Copyright 2013 American Scientic Publishers Journal of

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Printed in the United States of America Vol. 13, 56315635, 2013

RESEARCH ARTICLE
Effect of Carbon Nanotube Addition on the Wear
Behavior of Basalt/Epoxy Woven Composites
M. T. Kim1 , K. Y. Rhee2 , B. H. Lee3 , and C. J. Kim3
1
Department of R&D, Gumi Electronics and Information Technology Research Institute,
Gumi, 730-853, Korea
2
Department of Mechanical Engineering, Kyung Hee University, Yongin, 449-701, Korea
3
Deagu-Gyeongbuk R&D Center, Korea Automotive Technology Institute, Deagu, 704-230, Korea

The effect of acid-treated carbon nanotube (CNT) addition on the wear and dynamic mechan-
ical thermal properties of basalt/epoxy woven composites was investigated in this study.
Basalt/CNT/epoxy composites were fabricated by impregnating woven basalt bers into epoxy resin
mixed with 1 wt% CNTs which were acid-treated. Wear and DMA (dynamic mechanical analyzer)
tests were performed on basalt/epoxy composites and basalt/CNT/epoxy composites. The results
showed that the addition of the acid-treated CNTs improved the wear properties of basalt/epoxy
woven composites. Specically, the friction coefcient of the basalt/epoxy composite was stabilized
in the range of 0.50.6 while it fell in the range of 0.30.4 for basalt/CNT/epoxy composites. The
wear volume loss of the basalt/CNT/epoxy composites was approximately 68% lower than that
of the basalt/epoxy composites. The results also showed that the glass transition temperature of
basalt/CNT/epoxy composites was higher than that of basalt/epoxy composites. The improvement
Deliveredofby
of wear properties Publishingcomposites
basalt/epoxy Technology by to:
the Chinese University
addition of of CNTs
acid-treated Hong wasKong caused by
the homogeneous load IP:transfer
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between basalt bers10 Dec
and 2015
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matrix due to the reinforcement of
CNTs. Copyright: American Scientific Publishers
Keywords: Basalt Fiber, Wear Property, Woven, Friction Coefcient.

1. INTRODUCTION mechanical strength than the epoxy/basalt or unmodi-

The use of basalt bers as reinforcing materials in the
composite materials is increasing in motorcar, shipbuild-
ing, aviation, electronic, and chemical industries because
they are better than glass bers under the characteristics:
specic durability, temperature of application, chemical
stability, especially in alkaline environments. Particularly,
they can be produced by the application of one-phase tech-
nology and the cost of production is as low as the cost of
production of glass bers. Therefore, many research results
have been reported on the mechanical properties of basalt
ber reinforced composites.14
Recently, hybrid basalt/polymer composites reinforced
with CNTs are attracting an attention because it is
expected that the basalt/CNT/polymer composites may
produce better material properties than that of basalt/
polymer composites. Chen et al. fabricated the acid and
ether functionalized CNT lled epoxy/basalt ber compos-
ites and reported that this composite showed the greater
Author to whom correspondence should be addressed.
ed CNT/basalt composites.5 Lee et al. applied silane
treatment of CNTs to improve dispersion and interfacial
characteristics of CNTs in the epoxy matrix and investi-
gated the effect of silane treatment of CNTs on the tensile
properties of CNT/epoxy/basalt multiscale composites.6
Their results showed that the tensile strength and Youngs
modulus of the silane-treated CNT/epoxy/basalt multiscale
composites were 17% and 21%, respectively, greater
than that of the acid-treated CNT/epoxy/basalt compos-
ites. However, no research result has been reported on
the effect of CNTs addition on the wear properties of
CNT/epoxy/basalt.
In this study, the effect of CNTs addition on the
tribological and dynamic mechanical thermal proper-
ties of basalt/epoxy composites was investigated. CNTs
were surface-modied with acid treatments. Wear and
DMA tests were performed on basalt/epoxy and acid-
treated basalt/CNT/epoxy composites. The worn surfaces
of both composites were examined with SEM to deter-
mine the wear mechanisms with respect to the addition of
the CNTs.

