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Letters to the Editor / Carbon 42 (2004) 2735–2777

Enhancement of the mechanical properties of carbon nanotube/phenolic composites using a carbon nanotube network as the reinforcement
Nyan-Hwa Tai a, Meng-Kao Yeh
a

b,*

, Jia-Hau Liu

b

Department of Materials Science and Engineering, National Tsing Hua University, Hsin-Chu 30013, Taiwan b Department of Power Mechanical Engineering, National Tsing Hua University, Hsin-Chu 30013, Taiwan Received 7 April 2004; accepted 2 June 2004 Available online 20 July 2004

Keywords: A. Carbon nanotubes, Resins; B. Mixing; C. Scanning electron microscopy; D. Mechanical properties

Both theoretical analyses and experimental studies have demonstrated that carbon nanotubes (CNTs) have extremely high strength and modulus [1,2]. The outstanding intrinsic mechanical properties have attracted researchers to adopt CNTs as a reinforcement for composites. On the other hand, several primary drawbacks of adopting CNTs as the reinforcement were reported. These involved non-uniform dispersion of CNTs in matrix, less effective load transfer from matrix to CNTs, weak interactions between shells in CNT, and alignment control of CNTs in matrix [3–5]. Some of the studies revealed that the introduction of CNTs in polymer enhances both the mechanical and physical properties [6–8], although the efficiency is not as high as expected. Nevertheless, negative influences were also reported [9]. The diverse results may be due to different parameters which were adopted during fabrication, workmanship, pre-treatment of CNTs, and microstructure of the material system. Based on theoretical analysis, previously published articles indicated that the maximum shear stress at the interface increases with increasing CNT wall thickness [10] while effective Young’s modulus decreases with increasing layer number [11]. Melt mixing is generally adopted to introduce CNTs into resin. However, the agglomeration of CNTs in matrix generates defects in composites and thus reduces the mechanical properties of the composites. In this study, dispersed CNTs and network CNTs synthesized from the thermal chemical vapor deposition method (CVD) were adopted as the reinforcement. In the case of adopting dispersed CNTs as the reinforcement, CNTs were obtained from the milling process of the as-grown CNTs. The composites reinforced by the dispersed

Corresponding author. Tel.: +886-3-574-2595; fax: +886-3-5726414. E-mail address: mkyeh@pme.nthu.edu.tw (M.-K. Yeh). 0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2004.06.002

*

CNTs were fabricated through the melt mixing method. On the other hand, the network CNT composites were fabricated through the resin infiltration method by introducing the resin into the CNT network. Comparisons in mechanical properties between the network CNT composites and the dispersed CNT composites are the focus of this work. Moreover, fracture morphologies were also examined and discussed. CNTs used in this study are multi-walled carbon nanotubes (MWNTs) derived from the CVD process by using benzene, hydrogen, ferrocene, and thiophene as carbon source, carrier gas, catalyst precursor, and growth promoter, respectively. Most of the CNT diameters used in this work were less than 100 nm. The as-prepared MWNTs are highly entangled and often aggregated into network with diameters of several to 10 cm; the network was then adopted as the 3-D CNT preform for composites. Tensile tests were performed on the MWNTs/phenolic composites; the rectangular specimens with the size of 6.0 cm · 1.0 cm · 0.2 cm were cut from a panel with the size of 6.0 cm · 3.0 cm · 0.2 cm. Stain gages mounted on the specimens were used for strain measurement. Fig. 1(a) shows tensile strength of the composites reinforced by different contents of dispersed CNTs and network CNTs. The tensile strength increases with the amount of reinforcement in both cases. In the composites reinforced by the dispersed CNTs, no significant increase in strength can be obtained when CNT content is over 2.0 wt%. On the other hand, in the composites reinforced by the network CNTs, the tensile strength increases with CNT additives. An increment in tensile strength of nearly 97.0% was attained when 3.0 wt% MWNTs were introduced to the composites. No plateau in tensile strength was observed for network CNT composites in this work. Fig. 1(b) shows Young’s modulus of the dispersed CNT and network CNT composites. The Young’s modulus increases with CNTs content. However, under

