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Self-assembled natural rubber/multi-walled carbon nanotube composites using latex compounding techniques
Zheng Peng
a

a,* ,

Chunfang Feng

a,b

, Yongyue Luo a, Yongzhen Li a, L.X. Kong

c,**

Chinese Agricultural Ministry Key Laboratory of Tropical Crop Product Processing, Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 524001, PR China b School of Materials, Hainan University, Haikou 571737, PR China c Centre for Material and Fiber Innovation, Institute for Technology Research Innovation, Deakin University, Geelong Vic 3217, Australia

A R T I C L E I N F O

A B S T R A C T

Article history: Received 9 December 2009 Accepted 10 August 2010 Available online 15 August 2010

Functionalization of multi-walled carbon nanotubes (MWCNTs) plays an important role in eliminating nanotube aggregation for reinforcing polymeric materials. We prepared a new class of natural rubber (NR)/MWCNT composites by using latex compounding and selfassembly technique. The MWCNTs were functionalized with mixed acids (H2SO4/ HNO3 = 3:1, volume ratio) and then assembled with poly (diallyldimethylammonium chloride) and latex particles. The Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy were used to investigate the assembling mechanism between latex particles and MWCNTs. It is found that MWCNTs are homogenously dispersed in the natural rubber (NR) latex as individual nanotubes since strong self-aggregation of MWCNTs has been greatly depressed with their surface functionalization. The well-dispersed MWCNTs produce a remarkable increase in the tensile strength of NR even when the amount of MWCNTs is only 1 wt.%. Dynamic mechanical analysis shows that the glass transition temperature of composites is higher and the inner-thermogenesis and thermal stability of NR/MWCNT composites are better, when compared to those of the pure NR. The marked improvement in these properties is largely due to the strong interfacial adhesion between the NR phase and MWCNTs. Functionalization of MWCNTs represents a potentially powerful technology for signicant reinforcement of natural rubber materials. 2010 Elsevier Ltd. All rights reserved.

1.

Introduction

Natural rubber (NR), one of the most important biosynthesized polymers, has excellent chemical and physical properties, such as outstanding elasticity, exibility, antivirus permeation, and good formability and biodegradability [1] and is widely used in various areas such as tyres, sport elastomers, sealing materials and dairy rubber item [2,3]. The raw NR latex is generally reinforced with carbon black [4], ultra-ne calcium carbonate [5], modied montmorillonite

[6], silica [7] and starch [8] before being manufactured to products as the mechanical properties of raw NR including tensile strength and tear resistance in most cases cannot meet the requirements of applications. However, the reinforcement is not so effective for natural rubber latex due to large dimension and agglomeration of these traditional reinforcing materials. Therefore, it is essential to exploit a new way to enhance the mechanical properties of latex products. Several inorganic nano-materials have already been studied and applied extensively, such as nanosilica [9], nano-clay [10], nano-calcium

* Corresponding author: Fax: +86 759 222 1586. ** Corresponding author. E-mail addresses: zhengpeng8@yahoo.com (Z. Peng), lingxue.kong@deakin.edu.au (L.X. Kong). 0008-6223/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2010.08.025

