RJTA Vol. 12 No.

2 2008

Comparison of Mechanical Properties of Various Types of Carbon Nanotubes in Polypropylene Fiber

Priyanka Katiyar, T V Sreekumar*, Kingsuk Mukhopadhyay, Anurag Srivastava and K U Bhasker Rao Defence Materials & Stores Research & Development Establishment, G. T. Road, Kanpur, India-208013

ABSTRACT
Textile fibers reinforced with carbon nanotubes (CNT) show significant improvement in mechanical properties. Being lightweight and stronger than ordinary textile grade fibers, they can be used for different reinforcement applications. This paper reports a study on the comparison of the mechanical properties of composite fibers made of polypropylene (PP) and CNT obtained from different sources. A single walled nanotube from Carbolex USA, mutiwalled nanotubes from Iljin, Korea and DMSRDE Kanpur are used for the study. The composite fibers are made in two varieties viz. 0.5wt% and 1wt% concentration of CNT. It is observed that the mechanical properties, such as tenacity and modulus, increased with increased concentrations of the CNT irrespective of the brand and nature of the synthesis. The composite fibers made of multi walled CNT produced by DMSRDE give the best results in terms of spinnability and mechanical properties. The tenacity of the DMSRDE fibers is as high as ~9gpd and modulus as high as 114gpd. Keywords: Carbon nanotube, Draw ratio, Elongation, Modulus, Polypropylene, Tensile strength Mechanical properties of polypropylene (PP) are generally modified by melt mixing with particulates (talc, mica, clay) (Liu & Wu, 2001) and fibrous (glass, jute, aramid and carbon fibers) fillers (Assouline, Pohl, Fulchiron, Gerard, Lustiger, Wagner & Marom, 2000) as well as by melt blending with other polymers (Duvall, Sellitti, Myers, Hiltner & Baer, 1994). Reinforcement with nanoscale improves mechanical properties, polymer crystallization behaviour, conductivity, etc (Thostenson, Ren & Chou, 2001; Bhattacharrya, Sreekumar, Liu, Kumar, Ericson & Hauge, 2003). The addition of nanostructured polyhedral silsesquioxane (POSS) (Fu, Yang, Somani, Zong, Hsiao, Phillips, Blanski & Ruth, 2001), vapor grown carbon nanofiber (Lozano & Barrera, 2001), as well as montmorillonite clay (Ma, Zhang, Qi, Li & Hu, 2002) increases the crystallization rate of polypropylene. Due to their high tensile strength and modulus, carbon nanotubes are excellent candidates for the nano-reinforcement of a variety of polymer matrices (Baughman, Zakhidov & de Heer, 2002).
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1.

Introduction

Carbon nanotubes have exceptional physical, mechanical, electrical, thermal and optical properties and are heralded to be the ultimate reinforcing material for polymer and other matrices (Baughman, Zakhidov & de Heer, 2002). Significant breakthroughs have been reported in the processing of carbon nanotubes and carbon nanotube/polymer composite films and fibers (Sreekumar, Liu, Min, Guo, Kumar, Hauge & Smalley, 2004). Property improvements with carbon nanotubes include enhanced tensile modulus, tensile strength, torsional modulus, compressive strength, fatigue behavior, toughness, glass transition temperature, electrical conductivity, thermal conductivity, solvent resistance and reduction in thermal shrinkage as well as anisotropic optical properties (Sreekumar, Liu, Min, Guo, Kumar, Hauge & Smalley, 2004).
* Corresponding author. Fax: (91) 512 2450 404 E-mail address: sreekumar.veedu@gmail.com

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To obtain the full potential of carbon nanotubes (CNTs) (Baughman, Zakhidov & de Heer, 2002), they should be well dispersed in the polymer matrix and should have efficient load transfer between them. Poor interaction leads to poor CNT dispersion in the matrix as observed in the case of polypropylene (Bhattacharrya, Sreekumar, Liu, Kumar, Ericson & Hauge, 2003), while its dispersion in polyacrylonitrile (PAN) (Sreekumar, Liu, Min, Guo, Kumar, Hauge & Smalley, 2004) and polyvinyl alcohol (PVA) (Zhang, Liu Sreekumar, Kumar, Hu & Smith, 2004) was quite good. Various interaction mechanisms have been suggested in the literature. Most of the commercially available CNTs are highly entangled or contain large quantities of impurities. This paper reports a study conducted at DMSRDE to compare the dispersion of various nanotubes in PP matrix and the mechanical properties of various composite fibres made of PP and CNT from different sources. The CNTs were obtained from (a) ILJIN, Korea (MWNT); (b) CarboLex, USA (SWNT); and (c) DMSRDE (MWNT). The novelty of this study is that the tubes produced at DMSRDE were never studied for fibre forming properties before as they are not available commercially. It was observed that the composite fibers made from CNTs produced at DMSRDE produces better mechanical properties in terms of tenacity and modulus than the SWNT from CarboLex, USA.