J. Nanosci. Nanotechnol. 2013, Vol. 13, No. 8 1533-4880/2013/13/5631/005 doi:10.1166/jnn.2013.7037 5631

 Effect of Carbon Nanotube Addition on the Wear Behavior of Basalt/Epoxy Woven Composites
2. EXPERIMENTAL DETAILS
2.1. Materials and Fabrication
RESEARCH ARTICLE
The basalt bers and carbon nanotubes used were woven
type basalt bers (EcoB4-F260, Secotech, Korea) with
area density of 260 g/m2 and the multi-walled carbon
nanotubes, (MWCNTs, CM-95, Hanhwa Nanotech, Korea)
prepared by a chemical vapor deposition method, respec-
tively. The reagents used for the acid treatment were
nitric acid (6062%, Junsei Chemical, Japan), sulfuric
acid (95%, Junsei Chemical), acetone (99.5%, Dae Jung
Chemical, Korea), and ethanol (99.5%, Aldrich, USA).
The epoxy used was diglycidyl ether of bisphenol A
(YD-115, Kukdo Chemical, Korea), and the curing agent
was polyamidoamine (G-A0533, Kukdo Chemical, Korea).
The acid treatment of CNTs were performed by following
the procedure described in Ref. [7]. The basalt/CNT/epoxy
composites were fabricated as follows. The epoxy resin
mixed with hardener (2:1, v/v) were made using 1 wt%
acid-treated CNTs. Eight plies of basalt fabrics were then
impregnated into the matrix, and the composites were
cured in an auto-clave (ISA-CA30, Ilshin Co., Korea) at
3 kgf/cm2 and 120  C for 2 hours.
2.2. Characterization
The Fourier transform Delivered by Publishing
infrared Technology
(FT-IR) spectra
recorded on a JASCO FT-IR IP: 172.77.34.188
spectrometer with On:
pellets to observe the functional group Copyright:
on theAmerican
CNTs. Scientific
Dynamic mechanical analysis was analyzed using a
dynamic mechanical analyzer (DMA, Q-800, TA Instru-
ment, USA) in single cantilever mode. A temperature
range from 25 to 200  C was applied at a heating rate
of 10  C/min at a frequency of 1 Hz. The wear test was
performed with a wear test machine (MPD Friction and
Wear Tester, Korea) following the ball-on-disc procedure
of ASTM G 99.8 The wear specimens were machined to
a diameter of 30 mm and height of 10 mm, and cleaned
with acetone. The counter wear material used was a zir-
conia ball ( 12.7 mm diameter). The sliding distance,
speed, and applied load were 3,500 m, 0.06 m/s, and 10 N,
respectively, for all the tests. At least three tests were per-
formed for each specimen to ensure the reliability of test
results. The worn surfaces of the specimens were exam-
ined using an optical microscope and SEM.
3. RESULTS AND DISCUSSION
The FT-IR analysis was made on the CNTs before and
after acid treatment to determine the chemical change on
the surface of CNT due to the acid treatment. Figure 1
exhibits FT-IR spectra of the pristine and acid-treated
CNTs. As shown in the gure, for the pristine CNTs,
the peaks at 3440 cm1 and 1048 cm1 are attributed to
the presence of hydroxyl groups (OH) on the surface
5632
Kim et al.
Fig. 1. FT-IR spectrum of (a) pristine CNTs, (b) acid-treated CNTs.
of the CNTs, which resulted from either oxidation during
purication of the raw material or atmospheric moisture
present on the CNTs.9
For the acid-treated CNTs, the IR spectrum has two
new peaks at 1715 cm1 and 1169 cm1 , which corre-
sponds to the C O and C O stretching vibrations of the
carboxylic groups (COOH), respectively. An absorption
peak at 3440 cm1 is observed for the OH functionality,
and a peak at 1381 cm1 is due to the OH bonding defor-
was to:mation
Chinese UniversityThis
in COOH. of Hong Kong
indicates that the acid treatment
KBrThu, of
10 Dec 2015 23:21:21
CNTs creates OH and COOH groups on the CNTs.
Publishers
The effects of the CNTs addition on the mechanical
thermal properties of the basalt/epoxy composites were
determined by comparing the storage modulus and tan
of basalt/epoxy composites with that of basalt/CNT/epoxy
composite. Figure 2(a) shows the variation of storage mod-
ulus as a function of temperature for both composites. As
shown in the gure, the storage modulus of basalt/CNT/
epoxy composites was greater than that of basalt/epoxy
composites in the range of glass transition region, whereas
no signicantly differences in the rubbery plateau region.
The storage modulus drop is related to an energy dissipa-
tion involving cooperative motions of the polymer chain,
which indicates that the addition of acid-treated CNTs
obstructs the mobility of the epoxy matrix molecules in
the glass transition region. Figure 2(b) shows the varia-
tion of tan values as a function of temperature for both
composites. As shown in the gure, the glass transition
temperature that is determined from the peak position of
tan increased by the addition of acid-treated CNTs. This
phenomenon has also been observed in studies conducted
by other researchers.1013 The increase of glass transition
temperature of the basalt/CNT/epoxy composite occurs
because the acid treatment of CNTs induces improved
interfacial strength between the CNTs and epoxy matrix,
which reduces the mobility of the epoxy matrix molecules
around the CNTs. Therefore, the thermal stability of the
basalt/CNT/epoxy composite is greater than that of the
J. Nanosci. Nanotechnol. 13, 56315635, 2013
Kim et al. Effect of Carbon Nanotube Addition on the Wear Behavior of Basalt/Epoxy Woven Composites