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carbonate [11] and they are more effective to the reinforcement of NR than those traditional llers. In recent years, carbon nanotubes (CNTs), as quasi one-dimensional nano-materials, have become a potential candidate for a wide range of application such as electronics, composite fabrication and gas storage [1214] since the publication of the landmark paper by Iijima [15]. Compared with other nano-llers, CNTs as an ideal reinforcing ller are expected to provide a better enhancement effect in polymer composites, due to their inherent superior properties [16]. Consequently, CNTs have been widely exploited in different polymers. Sekitani et al. [17] dispersed single-walled carbon nanotubes as chemically stable dopants in a vinylidene uoride-hexauoropropylene copolymer matrix to form a composite lm, by using an ionic liquid of 1-butyl-3-methylimidazolium bis(triuoromethanesulfonyl)imide. Yu et al. [18] prepared conductive multi-walled carbon nanotube/polystyrene composites based on latex technology. Yet, little work has been done in the eld of latex reinforcement with carbon nanotubes, because of their poor compatibility with NR phase. From the standpoint of surface chemistry, the improvement of CNT dispersion in the polymeric matrix by forming oxygen functional groups on CNTs surface via chemical modication plays an important role in reinforcing polymers [1921]. In our previous work, we developed a novel process that incorporates the latex compounding and self-assembly techniques to prepare polyvinyl alcohol/silica composites [22], and rubber/silica composites [23]. It was found that the chemical and physical properties of these nanocomposites, compared with the polymer host, were signicantly enhanced. In the present work, the surface of carbon nanotubes is modied with mixed acids and polyelectrolyte to improve the solubility of multi-walled carbon nanotubes (MWCNTs), leading to the successful introduction of a novel self-assembly process for the preparation of NR/MWCNT composites. The self-assembly mechanism between MWCNTs and latex particles is studied and the impacts of MWCNTs on the morphology and mechanical properties of the composites including dynamic mechanical properties are also investigated.

(H2SO4/HNO3 = 3:1, volume ratio) solution [24]. The mixture was heated for 1.5 h and then diluted in a 1000 mL beaker with 800 mL deionized water. After cooling to room temperature, the mixture was ltered through 200 nm pore diameter membrane and washed with deionized water until neutral. The resulted black solid was then dried under vacuum freeze-dryer for 48 h.

2.3.

Preparation of NR/MWCNT composites

The composite (NR/MWCNTs = 99:1 w/w) was prepared according to the following procedures. 1.08 g acid treated MWCNTs and 0.54 g SDS were dispersed in 100 mL water and treated with an ultrasonic vibrator for 0.5 h [25], and its pH was adjusted to 10 with 0.2 M KOH to obtain a negatively charged MWCNT dispersion. 50 mL positively charged PDDA solution (0.5 wt.%, pH 10) was dropped into the MWCNT dispersion, which was magnetically stirred for 0.5 h. Afterwards, MWCNT/PDDA aqueous dispersion was then dropped into 180 g negatively charged latex (pre-vulcanized, pH 10) accompanying with gentle magnetic stir at room temperature for 24 h. Finally, the mixture was cast on glass plates and dried at 50 C to obtain NR/MWCNT composite lms. The same process was also employed to prepare the reference samples of NR composites reinforced with untreated MWCNTs.

2.4.

Characterizations

2.
2.1.

Experimental
Materials

Latex with a total solid content of 60% was sourced from Qianjin State Rubber Farm (Zhanjiang, PR China) and was then pre-vulcanized. MWCNTs (average diameter: 1030 nm; average length: 515 lm; purity: P95%) was obtained from the Tannamigang Co., (Shenzhen, PR China). The surfactant used for dispersing the MWCNTs was sodium dodecyl sulfate (SDS) (90%) provided by Merck Chemical Co., and poly (diallyldimethylammonium chloride) (PDDA) (mol wt.% ca. 100,000 200,000; 20 wt.% in water) was brought from SigmaAldrich (SigmaAldrich, Louis, MO). All inorganic acids were AR grade.

Surface chemistry of MWCNTs after oxidation was investigated with a PerkinElmer Spectra GX-I Fourier transform infrared spectroscopy (FTIR) (PerkinElmer, Fremont, CA) with a resolution of 4 cm1 in the transmission mode. The MWCNT dispersion was dropped on a copper network for transmission electron microscopy (TEM) observation with an accelerating voltage of 100 kV (JEOL, Peabody, MA). Scanning electron micrographs (SEM) of the composites were taken with a Philips XL30-EDAX instrument (Philips, Eindhoven, Netherlands) at an acceleration voltage of 10 kV. The fracture surface was obtained after the brittle failure of bulk sample in liquid nitrogen. The dynamic-mechanical thermal analysis (DMA) is taken on rectangular specimens (10 4 0.1 mm) in tensile mode at a frequency of 5 Hz using a Dynamic Mechanical Analyzer (DMA242C, Netzsch). Tensile test experiments were conducted on an Instron Series IX Automated Materials Testing System (Instron, Acton, MA) at room temperature with a cross head speed of 500 mm/min and the sample length between the jaws was 25 mm, and the sample width was 4 mm.

