COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 67 (2007) 18131822
www.elsevier.com/locate/compscitech

Physical and chemical characteristics of multiwalled carbon

nanotubes functionalized with aminosilane and its inuence on
the properties of natural rubber composites
A.M. Shanmugharaj, J.H. Bae, Kwang Yong Lee, Woo Hyun Noh,
Se Hyoung Lee, Sung Hun Ryu *
College of Environment and Applied Chemistry, Kyung Hee University, Yongin, South Korea
Received 22 April 2006; received in revised form 12 October 2006; accepted 27 October 2006
Available online 2 January 2007

Abstract
Surface functionalization of multiwalled carbon nanotubes is carried out by acid treatment followed by reaction with multifunctional
silane, 3-aminopropyltriethoxysilane. The chemical interaction of silane with the oxidized nanotube surface is conrmed by Fourier
transform infrared spectroscopy (FT-IR). Energy dispersive X-ray analysis (EDX) studies also indicate the presence of silane on the surface of the carbon nanotubes. X-ray diraction reveals the change in the crystalline phases due to surface functionalization. Raman spectroscopy of the acid treated CNT further corroborates the formation of surface defects due to the introduction of carboxyl groups.
Thermogravimetric analysis of the functionalized CNT exhibits a multiple peaks in the temperature range of 200650 C that corresponds to the degradation of chemically grafted aminosilane on the CNT surface. The inuence of silane functionalized carbon nanotubes on the rheometric and mechanical properties of natural rubber vulcanizates is investigated. Rheometric properties like scorch time
and optimum cure time increases. Modulus and tensile strength increase due to higher polymer-ller interaction between the carbon
nanotube and NR vulcanizates.
2006 Elsevier Ltd. All rights reserved.
Keywords: A. Polymer-matrix composites; B. Surface treatments surfaces; B. Strength; D. Infrared (IR) spectroscopy

1. Introduction
Since the discovery of carbon nanotube (CNT) by Iijima
[1], it has become a potential candidate for a wide range of
applications such as nanoelectronics [2], composite fabrication [3] and gas storage [4]. Extensive research has been
done by incorporating dierent types of CNTs as nanoreinforcements, nano-wires and nano-conductors into
polymeric materials to form new composites that possess
high mechanical strength, electrical and thermal conductivity. These high performance composite materials may nd
application in space and aircrafts [5,6]. Good interfacial

Corresponding author. Tel.: +82 31 201 2534; fax: +82 31 201 1946.
E-mail address: shryu@khu.ac.kr (S.H. Ryu).

0266-3538/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.10.021

adhesion between CNT and polymer is essential to enhance

the mechanical properties of the polymerCNT composites
[7]. While CNTs have been widely used with dierent kinds
of polymers, very little work has been done on incorporating the CNTs in rubber.
Elastomeric materials are usually reinforced with carbon
black or silica, although the full eects of these llers are
diminished due to their agglomeration [8,10]. It becomes
crucial to incorporate well-dispersed nano-llers into rubber to obtain benecial mechanical and physical properties.
Incorporation of nanotubes in elastomers like silicone rubber dramatically improves the properties of the resultant
composites [9,11]. Although rubbers are thermal and electrical insulator, incorporation of conductive llers into
these materials could produce composite materials with
some electrical conductivity. Potential applications of

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A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

