Applied Mechanics and Materials Vol 661 (2014) pp 8-13 Submitted: 2014-05-12

© (2014) Trans Tech Publications, Switzerland Revised: 2014-06-13

doi:10.4028/www.scientific.net/AMM.661.8 Accepted: 2014-06-13
Online: 2014-10-01

Study on Dispersion and Characterization of Functionalized MWCNTs

Prepared by Wet Oxidation
I. S. Zaine1, a, N. A. M. Napiah1,b, A. M. Yusof2,c, A. N. Alias1,
A. M. M. Ali3 and S.H. Khalid1,d
1
Department of Applied Sciences, Universiti Teknologi MARA Malaysia, 13500, Permatang Pauh,
Pulau Pinang, Malaysia
2
Faculty of Mechanical Engineering, Universiti Teknologi MARA Malaysia, 13500, Permatang Pauh,
Pulau Pinang, Malaysia
3
Faculty of Applied Sciences, Universiti Teknologi MARA Malaysia, 40450, Shah Alam, Selangor,
Malaysia
a
intan.zaine@ppinang.uitm.edu.my, bnoorezal113@ppinang.uitm.edu.my,
c
azmi349@ppinang.uitm.edu.my, dsitihajar057@ppinang.uitm.edu.my

Keywords: Dispersion, functionalized, MWCNTs, Raman spectroscopy, UV-Vis spectroscopy.

Abstract. The study of functionalized multi-walled carbon nanotubes (MWCNTs) is necessary for
future manipulation of the material. In this study, the MWCNTs was functionalized by refluxing
commercial MWCNTs (a-MWCNTs) in concentrated HNO3/H2SO4 (3:1 v/v) at 100oC for 6 hours.
The dispersion of a-MWCNTs and functionalized MWCNTs (f-MWCNTs) were observed after 1
hour sonication in ethanol. Both samples were characterized by UV-vis spectroscopy for dispersion
behavior. The dried f-MWCNTs and a-MWCNTs were characterized by Raman spectroscopy to
estimate the defect level. The morphology of the samples were analyzed by Transmission Electron
Microscopy (TEM). The f-MWCNTs was well dispersed in ethanol within 2 weeks of observations
period. The colloidal stability of a-MWCNTs was low as it was easily sediment after 24 hours. The
UV-vis spectra of f-MWCNTs show maximum absorbance at 250 nm meanwhile no absorbance was
observed for a-MWCNTs. Analysis from Raman spectrum shows that the f-MWCNTs have relative
intensity of 1.101 which is higher than a-MWCNTs that have relative intensity of 0.935. The image
from TEM revealed that the f-MWCNTs have structural defects and the absence of amorphous
carbon on sidewall meanwhile the a-MWCNTs indicate otherwise.

Introduction
Among carbon nanotubes (CNTs) family, multi-walled carbon nanotubes (MWCNTs) have received
special interest as a sensor [1], supercapacitor [2], medical implant [3] and solar cell [4] since
discovered by Iijima in 1991. MWCNTs are known to be chemically inert against common chemical
reactions. This nature restricts their dispersion into desired surfactant and become one of the factors
that decreased the unique properties of MWCNTs. The nanotubes tend to agglomerate in nearly all
surfactant due to the multiple van der Waals forces and π-π interactions. Therefore, it is essential to
functionalize the MWCNTs to enhance its dispersion into desired surfactant. Functionalization is a
chemical process that inserts functional groups on the sidewall of carbon nanotubes [5]. Through
functionalization, the interactions between the nanotubes become weak and allow the formation of
hydroxyl and carboxyl groups on the surface of nanotubes. Due to simple and low cost method, wet
oxidation [6] has been widely accepted to functionalize carbon nanotubes instead of plasma oxidation
[7]–[10], ozone oxidation [11] and air oxidation [12], [13]. The wet oxidation is commonly made by
refluxing MWCNTs in oxidizing agents such as HNO3 and H2SO4, in ratio 1:3 v/v. In this study, the
dispersion of functionalized MWCNTs in ethanol after refluxing in HNO3/H2SO4 (3:1 v/v) at 100oC
for 6 hours was investigated. The effects of the oxidation agents on MWCNTs were studied via
Raman spectroscopy and TEM. All the data obtained were compared to commercial MWCNTs.