If the rough surface was produced by the CNT with smooth outer surface. When 3 wt% CNTs were used for reinforcement in network CNT composites. respectively. respectively.8%. between CNT and matrix is observed. shows the FESEM images of the as-synthesized CNTs and the dispersed CNTs. In addition. 2(d). The lower increment in modulus than that in tensile strength implies that the continuity of the as-synthesized CNTs contributes more effect in strength than in strain. This work demonstrated that network CNTs produce better mechanical properties of composites than dispersed CNTs because the CNTs in network are longer. 2(c) shows the morphology of the fracture surface of the dispersed CNT reinforced composites with the CNT content of 1. CNT pullout and in-print denoted by (A). including carbon nanotube pull-out. The conclusion is correct for most of the cases. in-print.5 wt%. the same CNT additive. network and dispersed CNTs were adopted as reinforcements for fabricating CNTs/phenolic composites.0%. 2(e). and crack front impediment. 2(f) could also be produced by the debonding of a nanotube bundle or by the debonding of a large diameter CNT with amorphous carbon coated. 2(d). are depicted in the figure. Long CNTs on fracture surface are probably due to the weak interfacial strength between CNT and matrix. 1. it was observed that CNTs several lm in length were lying on the surface.Letters to the Editor / Carbon 42 (2004) 2735–2777 2775 Fig. less agglomerated. Moreover.0 wt% the modulus increases 49. and a4. several failure morphologies. as a result. in this study. 2(f). a3. However. In addition. . the network CNTs have significant influence in strength but produce less improvement in strain. including a1. The rough surface may result from the rough outer surface of the large diameter CNTs and perfect wetting between resin and CNTs. the tensile strength and modulus were increased up to 97. as shown in Fig. is observed. 2(a). (a) Tensile strength and (b) Young’s modulus of the composites reinforced by different types and amounts of CNTs. The morphology also shows random orientation of CNTs in composites. on the fracture surface of the dispersed CNT composites. CNTs lying on the fracture surface contributes less reinforcing effect. it has often been reported that weak bonding between CNTs and matrix reduces the load transfer from matrix to CNTs. photo images of the network CNTs and the milled CNTs. This increase is primarily due to the entanglement of the CNTs in the network. a rough surface in CNT is not a pre-condition for producing a rough interfacial surface. the large diameter groove shown in Fig. respectively.0% and 49. which reinforces the composites much more effectively. Fig. a rough debonded surface. and contain fewer defects. However. ripple-like failure mode along the CNT.8% while. Fig. which indicates brittle failure mode of the phenolic matrix during fracture. The fracture morphology implies that propagation of the crack front was hindered or restrained by the CNT. it implies that a strong interfacial bonding between matrix and reinforcement was generated. leaves the CNTs on one surface which is matched by in-print groove on the other surface. In this study. Furthermore. In the network CNT composites with the CNT content of 3. in other words. are observed in this work. Enhancement of mechanical properties of the reinforced composites is greater when using network CNTs than when using dispersed CNTs. Of course. Fig. as mentioned previously. a2. The crack front propagates preferentially along the weaker interface and. the tensile strength increases 97. as denoted by (C) in Fig. 2(b) shows the stripe-like surface. and (B). Generally. CNT pullout is detected on the fracture surface of the network CNT composites. as denoted by (D) in Fig. although brittle fracture is still the primary failure mode. the increment in modulus is not as high as that in tensile strength. as depicted in Fig.

Nanobeam mechanics: elasticity. References [1] Wong EW. (d) 1. . Taiwan. strength. Morphologies of fracture surface of the composites reinforced by dispersed and network carbon nanotubes (a) feature of the as-synthesized CNTs: the FESEM images of network CNTs (a1) and dispersed CNTs (a2). and toughness of nanorods and nanotubes. B: CNT in-print. composites A: CNT pull-out.5 wt% dispersed CNT. photo images of network CNTs (a3) and dispersed CNTs (a4). Science 1997. (e) 1. Lieber CM. Sheehan PE.5 wt% dispersed CNT composites.5 wt% network CNT composites.5 wt% network CNT composites. D: ripple-like fracture pattern (f) 1.277(26):1971–4. (c) 1. C: CNT lying on fracture surface. 2. Acknowledgements This work is supported by the Ministry of Education (A-91-E-FA04-1-4) and National Science Council (NSC92-2120-E-007-004).2776 Letters to the Editor / Carbon 42 (2004) 2735–2777 Fig. (b) phenolic matrix without CNT additive. ROC.

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