composites. The polymer and CNTs were vacuum dried at 1500C for 12h. Before feeding for melt compounding, the polymer and CNTs were mechanically mixed. The melt compounding was performed using a laboratory scale Haake Rheomix internal mixer operating at 50rpm for 30min at 2300C. PP/CNT composites containing 0.5% and 1% concentrations of various types of CNTs were prepared. A controlled polypropylene sample without any nanotubes was also processed in the Haake Mixer under the same conditions. 2.3 Preparation of PP-CNT Composite Fiber

The melt compounded PP/CNT composite samples were cut into small pieces and dried at 150oC under a vacuum for at least 24h. They were spun into fibres using a small scale melt spinning machine manufactured by the Bradford University Research Ltd., UK (Figure 1), with a single holed spinneret of 1mm diameter. The fibre spinning was carried out at 200oC with ram speed of 1.4mm/min. The take up speed was kept at 50m/min and 25m/min for 0.5% and 1% tubes respectively. Composite fibres having 0.5% and 1.0% CNTs were subsequently drawn to a draw ratio of 8 at 100oC and a draw ratio of 40 at 110oC respectively. The mechanical properties of drawn fibers were tested on a Favimat fibre tester that had a load cell capacity of 1kg provided by Textechno, Germany. The gauge length was kept at 20mm with a testing rate of 20mm/min.

2.
2.1

Experimental
Material

Fibre grade polypropylene chips with a melt flow index of ~13 were obtained from a local market. SWNTs were obtained from CarboLex Inc., Lexington, USA with approximate diameters between 1-2nm. They were prepared by the arc discharge method. Two types of MWNT were used in this study, one was purified nanotubes indigenously developed at DMSRDE and the other obtained from ILJIN, Korea. The diameters of both MWNTs were ~10-20nm. Both MWNTs were produced using the CVD method. 2.2 Preparation of PP-CNT Composites:

Fig. 1. Laboratory Melt Spinning System

3.

Results and Discussion

A simple melt compounding route was adopted for the preparation of PP and various types of CNT
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The tubes obtained from ILJIN and CarboLex were highly entangled in nature while the DMSRDE tubes seems to be well separated as seen by SEM (Figure 2). Also, in the case of

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CarboLex, a lot of impurities could be seen either coated on the tube bundle or as spheres. The optical microscopy results of the PP-CNT composites in the melted state are given in Figure 3, which shows significant amounts of nanotube aggregates in all the cases. Large and non dispersed chunks of nanotubes are seen in the case of the CarboLex SWNT. One main reason for this could be the high entanglement of the tubes and the presence of high Van der Waals interaction. For better mechanical properties, good dispersion without any aggregates is essential as the aggregates act as weak links which serve as stress concentration points that can initiate breaks while the fiber is being drawn. Increased aggregates can cause the rheology of the polymer to change, making the processing of the fibres increasingly difficult. Additionally, the aggregation of nanotubes causes the formation of irregular fibre surfaces with large variations in denier. By visual inspection, it was observed that there are greater amounts of irregular fibre surfaces formed in the composite fibres containing ILJIN tubes.

It was also noticed that spinning the fibre was difficult when the CNT content in the matrix was increased. The material flow property was reduced and the spun fibre became more rigid. Thus, composite fibres with concentrations higher than 1% CNT can not be achieved. The same problem occurred during the fibre drawing . With 1% CNT, fibre breakage occurred during the drawing process most of the time. It was not because the fibres were weak, but because of the fibers low extensibility. This was evident from the higher modulus of PP/CNT composite fibre with 1% CNT. Figure 4 shows a photograph of the processed polypropylene and PP/CNT composite fibre with DMSRDE nanotubes. The fibres obtained are very uniform with thousands of meters of continuous filaments being produced without any filament breakage.

(a)

(a)

(b)

(b)

(c)
Fig. 3. Optical microscopy images of various melt mixed PP/NT composites (a) PP/ MWNT (ILJIN) (b) PP/ SWNT (CarboLex) (c) PP/ MWNT (DMSRDE)

(c)

Fig.2. SEM images of carbon nanotubes used in the experiment (a) MWNT (ILJIN) (b) SWNT (CarboLex) (c) MWNT (DMSRDE)
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Fig. 4. Pure PP and PP/MWNT (DMSRDE) fibres The mechanical properties of various PP/CNT composite fibres and pure PP fibre are summarized in Tables 1 and 2. It is observed, from Figures 5 and 6 that as the concentration of carbon nanotubes increases, the fibre breaking strength and modulus increases. At 1%, the CNT concentration PP-CNT (DMSRDE) shows maximum tenacity i.e. 9.07gpd. For both 0.5% and 1% PP-CNT (DMSRDE) composite fibres, the modulus of PP improves significantly. The modulus of pure PP at a draw ratio of 8 is 49.8gpd which improves to 61gpd. At a draw ratio of 40 with 1% CNT, the modulus of PP increases from 91.8gpd to 113.9gpd. The tensile strength also improves from 5.17 to 5.73gpd with 0.5% of DMSRDE tubes. Both DMSRDE and ILJIN nanotube composite fibers show a tenacity of