carbon nanotube lled rubber composites could vary from

industrial applications such as rubber hoses, tire components, sensing devices to electrical shielding and electrical
heating.
Although polymer composites based on multiwalled
CNTs show an increase in tensile strength and youngs
modulus, the change is not remarkable due to poor adhesion and weak van der Waals forces, which give rise to
lower stress transfer ability in the composites. In order to
achieve high stress transfer [8,10], strong bonding between
CNTs and polymer chains is necessary. Recent reports on
the chemical compatibility and dissolution properties of
CNTs have promoted a great deal of interest in developing
modication or functionalization of their surface [9,11]. It
has been reported that an acid treatment of CNT could
improve the processability and performance of composites
by introducing carboxylic acid groups on the surface of
CNT, which leads to stabilization in polar solvents and
helps to covalently link polymers [12]. Other possible surface modication techniques include plasma, thermal and
laser ablation [13,14]. The inuence of surface functionalized CNTs on the properties of the polymer nanocomposites has been investigated by various researchers [1518].
Recent reports discuss the chemical functionalization of
multiwalled CNT using silane coupling agents [1921].
Introduction of magnetic silica nanoparticles on the surface of CNT oered high potential applications as separation tools for the purication of proteins [22].
In this paper, multiwalled CNT surface has been functionalized with 3-aminopropyltriethoxysilane and it has
been characterized using X-ray diraction (XRD), Fourier
Transform Infrared Spectroscopy-attenuated total reectance (FTIR-ATR), Raman spectroscopy (FT-Raman),
Scanning electron microscopy/energy dispersive X-ray
analysis (SEM/EDX), thermogravimetric analysis (TGA),
elemental analysis and 1H NMR. The inuence of functionalized carbon nanotubes on the rheometric, and
mechanical properties of the nanotube lled Natural rubber (NR) have also been discussed.
2. Experimental
Multiwalled CNT (MWNT) was obtained from Iljin Co.
Potassium dichromate and 3-aminopropyltriethoxysilane
of chemically pure grades were procured from Aldrich
chemical company, USA. Natural rubber (SMR 5) was
purchased from Rimpex Co. Ltd. Polymerized trimethyl
quinoline (TMQ), mercapto benzothiazole sulphenamide
(MBTS) and tetramethyl thiuram disulde (TMTD) were
purchased from Qingdao Rubber Chemicals Co. Ltd.,
Korea. Zinc oxide (ZnO), stearic acid, sulfur; concentrated
sulfuric acid and acetone were procured from standard
local suppliers.
One gram of MWNT was rst chemically treated with
50 ml of 10 N sulfuric acid in the presence of 2 g of potassium dichromate for 30 min at 80 C. It was then ltered
and washed with hot and cold water several times to

remove the chromic acid and dried in oven at 100 C. Then

the calculated amount of 3-aminopropyltriethoxysilane
(0.01, 0.02 and 0.05 g relative to 1 g of MWNT) dissolved
in acetone was added to the carbon nanotube dispersed
in water and the stirring was continued for 30 min at
80 C. Pure, acid treated and silane functionalized CNT
were designated as NTP, NTA, NTS1 (0.01 g of silane in
1 g of CNT), NTS2 (0.02 g of silane in 1 g of CNT) and
NTS5 (0.05 g of silane in 1 g of CNT).
X-ray diraction studies were carried out in the 2h range
of 550 using X-ray diractometer (Macscience) operating
at the voltage of 40 V. FT-IR characterization (PerkinElmer 2000 spectrophotometer) of pure and functionalized
CNTs was done in the frequency range of 4000400 cm1
with the resolution of 4.0 cm1. Morphological study of
pure and functionalized CNTs was carried out using
Steroscan 440 scanning electron microscope (Leica Cambridge) (SEM) equipped with energy dispersive x-ray analysis (EDX). Structural characterization of CNT and its
natural rubber composites were done using Raman spectroscopy (RFS/100s, Bruker, Germany). Raman lasers
with wavelength of 1064 nm were used to characterize the
functionalized CNTs. Thermal studies were done using
thermogravimetric analysis (TGA 7, Perkin-Elmer, USA)
in the temperature range of 50850 C at a heating rate
of 10 C/min.
The natural rubber compounds with dierent formulations (Table 1) were prepared in an open two roll mill at
room temperature set at the friction ratio of 1:1.1 with
the nip gap of about 1 mm. The mixing time of 19 min
was kept uniformly for all compounds. Gum natural rubber, pure CNT lled natural rubber and silane functionalized CNT lled natural rubber vulcanizates were
designated as NR, NRNTP and NRNTS2.
The vulcanization behavior of pure and CNT lled natural rubber composites were determined at the processing
temperatures of 150 C using oscillating disc rheometer
(ODR, Alpha Technologies, and USA). Dierent kinetic
parameters such as cure rate, degree of crosslinking or conversion, were calculated from the torquetime curves. The
cure rate index (CRI) of the compounds cured with the

Table 1
Compounding formulation
Sr. no.

