT in the calculation. The CTE of PS is about 28 and 154.4 kcal/mol, respectively. The small difference in pullout energy, arising from radial tube deformation, is trivial. It is noticed from Fig. 4 that the energy of single wall CNT at pullout is 0 Kcal/mol while that of double wall CNT is approximately 100 Kcal/mol. The negative energy of the double wall CNT comes from the interaction between the outer and inner tubes, putting the atoms of the inner tube under a compressive load. The shear stress between the CNT and the polymer, i , estimated from the molecular simulation is about 160 MPa,16 which is comparable to an estimated interfacial strength of i 500 MPa for the CNT/ polyurethane system, suggested by Wagner, et al.,3 based on obtained fragmentation experiments. It has been indicated that the estimated i is about an order of magnitude higher than most advanced microber reinforced composites.3 We FIG.is 2.copyrighted Adhesion energy between in a graphene sheet Reuse and random PScontent chain on This article as indicated the abstract. of AIP is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP: believe that this high interfacial shear stress could be attriba per monomer basis.
FIG. 1. Adhesion energy between a graphene sheet and a random coil of a PS molecule, n is the number of monomer units of the PS chain.

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tions. While all of these factors may contribute considerably to single-wall CTN/PS systems, the former two may be more important in governing the interfacial characteristics of multiwall CNT/PS systems.
P. G. Collins and Ph. Avouris, Sci. Am. 283, 38 2000. P. M. Ajayan and O. Z. Zhou, Carbon Nanotubes: Synthesis, Structure, Properties, and Applications, edited by M. S. Dresselhaus, G. Dresselhaus, and Ph. Avouris Springer, Berlin, 2000. 3 H. D. Wagner, O. Lourie, Y. Feldman, and R. Tenne, Appl. Phys. Lett. 72, 188 1998. 4 H. D. Wagner and O. Lourie, Appl. Phys. Lett. 73, 3527 1998. 5 H. D. Wagner and O. Lourie, Compos. Sci. Technol. 59, 975 1999. 6 L. S. Schadler, S. C. Giannaris, and P. M. Ajayan, Appl. Phys. Lett. 73, 3842 1998. 7 Z. Jia, Z. Wang, C. Xu, J. Liang, B. Wei, D. Wu, and S. Zhu, Mater. Sci. Eng., A 271, 395 1999. 8 B. H. Chang, Z. Q. Liu, L. F. Sun, D. S. Tang, W. Y. Zhou, G. Wang, L. X. Qian, S. S. Xie, J. H. Fen, and M. X. Wan, J. Low Temp. Phys. 119, 41 2000. 9 HyperChem Computational Chemistry, Hypercube, Inc., Canada, 1996. 10 T. Hertel, R. E. Walkup, and P. Avouris, Phys. Rev. B 58, 13870 1998. 11 B. T. Kelly, Physics of Graphite Applied Science, London, 1981. 12 Materials Science and Engineering Handbook, edited by J. F. Shackelford and W. Alexander CRC, Boca Raton, FL, 1990. 13 K. Liao and Y. M. Tan, Composites, Part B 32, 365 2001. 14 To calculate radial stress using the concentric cylinder model, the elastic modulus in the radial direction of CNT, E r , needs to be known. From Lu Ref. 15, C 33 of single wall CNT and multiwall CNT are calculated to be 0.397 and 0.41 TPa, respectively. E r is related to C i j by E r C 33 2 C 2/ 13/( C 11 C 12) . From data of graphite crystal Ref. 11, the contribution from the second term of the previous equation is very small ( 1%), therefore E r for single-wall and multiwall CNT are taken as 0.39 and 0.41 TPa in our calculations. Here C 11 is the stiffness coefcient in the axial direction of the tube while C 33 is that in the direction of the basal plane. 15 J. P. Lu, Phys. Rev. Lett. 79, 1297 1997. 16 The total work done, W , in pulling out the carbon nanotube from the polymer matrix can be related to the interfacial shear stress, i , by the xL 2 relation W x 0 2 r ( L x ) i dx , or W r i L , where r and L are the outer radius and length of the carbon nanotube, respectively, and x is the coordinate along the longitudinal tube axis.
1 2

FIG. 4. Energies of single-wall and double-wall CNT as it is being pulled out from the PS matrix.

uted, to a large extent, to the intimate contact between the CNT and the polymer matrix. In summary, it is found, through molecular simulation and elasticity calculations, that for a CNT-PS system with no chemical bonding, the ber/matrix adhesion comes from 1 electrostatic and van der Waals interaction, 2 mismatch in CTEs, and 3 radial deformation induced by atomic interac-

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