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (ID: 128.210.126.199, Purdue University Libraries, West Lafayette, USA-27/05/15,17:25:12)
 Applied Mechanics and Materials Vol. 661 9

Materials and methods

In this work, two types of MWCNTs were used: 1) the commercial MWCNTs (a-MWCNTs), and b)
the functionalized MWCNTs (f-MWCNTs). The a-MWCNTs with a purity of > 95%, outer diameter
of > 50 nm and length of 10-20 µm was purchased from Chengdu Organic Chemicals Co., Ltd.,
Chinese Academy of Sciences. The HNO3 (65 wt%), H2SO4 (95-98 wt%) and ethanol were obtained
from R&M marketing, United Kingdom. The distilled water was used for washing process. Fig. 1
shows detail preparation of f-MWCNTs.
HNO3:H2SO4
a-MWCNTs
(3:1 v/v)

The mixture was refluxed for 6 hours at 100o

The mixture was allowed to cool at

room temperature

The mixture was filtered. The precipitate, assigned

as f-MWCNTs was washed several times by
distilled water until the water pH approximately at 7

The f-MWCNTs was dried overnight at 80o in

an oven to remove volatile solvents

The dry f-MWCNTs was The dry f-MWCNTs was

dispersed in ethanol before analysed by Raman
sonicated for 1 hour spectroscopy and TEM

The colloidal was diluted by a factor

The colloidal was of 30 before analyzed by UV-vis
observed for two weeks spectroscopy

Fig. 1 Preparation of f-MWCNTs

UV-vis spectroscopy was recorded using spectrometer (Perkin Elmer Lambda 35) operating between
220 and 800 nm. The defect formed in the structure of f-MWCNTs was measured using inVia Raman
microscope spectrometer (Renishaw). For Raman measurements, the sample was excited with HeNe
laser at 633 nm (1.961 eV). The morphological characterization was examined by using transmission
electron microscope (Phillips CM12).

Result and discussion

A) Dispersion analysis
The dispersion of a-MWCNTs in ethanol was low as it was easily sediment after 24 hours. The
sedimentation was probably caused by agglomeration of nanotubes and lack of hydrogen bonding [5].
After oxidation process, the dispersion of MWCNTs in ethanol was improved since the f-MWCNTs
form a stable colloidal within 2 weeks of observation period. This suggests that the sidewall of
f-MWCNTs had been modified with the presence of functional group after oxidation process. These
functional groups are polarized that allows the f-MWCNTs to repel each other, keeping the solution
dispersed although after 2 weeks. The polarized functional groups also help to weaken the van der
Waals forces among individual MWCNTs.
10 Applied Solutions of Engineering Science

B) UV-vis spectroscopy
The UV-vis spectra can be used as scientific evidence to support the dispersion analysis. This is due
to the fact that the individual CNTs are active in the UV-vis region meanwhile the bundle CNTs are
hardly active in the wavelength between 200 and 1200 nm [14]. According to the literature, there
exist a relation between the amount of CNTs individually dispersed in surfactant and the intensity of
the corresponding absorption spectra [14], [15]. As illustrated in Fig. 2, the UV-vis spectra of
f-MWCNTs after 1 hour sonication shows an absorbance with a maximum value occur at 250 nm
before gradually decreases. For a-MWCNTs there was no absorbance observed within UV-vis
spectra. The a-MWCNTs exist as big aggregates and bundles in ethanol although after sonication due
to the absence of functional group. From the other side, it is suggested that the energy provided during
sonication also was not enough to overcome the van der Waals forces in the MWCNTs bundles.
These arguments are in parallel with the dispersion analysis.

Fig. 2: UV-vis spectra for f-MWCNTs after 1 hour sonication in ethanol.

C) RAMAN spectroscopy
The Raman spectra of the a-MWCNTs and f-MWCNTs are presented in Fig. 3. For both sample, two
peaks were appeared at around 1330 cm-1 (D-band) and 1580 cm-1 (G-band). The D-band corresponds
to the disordered or sp3-hybridized carbons in the CNTs wall and the G-band is assigned to vibrations
of sp2-bonded carbon atoms in graphene-like structures, such as the CNTs [8]. This result indicates
that the oxidation agents did not destroy the graphitic structure of CNTs since the peaks were not
shifted after the oxidation process. An increase in the D-band intensity has been shown to be an
indication of side-wall sp2→sp3 hybridization from covalent binding of functional various moieties
[16].

Fig. 3: The Raman spectra of a-MWCNTs and f-MWCNTs.

 Applied Mechanics and Materials Vol. 661 11

The relative intensities of the D-bands and G-bands were widely used for characterizing the presence
of defects at sidewall of nanotubes. As shown in Table 1, the f-MWCNTs have the highest values of
ID/ IG ratios as compared to the a-MWCNTs, which indicate that some defect presence at sidewall of
carbon nanotubes after oxidation process. The sidewall defects can present in the form of rotated
bonds, vacancies and sp3 defects that is carbon atoms in the sp3 configuration and determinated by –H
or various functionalities [17]. The change of the ID/IG ratio also could be due to the changes in the
MWCNTs geometry caused by the binding of new functional groups or an electrophilic addition at
hexatomic-hexatomic boundaries [18]. The other used of ID/IG ratio is to estimate the in-plane crystal
size, La. In this work, La was calculated by formula proposed by Cancado et al. for nanographitic
material [19]. It found that La for MWCNTs was decrease after oxidation process suspected due to the
removal of impurities and amorphous carbon on sidewall of nanotubes.