Ingredients

Amount (phr)

1
2
3
4
5
6
7
8

Natural rubber (NR)

Zinc oxide (ZnO)
Stearic acid
Antioxidanta
Multiwall carbon nanotube
MBTSb
TMTc
Sulfur

100
5
2
1
1
1.2
0.6
2.5

a
b
c

Polymerized trimethyl quinoline.

Mercapto benzothiazole sulphenamide.
Tetramethyl thiuram disulde.

A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

same level of curative was calculated according to equation

as shown below
CRI 100=t90  tS2 

where t90 is the optimum cure time and tS2 is the scorch
time.
Tensile sheets were prepared by curing the natural rubber compounds in the hot press (Carver press) at the temperature of 150 C based on t90 obtained in ODR
measurements. Tensile dumbbell specimens were cut using
ASTM Die C and the tensile properties were determined
following ASTM D472 using Instron.
3. Results and discussion
Fig. 1 shows the X-ray diraction patterns of pure and
functionalized CNTs. The peak position of pure CNT
(NTP) at 25.6 (2h) slightly shift to 25.9 by modication
with chromic acid (NTA). The average d-spacing values calculated using Braggs law lies in the range of 3.443.48 A.
From the results, we can conclude that surface functionalization does not have much inuence on the average dspacing. However, it is interesting to observe broad hump
at lower diraction angle in the case of both pure and functionalized CNTs. These weak and broad peaks at lower
diraction angle in NTP, NTA and NTS are attributed to
the existence of dierent crystallite species [23]. Peak intensity and full width at half height maximum values are calculated for the NTP, NTA and NTS and the values are
reported in Table 2. It is interesting to note that the peak
width and peak intensity vary signicantly depending upon
functionalization of CNT surface. Earlier reports on X-ray
diraction of CNTs revealed that the changes in the peak
width and intensity could be correlated to the variation
in d-spacing [24] and lattice distortions [25]. In our case,
there is no signicant variation in d-spacing value by the
functionalization. Hence, it is expected that the increasement in peak width and intensity at 25.6 with the disappearance of hump at lower angle in functionalized CNTs

1815

Table 2
Peak width and intensity of X-ray diraction peaks
Sr. no.

Samples

Peak width

Peak intensity

1
2
3

NTP
NTA
NTS

1.56
1.60
2.86

510
968
447

can be attributed to the lattice distortion broadening due

to the defective stacking of tubules. Acid or silane treatment aects the carbon structures on the surface of the
CNT due to oxidation/surface interaction and thereby
leading to lattice distortions.
Fig. 2 shows the FT-IR spectra of pure and silane functionalized CNTs in the specic regions. The peak at
1602 cm1 is the characteristic stretching vibrations of C
C bonds related to the expected nanotube phonon modes.
A small peak at 3430 cm1 can be assigned to the vibrational modes of the OH groups, indicating the presence
of functional groups in the pure CNT [26]. Acid treatment
results in the appearance of new peak at 1720 cm1 that
corresponds to the >C@O stretching indicating the introduction of carboxylic groups due to surface oxidation
(not shown). However, silane treatment results in the
increase of peak intensity at 3437 cm1 which is attributed
to the NH stretching of the aminosilane attached to the
CNT surface. The peaks at 2926 and 2856 cm1 that are
due to >CH2 asymmetric and symmetric stretching conrms the presence of silane on the CNT surface. The
appearance of new peaks at 1715 (>C@O stretching),
1640 (NH bending vibration of amine group),
1463 cm1 (>CH2 bending vibration) further supports the
above fact. Appearance of new peaks at 1110 cm1 and
at 1046 cm1 that are corroborated to SiOSi stretching
and SiOC stretching further support the chemical interactions between silane and CNT. To understand the mechanism of interaction, 1H NMR characterization was done
for the silane functionalized CNTs and the results are
included in Fig. 3. Aminosilane functionalized CNTs exhibit peaks at d = 0.9 (2 H; NH2CH2CH2CH2Si