3.
3.1.

Results and discussion


Surface functionalization and dispersion of MWCNTs

2.2.

Treatment of MWCNTs with mixed acid

A typical procedure was as follows: 1.08 g of MWCNTs were added into a 250 mL ask charged with 20 mL of mixed acid

The water-solubility of MWCNTs dominates its dispersion in latex. The pure MWCNTs (p-MWCNTs) are very stable and their surface shows chemical-inert and hydrophobic properties unless being modied [26]. Therefore, we used mixing acid system (H2SO4/HNO3 = 3:1, volume ratio) to modify MWCNTs. An absorption band peaked at 1723 cm1 is clearly

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A B

%T

1723.502

1402.764

3431.734

4000.0

3000

2000

1500

1000

400.0

-1 Wavenumber (cm )

Fig. 1 Infrared spectra of (A) p-MWCNTs and (B) m-MWCNTs.

present in the FTIR spectra (Fig. 1) for acid modied MWCNTs (m-MWCNTs), a strong evidence suggesting the stretching vibration of carbonyl group (C@O) [27] while no band appears in the spectra of p-MWCNTs in the region of 1700 cm1. Combining with a stronger band at about 3431 cm1 assigned to the stretching vibration of hydroxy group (OH), we can draw a conclusion that carboxylic acid group (COOH) has been successfully introduced onto the surface of MWCNTs (Fig. 1). Such a modication on MWCNTs with acid and PDDA leads to a very stable dispersion of the CNTs in the solution after even more than 1 week (Fig. 2), while the p-MWCNTs gradually precipitates within 1 h. Therefore, the MWCNTs treated with mixed acid will lead to signicant improvement in solubility and chemical reactivity, which are essential for MWCNTs to disperse in the latex as observed by Huang et al. [28] on polymethyl methacrylate/acrylic acid. The difference between p-MWCNTs and m-MWCNTs dispersion is also conrmed by TEM (Fig. 3). It is found that mMWCNTs are dispersed in water as a form of individual tubes, no aggregation being observed (Fig. 3b), while the p-MWCNTs aggregated badly (Fig. 3a). The improvement in water-solubility of m-MWCNTs is largely contributed to the introduction of carboxyl groups onto the surface of MWCNTs and the interaction between MWCNTs and PDDA. Zhang et al. [29] studied the Poly(L-lactide)/multi-walled carbon nanotube composite and observed that the modication of CNTs surface has improved their water solubility and alleviated the aggregation of CNTs. In addition, surface modication of MWCNTs increases the degree of their random orientation in the solution and creates sections of irregular length (Fig. 3B). The shortening in length of MWCNTs also can enhance the dispersion because shorter nanotubes may have less opportunity to twist inter and intra MWCNTs.

Fig. 2 Photographs of MWCNTs dispersed in water: (A) p-MWCNTs; (B) m-MWCNTs.

3.2. The self-assembling mechanism between MWCNTs and latex particles


The self-assembly technique was rst introduced by Decher et al. in 1991 [30] and mainly used to fabricate layer-by-layer composites. In the present study, self-assembly together with latex compounding techniques is used to suppress the strong self-aggregation generally encountered for p-MWCNTs and

enhance the interfacial adhesion between MWCNTs and latex particles, to ultimately improve the properties and performance of developed NR/MWCNT composites. The process developed involves two assembly steps (Fig. 4). Before the rst assembly, the carboxylic group and hydroxy group were introduced onto the surface of MWCNTs through acidic treatment. The introduction of hydrophilic group greatly improves MWCNT water-solubility and makes it possible for MWCNTs to be dispersed in water-based latex. However, there is still a strong interaction between llers and matrix, and NR/MWCNT system could not form a stable

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Fig. 3 TEM micrographs of MWCNTs dispersed in water: (A)p-MWCNTs; (B) m-MWCNTs.