Table 1: Estimation of defect level and crystallite size of MWCNTs

Sample ID/IG Crystallite size, La (nm)
a-MWCNTs 0.935 40.50
f-MWCNTs 1.101 34.39

D) TEM analysis
Fig. 4 illustrates the morphology of a-MWCNTs and f-MWCNTs magnified at 50 nm and 100 nm
resolutions. It found that MWCNTs are random in size for both samples. Fig. 4 (a)-(b) revealed the
presence of amorphous carbon attached on the nanotube surface highlighted by circles. After
oxidation process, the overall level of amorphous carbon was reduced since it hardly seen the
amorphous on Fig. 4 (c)-(d). Comparing with a-MWCNTs, the morphology of f-MWCNTs seems
affected by oxidation process especially for smaller nanotubes due to the introduction of structural
defects at the outer sidewall. This defects as indicated with arrow in Fig. 4 (c)-(d) were in parallel
with the prediction from Raman spectra analysis mentioned earlier. The defects have found to cause a
distortion in the linearity of the MWCNTs structure. The distortion also could be due to removal of
amorphous carbon attached on the nanotube surface [20] and heptagon-pentagon pairs [21]. While
comparing this with Raman spectroscopy results, the functionalized nanotube in general still
maintaining its graphitic structures.

(a) (b) (c) (d)

Fig. 4: TEM image of (a)-(b) a-MWCNTs and (c)-(d) f-MWCNTs. Amorphous carbon is highlighted
by circles and sidewall defects is indicated with arrows.

Conclusion
The MWCNTs was well dispersed in ethanol after refluxing MWCNTs in concentrated
HNO3/H2SO4, which is necessary for future manipulation of the material such as fabrication of
composite film through electrophoretic deposition technique. Further investigations of the
f-MWCNTs revealed that the absorbance range fall within the UV-vis region which illustrates the
nanotubes become active after oxidation process. Analysis from Raman spectroscopy and TEM
showed that f-MWCNTs had some defects which provide a lot of active sites for further
functionalization. Finally, the wet oxidation is still a relevant process, that offer a simple and yet low
cost approach to functionalize MWCNTs, enhance its dispersion and at the same time remains its
graphitic structure.
12 Applied Solutions of Engineering Science

Acknowledgment
The work has been supported by the Malaysia Ministry of Education through its Research
Acculturation Grant Scheme (RAGS/2013/UITM/SG02/2).

Corresponding Author
Intan Syaffinazzilla Zaine
E-mail address: intan.zaine@ppinang.uitm.edu.my