NTP
1000
500

NTS

NT S
NT p

3600 3300
Wave number (cm-1)

2856

NT p

3000 2850
Wave number (cm-1)

1110
1046

NTS

NT S

1602

NT P

1800 1500
Wave number (cm-1)

Absorbance (arbitrary unit)

1500

NTS

Absorbance (arbitrary unit)

NTA

Absorbance (arbitrary unit)

2000

Absorbance (arbitrary unit)

Absorbance (arbitrary unit)

Intensity

2923

3437

2500

1715
1640
1519
1463

3000

NTP

1200 1000
Wave number (cm-1)

NTP
10

20

30

40

50

Angle (2)
Fig. 1. X-ray diraction results of pure and functionalized carbon
nanotube.

4000

3000
2000
Wavenumber (cm-1)

1000

Fig. 2. FT-IR spectra of pure and functionalized carbon nanotubes.

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A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

-CH2 of aminosilane

Solvent peak

NTS5

10

PPM
Fig. 3. 1H NMR spectra of silane functionalized carbon nanotube.

group); d = 1.2 (3H; OCH2CH3 group); d = 1.6 (2H;

NH2CH2CH2CH2 group); d = 2.2 (2H; NH2CH2
CH2CH2) and a small peak d = 2.0 (2H; NH2CH2
CH2CH2Si) indicating the presence of 3-aminopropyltriethoxysilane on the surface. Further, elemental analysis of
the aminosilane functionalized CNT indicates that the
atomic percentage of nitrogen atom is 4.3% relative to carbon conrming the introduction of aminosilane on the
nanotube surface. The possible chemical interaction of
OH groups generated on the carbon nanotube surface with
the ethoxy groups of silane leads to chemical grafting of
silane through SiOC linkages. Also there is a possibility
of hydrogen bonded interaction between C@O groups
with hydrolyzed silane on the surface of CNT. The probable mechanism of interaction is included in Fig. 4.
Scanning electron micrographs of pure and functionalized CNTs are shown in the Fig. 5. NTp shows thin brous
structures on the surface, which has more aggregation in

the bulk. However, individual brous structures are visible

with less aggregation, when the CNT is subjected to acid
treatment (NTA). The NTS exhibits aggregated structure,
which may be due to interaction between the functionalized
CNT due to hydrogen bonding. EDX analysis of pure and
functionalized CNTs is shown in Fig. 6. NTP shows only a
peak for carbon, while NTA shows two peaks for carbon
and oxygen, which indicates the surface oxidation. The
presence of silane in NTS is conrmed from the small peak
at around 1.8 keV (silicon atom). This is further supported
by the increase in O/C ratio (O/C ratio of NTA, 0.45 and
O/C ratio of NTS, 0.85), which is due to the relative
increase in oxygen atoms on the nanotube surface that
are present in 3-aminopropyltriethoxysilane.
Fig. 7 shows the Raman spectroscopy of pure and functionalized CNTs. Raman spectroscopy studies of carbon
nanotubes exhibit two strongest bands at approximately
1280 and 1580 cm1 that are corroborated as D-band

Fig. 4. Probable mechanism of interaction between aminosilane and carbon nanotube.

A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

1817

Fig. 5. SEM photographs of pure and functionalized carbon nanotubes.

NTS

X-ray counts

Si
NTS

Intensity (a.u)

NTA

NTA
NTP

NTp
0

1000
1500
-1
Raman shift (cm )

Energy (keV)
Fig. 6. EDX spectra of pure and silane treated carbon nanotubes.

and G-band [27]. The peak at 1283 cm1 (D band) of NTP

suggests the existence of amorphous carbonaceous material
adhered to the defective pentagon and heptagon structures
in the graphitized walls. However, acid or silane treatment
of CNT shifts the peak to the lower frequency (NTA,
1279 cm1, NTS, 1280 cm1). Similarly the peaks of Gband appear at 1592 cm1 (NTP), 1592 cm1 (NTA) and
1599 cm1 (NTS). On considering the intensity ratio
between D band and G band (ID/IG), it increases from
1.66 (NTP) to 1.85 (NTA) implying the generation of surface defects due to the acid treatment. Similarly silane