Fig. 4 The schematic of the self-assembly process.

dispersion to avoid aggregation. As the interaction between non-polar NR and polar m-MWCNTs is relatively weak, this may still lead to heavy self-aggregation of MWCNTs. Therefore, the rst assembly step is to assemble negatively charged template MWCNTs with positively charged PDDA molecular chain, using the electrostatic adsorption as driving force. As the surface of MWCNTs is covered with PDDA, the interaction between carbon nanotubes is greatly obstructed, and the selfaggregation of MWCNTs is further depressed. Due to a large difference in rigidity between MWCNTs and PDDA and the charge density of PDDA being signicantly higher than that on the surface of MWCNTs, all PDDA charges cannot form short-distance ion pairs with the surface charges of rigid MWCNTs. Therefore, the positive charge on PDDA cannot be completely neutralized by the negative charge on MWCNTs during the rst step assembly; the m-MWCNTs will maintain posi-

tive and be ready for the second assembly with negatively charged latex particles. This is demonstrated from TEM observation where short MWCNTs are attracted onto the latex particles (presented as dark circle pies) like little worms (Fig. 5a); MWCNTs with middle size are assembled around the latex particles surfaces as circles (Fig. 5b); and the long MWCNTs are individually dispersed, having various latex particles linked (Fig. 5c). After the second assembly, the latex particles and MWCNTs are strongly interacted and the MWCNTs are uniformly dispersed in NR matrix after drying.

3.3.

Morphology of NR/MWCNT composites

Generally, it is hard to individually disperse MWCNTs in polymer matrix, due to strong aggregation of p-MWCNTs [31] and high viscosity of the polymer. PDDA, as discussed in the above section, was used as a bridge to connect MWCNTs and latex

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Fig. 5 TEM micrographs of different length m-MWCNTs assembling with latex particles: (A) small size m-MWCNTs; (B) middle size m-MWCNTs; (C) large size m-MWCNTs.

Fig. 6 SEM micrographs of NR/MWCNT composites: (A) pMWCNTs dispersed in NR matrix; (B) MWCNTs treated with acid dispersed in NR matrix; (C) m-MWCNTs dispersed in NR matrix using self-assembly technique.

particles, aiming to alleviate the aggregation of MWCNTs and enhance interfacial adhesion between MWCNTs and NR matrix. Therefore the modication of MWCNTs with PDDA plays a critical role in preparing composites. As demonstrated from the fracture SEM morphology images of NR/MWCNT composites, the p-MWCNTs agglomerate and are not well distributed in NR (Fig. 6a), while the m-MWCNTs are not presented as congregated but loose nanotubes (Fig. 6b). In addition, some outcrops of the MWCNTs exist on the fracture surface, indicating that the interaction between the MWCNTs and the rubber macromolecules is enhanced. When the self-assembly process is used, the MWCNTs disperse in NR matrix as individual tubes

(Fig. 6c) and the interface between MWCNTs and NR seems very smooth which indicates the excellent compatibility between MWCNTs and NR matrix.

3.4.

Mechanical property

Natural rubber, as a typical elastomer, shows an excellent exibility. However, its insufcient mechanical properties cannot meet the requirement of applications unless it is reinforced with inorganic llers. The traditional inorganic llers

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Table 1 Mechanical properties of NR and NR/MWCNT composites. MWCNT loading (wt.%) 0 1 1 (p-MWCNTs) (m-MWCNTs) 24.9 (1.2) 30.0 (1.2)

Tensile strength 19.0 (1.2) (Mpa) Tensile modulus (Mpa) 100% Elongation 0.6 300% Elongation 1.0 500% Elongation 1.5 Elongation at 930 break (%)