References
[1] V. M. Aroutiounian, A. Z. Adamyan, E. A. Khachaturyan, Z. N. Adamyan, K. Hernadi, Z.
Pallai, Z. Nemeth, L. Forro, A. Magrez, and E. Horvath, “Study of the surface-ruthenated
SnO2/MWCNTs nanocomposite thick-film gas sensors,” Sensors Actuators B Chem., vol.
177, pp. 308–315, Feb. 2013.
[2] D. Ghosh, S. Giri, A. Mandal, and C. K. Das, “H+, Fe3+ codoped polyaniline/MWCNTs
nanocomposite: Superior electrode material for supercapacitor application,” Appl. Surf. Sci.,
vol. 276, pp. 120–128, Jul. 2013.
[3] R. A. Ahmed, A. M. Fekry, and R. A. Farghali, “A study of calcium
carbonate/multiwalled-carbon nanotubes/chitosan composite coatings on Ti–6Al–4V alloy for
orthopedic implants,” Appl. Surf. Sci., vol. 285, pp. 309–316, Nov. 2013.
[4] H. Niu, S. Qin, X. Mao, S. Zhang, R. Wang, L. Wan, J. Xu, and S. Miao, “Axle-sleeve
Structured MWCNTs/Polyaniline Composite Film as Cost-effective Counter-Electrodes for
High Efficient Dye-Sensitized Solar Cells,” Electrochim. Acta, vol. 121, pp. 285–293, Mar.
2014.
[5] A. G. Osorio, I. C. L. Silveira, V. L. Bueno, and C. P. Bergmann,
“H2SO4/HNO3/HCl—Functionalization and its effect on dispersion of carbon nanotubes in
aqueous media,” Appl. Surf. Sci., vol. 255, no. 5, pp. 2485–2489, Dec. 2008.
[6] T. A. Saleh, “The influence of treatment temperature on the acidity of MWCNT oxidized by
HNO3 or a mixture of HNO3/H2SO4,” Appl. Surf. Sci., vol. 257, no. 17, pp. 7746–7751, Jun.
2011.
[7] P. Mishra and S. S. Islam, “Surface modification of MWCNTs by O2 plasma treatment and its
exposure time dependent analysis by SEM, TEM and vibrational spectroscopy,” Superlattices
Microstruct., vol. 64, pp. 399–407, Dec. 2013.
[8] F. Pourfayaz, Y. Mortazavi, A. Khodadadi, S. H. Jafari, S. Boroun, and M. V. Naseh, “A
comparison of effects of plasma and acid functionalizations on structure and electrical property
of multi-wall carbon nanotubes,” Appl. Surf. Sci., vol. 295, pp. 66–70, Mar. 2014.
[9] J. Li, Z. Wu, C. Huang, H. Liu, R. Huang, and L. Li, “Mechanical properties of cyanate
ester/epoxy nanocomposites modified with plasma functionalized MWCNTs,” Compos. Sci.
Technol., vol. 90, pp. 166–173, Jan. 2014.
[10] K.-P. Yoo, K.-H. Kwon, N.-K. Min, M. J. Lee, and C. J. Lee, “Effects of O2 plasma treatment
on NH3 sensing characteristics of multiwall carbon nanotube/polyaniline composite films,”
Sensors Actuators B Chem., vol. 143, no. 1, pp. 333–340, Dec. 2009.
[11] S. Yang, X. Wang, H. Yang, Y. Sun, and Y. Liu, “Influence of the different oxidation
treatment on the performance of multi-walled carbon nanotubes in the catalytic wet air
oxidation of phenol.,” J. Hazard. Mater., vol. 233–234, pp. 18–24, Sep. 2012.
[12] A. Ansón-Casaos, M. González, J. M. González-Domínguez, and M. T. Martínez, “Influence
of Air Oxidation on the Surfactant-Assisted Purification of Single-Walled Carbon Nanotubes,”
Langmuir, vol. 27, no. 11, pp. 7192–7198, Apr. 2011.
[13] N. Dementev, S. Osswald, Y. Gogotsi, and E. Borguet, “Purification of carbon nanotubes by
dynamic oxidation in air,” J. Mater. Chem., vol. 19, no. 42, pp. 7904–7908, 2009.
 Applied Mechanics and Materials Vol. 661 13

[14] J. Yu, N. Grossiord, C. E. Koning, and J. Loos, “Controlling the dispersion of multi-wall
carbon nanotubes in aqueous surfactant solution,” Carbon N. Y., vol. 45, no. 3, pp. 618–623,
Mar. 2007.
[15] L. Jiang, L. Gao, and J. Sun, “Production of aqueous colloidal dispersions of carbon
nanotubes,” J. Colloid Interface Sci., vol. 260, no. 1, pp. 89–94, Apr. 2003.
[16] A. Fraczek-Szczypta, E. Dlugon, A. Weselucha-Birczynska, M. Nocun, and M. Blazewicz,
“Multi walled carbon nanotubes deposited on metal substrate using EPD technique. A
spectroscopic study,” J. Mol. Struct., vol. 1040, pp. 238–245, May 2013.
[17] F.-G. Banica, Chemical sensors and biosensors: fundamentals and applications. John Wiley &
Sons, 2012, p. 576.
[18] B. Scheibe, E. Borowiak-Palen, and R. J. Kalenczuk, “Oxidation and reduction of multiwalled
carbon nanotubes — preparation and characterization,” Mater. Charact., vol. 61, no. 2, pp.
185–191, Feb. 2010.
[19] L. G. Cançado, K. Takai, T. Enoki, M. Endo, Y. a. Kim, H. Mizusaki, a. Jorio, L. N. Coelho, R.
Magalhães-Paniago, and M. a. Pimenta, “General equation for the determination of the
crystallite size L[sub a] of nanographite by Raman spectroscopy,” Appl. Phys. Lett., vol. 88,
no. 16, p. 163106, 2006.
[20] O. Access, R. Yudianti, H. Onggo, Y. Saito, T. Iwata, and J. Azuma, “Analysis of Functional
Group Sited on Multi-Wall Carbon Nanotube Surface,” pp. 242–247, 2011.
[21] J. H. Lehman, M. Terrones, E. Mansfield, K. E. Hurst, and V. Meunier, “Evaluating the
characteristics of multiwall carbon nanotubes,” Carbon N. Y., vol. 49, no. 8, pp. 2581–2602,
Jul. 2011.
Applied Solutions of Engineering Science
10.4028/www.scientific.net/AMM.661

Study on Dispersion and Characterization of Functionalized MWCNTs Prepared by Wet Oxidation

10.4028/www.scientific.net/AMM.661.8