Fig. 7. Raman spectra of functionalized carbon nanotubes.

treatment (NTS) further increases the (ID/IG) value to

1.94 conrming the surface disorders. Shown in Fig. 8 is
the Raman radial breathing mode (RBM) frequency
regions of pure and functionalized CNTs. NTP exhibits
multiple peaks at the frequencies of 215, 350, 432 and
536 cm1. However, the peak at 432 cm1 vanishes with
the up and down shift in RBM frequency at 536 cm1,
when CNT is subjected to acid treatment. Similarly, silane
treatment leads to up-shift of the peaks at 215 cm1 and at
350 cm1. Earlier investigation on the inuence of the carbon nanotubes on the RBM frequency of Raman spectra
reveals that van der Waals and interlayer interaction
between CNTs plays a crucial role in the up-shift of the

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A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

288

566

NTS
200

NTA

530

350
432

350

203

Intensity (arbitrary unit)

370

NT P
300
600
-1
Raman shift (cm )

Fig. 8. RBM frequency modes of pure and functionalized carbon

nanotubes.

RBM frequency [28]. Acid treatment of the carbon nanotube increases the interlayer interaction by hydrogen bonding between the OH groups and C@O groups and
thereby results in the up-shift of the RBM frequency. The
interlayer interaction between the edge silane molecules
leads to the up-shift of the RBM frequencies for NTS.
Fig. 9 represents the thermogravimetric and dierential
thermogravimetric results of pure and functionalized
CNTs. Earlier reports on thermal degradation of MWNT

NTP

100

NTA
100
NTP

Weight loss (%)

Weight (%)

90

80

98
NTA
96

70
200

400

600

Temperature (0C)

60

NTS5

50
d/dt (arbitrary unit)

0.020

d/dt

0.015

NTA

NTP
100 200

300

400

500

600

700

0.010

Temperature ( C)

NT S5
0.005
NT A
0.000

NT P
100

200

300

400

500

600

700

Temperature (C)
Fig. 9. TGA and DTG curves of pure and functionalized carbon
nanotubes.

reveal that the onset of degradation starts at around

630 C, which is attributed to the degradation of graphene
walls with complete degradation at around 830 C [29].
Small weight loss at around 150190 C is observed for
NTP and it corresponds to the degradation of amorphous
carbonaceous material adhered on the surface of the regular graphitized walls [30]. The residual weight at 750 C is
about 90%. DTG curves further supports the above fact
(Fig. 8). Acid treated CNT exhibits a broad peak over
the range of 50450 C, which may be due to the degradation of the amorphous carbon and the acid groups present
in the surface. Degradation of acid functionalized CNTs
may involve complex degradation mechanisms and thereby
making the degradation peak broader in the DTG curve.
However, it is interesting to observe multiple degradation
steps in NTS5. Three degradation peaks in 50650 C is
attributed to the aminosilane grafted on the surface of
the carbon nanotubes. The initial degradation in the range
of 50175 C in Fig. 8 is attributed to the degradation of
freely adsorbed silane by hydrogen bonding with the functionalized CNT. Increase in temperature leads to the condensation reaction between the adsorbed silane and OH
groups present in the functionalized CNT surface and
thereby eliminates water and ethanol. The second and third
transitions are attributed to the break down of SiOC
bonds (bond energy 452 kJ/mol) and SiC bonds present
in grafted silane leading to a major weight loss. To understand the thermal stability, functionalized CNTs with various silane concentrations have been subjected to thermal
degradation and the results are included in Fig. 10. The
residual weight at 750 C for NTS1, NTS2 and NTS5 are
44%, 40% and 55%. For NTS5, large number of silane molecules present in the surface leads to the condensation reaction between adjacent silanes molecules forming a network
of SiOSi linkages over the CNT surface. From this
result, it is found that critical concentration of silane exists
to induce SiOSi linkages which increase the thermal stability of CNT. The above result is further supported by the
DTG curve. At low concentration of silane (for ex. NTS1
and NTS2), the onset of third degradation step starts at
around 530 C with degradation peak appears at 592 C
and essentially completed at 650 C. However, at higher
silane concentration (NT5), the onset of degradation starts
at 435 C with the degradation peak at around 520 C and
completes at 595 C. This degradation step is lower than
600 C where the degradation of graphene walls of carbon
nanotube starts. From these results, it can be concluded
that at lower silane concentration, the third degradation
step involves the degradation of graphene walls of carbon
nanotube surface and silane groups present on the surface.
In high silane concentration, however, the SiOSi linkages
formed between the adjacent silane molecules leading to
the degradation of only SiC bonds present in the grafted
silanes in the temperature range of 435595 C that results
in the protection of the graphene walls of CNTs.
Natural rubber composites lled with pure (NTP) and
silane functionalized carbon nanotubes (NTS2) were