0.7 1.2 1.9 932

0.8 1.3 2.3 962

need to be added into NR with a large amount to gain sufcient mechanical properties due to the relatively weak interfacial adhesion of the llers with NR. For example, more than 50% carbon black, in some cases, is needed before NR is manufactured to product [32]. However, incorporating even a very small amount of MWCNTs can markedly reinforce natural rubber. The selfassembled NR with 1 wt.% MWCNTs receives an increase of 58% in tensile strength (from 19.0 to 30.1 Mpa), and a similar increase in tensile modulus at different elongations (Table 1). Interestingly, the exibility of host NR is not affected by the introduction of MWCNTs as its elongation at break even receives a small increase even though the composite shows a dramatic enhancement in rigidity. This is different from other polymeric/inorganic composites where their valuable exibility is compromised although their rigidity usually increases [33]. Without modifying the MWCNTs, natural rubber composite reinforced with p-MWCNTs exhibits less improvement in its mechanical properties due to the aggregation of MWCNTs (Table 1). Similar to our previous work [22,23], the improved properties show a strong correlation with the morphology of the composites. The better the MWCNTs disperse, the better the properties of the composites. The theoretical modeling studies on the mechanical properties of NR/MWCNT composites will be the subject of our future work to understand the fundamental interactions between the carbon nanotubes and the NR.

Fig. 7 The temperature dependent loss factor for NR and NR/MWCNT composites: (A) NR; (B) p-MWCNT composite; (C) m-MWCNT composite.

of composites which are prepared through self-assembly process moves to 55 C from 69 C of the NR, while the Tg of composites with p-MWCNTs remains almost the same as that of the NR, because of the low interaction between NR and aggregated MWCNTs. This has been observed for polyvinylalcohol (PVA)/silica (SiO2) nanocomposites where Tg shifted from 65 C (PVA) to 76 C (PVA composite with 0.5 wt.% SiO2) when strong interaction between PVA and SiO2 was present [35]. Another interesting phenomenon is that the maximum tan d of the composites is lower than that of the NR (Fig. 7). In other words, the loss angle of NR is bigger than that of the NR/MWCNT composites, suggesting that NR is able to absorb more energy than NR/MWCNT composites do under an acute strain environment. The accumulation of absorbed energy will cause thermal degradation and further reduce the mechanical property of materials. Therefore, the inner-thermogenesis or thermal stability of prepared NR/MWCNTs with smaller tan d is better than that of NR [35]. This is crucial for the NR products to be used in distortional and rolling conditions.

4.
3.5. Dynamic thermal mechanical analysis

Conclusions

To further understand the reinforcement mechanism by MWCNTs, DMA is conducted for the NR and NR/MWCNT composites. NR possesses viscoelasticity, so hysteresis may occur. When alternating stress is imposed, strain will lag a phase angle. The lag is not only relevant to their chemical structure, but also external conditions [34]. A typical glass transition turn is observed in the DMA curves for NR and NR composites (Fig. 7). For composites, the movement of NR molecular chains is restricted due to strong interfacial adhesion between NR phase and MWCNTs. Compared to that of the NR, the glass transition temperature (Tg) of composites, corresponding to the peak temperature of the curves, moves to a higher temperature. Particularly, the Tg

A self-assembly process combining latex compounding technique has been successfully used to develop NR/MWCNT composites. After two steps of assembly, the strong selfaggregation of MWCNTs has been greatly depressed and MWCNTs are homogenously distributed throughout the NR matrix as individual nanotubes, due to an excellent interfacial adhesion of MWCNTs with NR phase. The introduction of well dispersed acid modied MWCNTs in the NR matrix contributes to a signicant improvement in tensile strength, tensile modulus at different elongations, and inner-thermogenesis or thermal stability for NR host while the exibility of NR matrix is still maintained. Compared to that of the pure NR, the Tg of NR/MWCNT composites move to a higher temperature.

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Acknowledgements
The nancial support from the Natural Science Foundation of China (contract Grant number: 50763006) and Ministry of Science and Technology R & D research institutes special fund (contract Grant number: 2008EG134285) is gratefully acknowledged.

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