(a)

RESEARCH ARTICLE
Fig. 4. Specic wear rate and maximum depth prole of basalt/epoxy
and basalt/CNT/epoxy composites.
(b)
in friction coefcient as a function of wear distance for
basalt/epoxy and basalt/CNT/epoxy composites. As shown
in the gure, the friction coefcient of the basalt/epoxy
composite was stabilized in the range of 0.50.6. In con-
trast, it fell in the range of 0.30.4 for basalt/CNT/epoxy
composites. This result indicates that the modied CNTs
improve dispersion and facilitate stronger interfacial bond-
ing between the CNTs and the epoxy matrix. Figure 4
shows the specic wear rate and the maximum depth pro-
le, respectively, for both composites. The mean depth
Delivered by Publishing Technology to:prole
Chinesewas University
obtained according
of HongtoKong
several points taken from
IP: 172.77.34.188 On: Thu,the
10cross-section in the worn area. Then, the specic wear
Dec 2015 23:21:21
Copyright: American Scientific
rate was Publishers
determined by the following equation:
V
Fig. 2. Basalt/epoxy and basalt/CNT/epoxy of (a) storage modulus, K= (1)
(b) tan as a function of the temperature. N l
V = 2rA (2)
basalt/epoxy composite. The effect of CNTs addition on where K is the specic wear rate, N is the applied load,
the tribological properties of basalt/epoxy composites was and l is the sliding distance, V is the wear volume loss,
investigated by comparing the friction coefcient and spe- A is the cross-sectional area of wear track obtained from
cic wear rate of basalt/epoxy composite with that of the depth prole using a surface prolometer, and r is the
basalt/CNT/epoxy composite. Figure 3 shows the change radius of the wear track.14 The maximum depth prole
of the basalt/epoxy composite was approximately 36 m,
while the maximum depth proles of the acid-treated
basalt/CNT/epoxy composites was approximately 30 m.
The specic wear rate of each composite was determined
based on the sectional shape of the wear track. As shown
in Figure 5, the basalt/CNT/epoxy composites exhibited
better wear resistance behavior than the basalt/epoxy com-
posite. Specically, the specic wear rate of the acid-
treated basalt/CNT/epoxy composites was approximately
68% lower than that of the basalt/epoxy composites.
The worn surfaces of the basalt/epoxy basalt/CNT/
epoxy composite specimens were examined using a
FESEM to investigate the changes in wear mechanism
associated with the CNT addition. Figure 5 shows the
worn surfaces of the basalt/epoxy and basalt/CNT/epoxy.
Fig. 3. The friction coefcient of basalt/epoxy and basalt/CNT/epoxy As shown in Figure 5(a), the worn surface of the basalt/
composites as a function of sliding distance. epoxy composites exhibits exfoliation and cracks of the

J. Nanosci. Nanotechnol. 13, 56315635, 2013 5633

 Effect of Carbon Nanotube Addition on the Wear Behavior of Basalt/Epoxy Woven Composites Kim et al.
RESEARCH ARTICLE