A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

100

30

NT S1

25

Torque (dNm)

NT S2
NT S5

80

Weight (%)

1819

60

20
15

NR
NRNTP

10

NRNTS2

5
40

0
0

0.04

10

15

20

25

30

Time (min)
Fig. 11. Rheometric graphs of gum NR, NR/CNT and NR/silane
functionalized carbon nanotubes.

d/dt

0.03

0.02

0.01

0.00
200

400

600

Temperature (C)
Fig. 10. TGA and DTG curves of NTS1, NTS2 and NTS5.

prepared by melt processing using two roll mill. The rheographic prole of gum NR, NR/carbon nanotube composites (NRNTP) and NR/silane functionalized carbon
nanotube composites (NRNTS2) at 150 C are represented
in Fig. 11. The vulcanization characteristics expressed in
terms of the dierence of minimum and maximum torque
value, DS = (MH  ML), scorch time, tS2, optimum cure
time, t90, for NR, NRNTP and NRNTS2 are reported in
Table 3. It is interesting to observe that the dierence
between the minimum and maximum torque DS increases
on loading pure (NRNTP) and silane functionalized CNT
(NRNTS2). However, NRNTP exhibits higher DS value
compared to NR vulcanizates, which may be attributed
to the presence of ller aggregation leading to resistance
to polymer chain mobility. However, DS decreases for
NR/NRNTS2 and it may be due to the decrease in the eective volume percentage of loaded CNT by silane functionalization. Scorch time, which is the measure of premature
vulcanization (tS2) and optimum cure of NR vulcanizates
(t90) increases for NRNTP or NRNTS2. Commercially

available puried MWNT possesses certain degree of functional groups such as carboxylic acid groups, phenolic
OH groups and quinone type oxygen atoms on the surface
[31]. The presence of these carboxylic acid groups and quinone oxygen atoms absorbs the basic accelerator species
[32] and thereby delays the onset of vulcanization (tS2)
and optimum cure time (t90) in NRNTP (Table 3). In the
present study, CNTs were subjected to chromic acid treatment that increases the number of acid functional groups
on the side walls of carbon nanotube. Though silane treatment leads to some coupling reaction between silane and
OH groups on CNT as observed in FT-IR, excess
functional groups like COOH and C@O groups present
on the surface absorbs the basic accelerator species and
thereby delays the scorch time and optimum cure time in
NRNTS2. Cure rate index (CRI) slightly decreases from
55.5 min1 (gum NR) to 52.6 min1 (NRNTP) on loading
pure carbon nanotube, whereas it increases signicantly
on loading NRNTS2 (83.3 min1) (Table 3). Increase in
cure rate index for NRNTS2 may be attributed to the
increase in chemical crosslinks due to the interaction of
grafted silane with NR matrix. Having similarities between
the cure characteristics of compounds in many respects, it
will be useful to analyze the kinetic aspect of cure reaction
to determine the detailed kinetic parameters, which inuence the cure reaction. So the kinetic parameters of the systems were evaluated using a model suitable for kinetic
analysis based on the experimental results.
The data on torque versus time obtained from curemeter
can be used to evaluate kinetic parameters with a series of
mathematical expressions. The degree of curing (a) at a
time, t, is dened as [33,34]

Table 3
Vulcanization characteristics of gum and carbon nanotube lled NR vulcanizates
Sr. no.