5.73gpd with 0.5% of CNT. Fibers containing the DMSRDE nanotube show a lower standard of deviation in the case of tenacity values i.e. 0.43 in comparison to ILJIN nanotubes composite fibers i.e. 0.89. This is due to the comparatively better dispersion and spinnability of DMSRDE tubes as both ILJIN and CarboLex tubes are highly entangled in nature and the DMSRDE tubes are well separated. Some improvement is observed with 1% CNT tubes. In comparing all the PP-CNT composite fibres, the composite fibres containing the DMSRDE produced nanotube are found to be better in terms of dispersibility, homogeneity of nanotubes and fiber mechanical properties. The composite fibres do not exhibit the natural draw that the 100% polypropylene fibre does. Processed PP fibres were drawn up to a draw ratio of 32 whereas 0.5% CNT were drawn up to a draw ratio of 8 with a take up speed of 50mm/min and the 1% CNTs composite fibers were drawn up to a draw ratio of 40 with a take up speed of 25mm/min. The introduction of nanotubes prevents the polymer chains from slipping past each other, thereby improving modulus and reducing the elongation.

Table 1. Comparison of mechanical properties of PP/CNT composite fibres with 0.5% tubes (Draw ratio = 8)
Processed PP Denier Elong. % Tenacity gpd Modulus gpd 15.27 2.59 22.96 2.39 5.17 0.54 49.80 3.91 PP/MWNT (DMSRDE) 16.84 1.42 14.84 1.8 5.73 0.43 60.69 4.97 PP/MWNT (ILJIN ) 15.17 2.8 20.42 5.16 5.73 0.89 60.14 10.8 PP/SWNT (Carbolex) 13.94 2.87 20.94 3.02 5.33 0.53 48.49 4.97

Table 2. Comparison of mechanical properties of PP/CNT composite fibres with 1% tubes (Draw ratio=40)
Processed PP Denier Elong. % Tenacity gpd Modulus gpd 8.99 12.80 7.72 91.80 PP/MWNT (DMSRDE) 17.07 14.07 9.07 113.9 83 PP/MWNT (ILJIN ) 14.18 11.53 8.41 117.84 PP/SWNT (Carbolex) 16.5 13.2 8.16 112.8

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10 9 8 7 6 5 4 3 2 1 0 0

DMSRDE ILGIN CARBOLEX

Tenacity 'gpd'

0.2

0.4

0.6

0.8

CNT concentration '%'

Fig. 1. Effect of CNT concentration on tenacity of PP/CNT composite fibers

160 140 120 Modulus 'gpd' 100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1 CNT concentration '%'
DMSRDE ILGIN CARBOLEX

Fig.6. Effect of CNT concentration on modulus of PP/CNT composite fibers

10
PROCESSED PP

9 8 7

DMSRDE CARBOLEX ILGIN

Tenacity 'gpd'

6 5 4 3 2 1 0 0 2 4 6 8 10 12 14 16

Elongation '%'

Fig. 7. Stress-strain curves of various PP/ CNT composite fibers (1% CNT)
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4.

Conclusions

Acknowledgements
The authors wish to acknowledge Dr. Anoop Anand and Mr. Rajendra Mohan for their help during melt mixing/fibre spinning and Mrs. D. Bhattacharjee for her valuable input in the preparation of this paper.

The carbon nanotubes produced at DMSRDE are well aligned and well separated. Other tubes are found to be more entangled. As a result, the DMSRDE tubes are found to be more evenly dispersed than Iljin and CarboLex. Due to this reason, the spinnability or ease of fibre spinning is better in the case of composites consisting of DMSRDE tubes. In all the cases above, the mechanical properties of polypropylene improvewith the addition of carbon nanotubes. The composite fibres made of multi walled nanotubes produced in DMSRDE show a significant improvement in mechanical properties as compared to the single walled nanotubes of CarboLex and the multi walled nanotubes of Iljin. The increase in tenacity of PP-CNT fibre is in the range of 10-18% and the modulus is approximately 22-27% as compared to pure PP fibres. Generally, by incorporating fillers of micron size into the fibre, mechanical properties, especially tenacity and elongation, are reduced. This is because these fillers act as weak linkages and become points of stress concentration. However, in the present case, all the mechanical properties, such as modulus, tensile strength and elongation are improved by the incorporation of carbon nanotubes. As we find many lumps or chunks of carbon nanotubes in the polymer matrix, one would expect a decrease in mechanical properties. On the contrary, we actually find a significant improvement in mechanical properties. One can conclude that CNTs in the present case reinforce the matrix very well. From the results, one can predict great improvements in the properties if the tubes are individually dispersed in the matrix and oriented in the direction of the fiber axis. This study gives further scope for more scientific studies, such as electrical conductivity and static charge dissipation etc as high static charge accumulation is one major problem associated with polypropylene fabrics. If one can make a conducting polypropylene fibre containing carbon nanotubes, inherently antistatic, then PP fabrics can be produced without sacrificing the mechanical properties or having to applyfinishes.

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