Fig. 5. SEM images of Delivered

worn surfacesby
(a) Publishing Technology
basalt/epoxy, (b) to: Chinese
basalt/CNT/epoxy composites. University
of Hong Kong
IP: 172.77.34.188 On: Thu, 10 Dec 2015 23:21:21
Copyright: American Scientific Publishers
epoxy matrix. It also shows the breakage of basalt properties (friction coefcient and wear rate) of the
bers, which are typical of wear mechanisms of woven basalt/epoxy composites is improved by the addition of
basalt/epoxy composites. The gure also exhibits a deep acid-treated CNTs. Second, the improvement of tribologi-
groove with wear debris on the wear track. This is caused cal properties of basalt/epoxy composites by the addition
by a relatively higher friction than that found for the of acid-treated CNTs is caused by the homogeneous load
basalt/CNT/epoxy composites. Similar wear characteristics transfer between basalt bers and epoxy matrix due to the
were observed for basalt/CNT/epoxy composites. How- reinforcement of CNTs.
ever, as shown in Figure 5(b), basalt/CNT/epoxy compos-
ites display a smooth and shallow wear track compared to Acknowledgments: This work was supported by a
the basalt/epoxy composites. It also exhibits wear debris grant from the Kyung Hee University in 2011 (KHU-
that adhered only to the surfaces without broad exfoli- 20111209).
ation and micro-cracking, which indicates more interfa-
cial strength between the CNT-modied epoxy and the References and Notes
basalt bers. The addition of functionalized CNTs by
the acid-treatment facilitates good dispersion of CNTs in 1. S. Carmisciano, I. M. D. Rosa, F. Sarasini, A. Tamburrano, and
M. Valente, Mater. Des. 32, 337 (2011).
the epoxy and improves load transfer to the basalt bers,
2. B. Wei, H. Cao, and S. Song, Composites Part A 42, 22 (2011).
thus resulting in the improved tribological properties of 3. T. Deak and T. Czigany, Mater. Sci. Forum 589, 7 (2008), two
the basalt/CNT/epoxy composites. authors.
4. Q. Liu, M. T. Shaw, and R. S. Parnas, J. Polymer Composites 27, 41
(2006).
4. CONCLUSION 5. W. Chen, H. Shen, M. L. Auad, C. Huang, and S. Nutt, Composites
Part A 40, 1082 (2009).
In this study, we investigated the effect of CNTs addi- 6. J. H. Lee, K. Y. Rhee, and S. J. Park, Mater. Sci. Engine A 527, 6838
(2010).
tion on the tribological and dynamic mechanical thermal
7. M. T. Kim, K. Y. Rhee, J. H. Lee, D. Hui, and A. K. T. Lau, Com-
properties of basalt/epoxy composites. The conclusions posites: Part B 42, 1257 (2011).
obtained from this study are as follows: First, the thermal 8. ASTM G 99: Standard test method for wear testing with a Pin-on-
stability (storage modulus and tan and the tribological Disk apparatus.

5634 J. Nanosci. Nanotechnol. 13, 56315635, 2013

Kim et al. Effect of Carbon Nanotube Addition on the Wear Behavior of Basalt/Epoxy Woven Composites

9. M. Monthioux, B. W. Smith, B. Burteaux, A. Claye, J. E. Fischer, 12. X. Chen, J. Wang, M. Ling, W. Zhong, T. Feng, X. Chen, J. Chen,
and D. E. Luzzi, Carbon 39, 1251 (2001). and F. Xue, Mater. Sci. Eng. A 492, 236 (2008).
10. S. M. Yuen, C. C. M. Ma, H. H. Wu, H. C. Kuan, W. J. Chen, S. H. 13. Y. Geng, M. Y. Liu, J. Li, X. M. Shi, and J. K. Kim, Composites

RESEARCH ARTICLE
Liao, C. W. Hsu, and H. L. Wu, J. Appl. Polym. Sci. 103, 1272 (2007). Part A 39, 1876 (2008).
11. M. Sangermano, E. Borella, A. Priola, M. Messori, R. Taurino, and 14. A. Dasari, Z. Z. Yu, Y. W. Mai, G. H. Hu, and J. Varlet, Compo.
P. Ptschke, Macro Mol. Mater. Eng. 293, 708 (2008). Sci. Technol. 65, 2314 (2005).

Received: 29 November 2011. Accepted: 14 March 2012.

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J. Nanosci. Nanotechnol. 13, 56315635, 2013 5635