Samples

DS = (MH  ML) (dNm)

tS2 (min)

t90 (min)

Cure rate index (1/min1)

1
2
3

NR
NRNTP
NRNTS

20.5
22.3
20.8

3.3
4.2
5.1

5.1
6.1
6.3

55.5
52.6
83.3

A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

where, M0, Mt and Mh are the torque values at the time

zero, at a given time of curing and at the end of the curing,
respectively.
The isothermal vulcanization kinetics of the rubber
compounds are characterized by two general model equations namely nth order and autocatalytic model equations.
The nth order kinetics model, the simplest model to represent the overall curing process, is given by [35],
n

da=dt kT 1  a

0.03

NR
NRNTP
NRNTS2

0.02

d/dt

a M t  M 0 =M h  M 0

0.01

where n is the reaction order and k denotes the temperature

dependent rate constant. The nth order kinetic equation
predicts that the maximum reaction rate occurs at the very
beginning of the reaction, whereas the autocatalytic equation demonstrates that the maximum reaction rate will be
at any point of time other than time t = 0. This discrepancy
occurs because the conversion rate is not only related to the
amount of unreacted material, but also related to the reaction product. From ODR results, it is observed that the
maximum rate of conversion occurs at the time greater
than zero. So the model for autocatalytic reaction equation, as given below, [36] can be used for the cure kinetics
characterization of NR/CNT composites.
da=dt kT am 1  an

where k is the rate constant and m and n are reaction orders

that are dependent on temperature. The values of k, n and
m for all systems were calculated using non-linear regression analysis and those are listed in Table 4. It was observed from the kinetics and the sum of the values of n
and m, related to the reaction order, changed for gum
NR, NRNTP and NRNTS2. The conversion rate curve obtained from model parameters and the experimental values
were closely tted for almost all the systems throughout the
entire degree of conversion. The suitability of autocatalytic
model for cure kinetic analysis was established by tting
the above model parameters with the experimental values,
which show a close tting with each other for the cure rate
versus cure conversion curves. Also, the choice of this model is supported by the close correlation between the rate
constant (k) values determined from the results obtained
from optimum cure time (t90). Fig. 12 shows that the plot
of da/dt versus the degree of conversion for NR and
NR/CNT composites. In this plot, a comparison is also
made between the experimental curves (points) and the
model curves (solid lines). The model curves show a close
tting with experimental curves with the R2 (correlation

Table 4
Kinetic parameters of gum NR, NR/CNT and NR/silane functionalized
CNT composites
Samples

Temperature (C)

Gum NR
NRNTP
NRNTS2

150
150
150

0.06
0.06
0.06

0.75
0.97
0.89

0.71
0.68
0.82

0.00
0.0

0.2

0.4

0.6

0.8

1.0

Fig. 12. Vulcanization rate, da/dt, versus a curves of NR, NRNTP,

NRNTS2. Solid lines represent the theoretical curve obtained from Eq. (4).

coecient) value very close to unity (0.99). All the compounds show the maximum conversion amax = 0.48. The
slower conversion for carbon nanotube lled NR composites may be attributed to the eect of viscosity of compounds that hindered the formation of crosslinks between
adjacent polymer chains.
Stressstrain curves for gum NR, NRNTP and NRNTS
composites are shown in Fig. 13. NTP and NTS2 exhibit
higher stress over the range of strain compared to its control NR. Table 5 shows that the modulus at various strain,
tensile strength and elongation at break values of NR and
its composites. The modulus at 100%, 200% and 300%
elongation increases by about 34% (NRNTP) and 27%
(NRNTS) on loading pure and functionalized carbon nanotube. It is well known that the properties of an elastomer
are controlled by the nature and the degree of crosslink
in the network and ller-polymer interactions. In the case
of NRNTP, main factors that inuence the modulus of
the rubber composites are the nanotube aggregation and
the physical interactions between the nanotubes and rubber
chains. It is assumed that within the range of Gaussian
deformation for NR molecules these interactions are

30
NRNTS2
NR

Tensile stress (MPa)

1820

NRNTP

20

10

0
0

200

400

600

Elongation (%)
Fig. 13. Stressstrain graphs of gum NR, NRNTP and NRNTS2.

A.M. Shanmugharaj et al. / Composites Science and Technology 67 (2007) 18131822

1821

Table 5
Mechanical properties of NR/carbon nanotube composites
Sr. no.

Samples

Modulus (MPa)
100%

200%

300%

1
2
3

NR
NRNTP
NRNTS2

1.65
2.22
2.11

3.46
4.63
4.35

6.03
8.12
7.53

reasonably stable and close to ane deformation. Thus the

nanometer scale diameters and micrometer scale lengths of
nanotubes, i.e., their large aspect ratio, allow them to be
considered as extra molecular chains in the composites that
may provide additional sources of entanglements or physical crosslink in the crosslinked network compared to NR.
Therefore, for the same extent of vulcanization, NRNTP
have more crosslinks than the pure NR sample [37].
Although it is not easy to identify the presence of chemical
reaction between CNT and NR matrix, CNTs can act as an
eective crosslink even in an unvulcanized rubber at least
during short-term loading [36]. Additive eects of the physical and chemical crosslinks of the chains play an important role at the beginning of the deformation and gives
higher modulus than pure NR. However, it is interesting
to observe that the modulus does not vary much for
NRNTS2 compared to NR and NRNTP. The above interpretation is further supported by the increase in volume
fraction of the swollen rubber in the gel (Vr) calculated
using swelling studies. Vr increases from 0.217 (NR) to
0.238 (NRNTP). Similarly it increases to 0.231 on loading
silane functionalized CNT in NR vulcanizates (Table 5).
However, mechanical properties like tensile strength and
elongation at break decreases to about 7.8% and 18% for
NRNTP compared to gum NR vulcanizates, which may
be attributed to aggregation of CNT in the resultant NR
matrix. When the deformation is increased, some of the
physical crosslink may dissipate as polymer chain slides
over the nanotube resulting in the decrease of properties.
Interestingly, tensile strength increases to about 20.8%
without signicant loss in elongation at break in the case
of NRNTS2. Introduction of silane on the surface of carbon nanotube results in higher polymer-ller interaction
due to the formation of excess chemical crosslinks between
the silane and NR that restricts the polymer slippage with
increasing deformation.
4. Conclusions
Surface oxidation and chemical functionalization of CNT
is investigated using aminosilane and its characterization is
carried out using various characterization tools. Chemical
interaction between silane and CNT is conrmed by the
FT-IR peaks at 1110 and 1043 cm1 that are corresponded
to SiOSi and SiOC stretching vibrations. Raman spectroscopy results of the functionalized CNT reveal the formation of surface defects due to the introduction of carboxyl
groups. Presence of silane on the CNT surface has been fur-

Tensile strength (MPa)

Elongation at break (%)

Vr

21.7
20.0
26.2

593
481
559

0.217
0.238
0.231

ther corroborated by the energy dispersive X-ray analysis,

elemental analysis and 1H NMR. X-ray diraction studies
further reveal the change in the crystalline phases due to
silane functionalization. Thermogravimetric analysis of the
functionalized CNT exhibits three new peaks at around
250 and at around 520 C indicating the chemical interaction
between the silane and CNTs. It also shows the formation of
SiOSi bond between silane on the CNT surface and it
becomes predominant at above critical concentration. The
inuence of silane functionalized carbon nanotube on the
rheometric and mechanical properties of the NR vulcanizates was determined. Loading of pure carbon nanotube or
silane functionalized carbon nanotube in NR vulcanizates
increases the scorch time and optimum cure time signicantly due to absorption of basic accelerator by acid groups
and quinone type oxygen atoms. NR/silane functionalized
carbon nanotube composites exhibits higher modulus, tensile strength and elongation at break compared to NR vulcanizates due to the higher polymer-ller interaction between
the silanized carbon nanotube and NR vulcanizates.
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