Effect of nanotube content on mechanical

properties of basalt fibre reinforced polyamide 6

L. Meszaros*, I. M. Gali, T. Czigany and T. Czvikovszky
In this study, 30 mass-% basalt fibre and 0?52 mass-% multiwall carbon nanotube (MWCNT)
reinforced polyamide 6 hybrid systems were prepared by extrusion and injection moulding. The
effect of nanotube content on the mechanical properties was investigated by tensile and flexural
tests. The results showed that the combination of macroscopic and nanosized reinforcements
improved the mechanical properties significantly, and synergetic effects can also be observed.
Good dispersion of the MWCNT was proven by transmission and scanning electron microscopy.
Keywords: Nanocomposites, Nanotubes, Hybrid composites, Basalt fibre

This paper is part of a special issue on Latest developments in research on composite materials

Introduction solution to achieve proper dispersion is using conven-

At the beginning of the twenty-first century, it was
proven that the application of new types of carbon based
nanoparticles (fullerenes) can significantly influence the
physical properties of engineering polymers. However,
these positive effects were less observable concerning
mechanical properties. Some of the mechanical proper-
ties did not reach the originally expected values,
although according to the theoretical models, at least
one order of magnitude increase was expected, e.g. in
tensile and flexural strength. The reason for this low
effectiveness was explained by the high aggregation
behaviour, high impurity content and imperfect struc-
ture of the nanoparticles.13 In the last few years,
nanotubes of high purity and better structure appeared
on the market, and their aggregation susceptibility was
decreased by functionalisation. The functionalised
nanotubes are easily dispersible in the polymer matrix,
and the adhesion to the matrix is also stronger than in
case of the pristine ones. The disadvantage of the
functionalisation is that it breaks up the perfect structure
of the nanotubes, which affects the physical properties of
the nanotubes. The functionalisation modifies the ther-
mal and electrical conductivities and decreases the
mechanical properties of the nanotubes.4,5 There is
another way to decompose the aggregates and obtain a
well dispersed system in the composites: it is to use higher
shear forces during melt mixing. Better dispersion can be
achieved by optimising the processing parameters (tem-
perature, processing velocity, using shear elements during
extrusion, etc.). The apparent viscosity can also be
modified using fillers. The disadvantage of this method
is that it shortens the length of the nanotubes, but the rate
of shortening is low, and this does not cause signifi-
cant decrease in the composite properties. A promising
Department of Polymer Engineering, Faculty of Mechanical Engineering,
Budapest University of Technology and Economics, Muegyetem rkp. 3, H-
1111 Budapest, Hungary
*Corresponding author, email meszaros@pt.bme.hu
tional fibres and nanoparticles together as reinforcement.
The conventional fibre has a reinforcing effect and
increases the apparent melt viscosity, which helps to
disperse the nanoparticles properly; hence, a synergistic
effect is expectable.69
Besides the good dispersion of nanoparticles, the main
advantage of the three component composition is that
the reinforcing materials do not substitute each other,
but they have different functions. In these types of
hybrid systems, the conventional fibre reinforcement
ensures the high modulus of elasticity, tensile strength
and predictable anisotropy. The nanoparticles affect the
degree of crystallinity and improve the tensile mechan-
ical properties. In thermoset laminates, the nanoparti-
cles increase the interlaminar shear strength and reduce
the crack propagation rate. These materials exhibit both
the beneficial properties of conventional fibre reinforced
composites and nanocomposites.2,3,1014
Vlasveld et al.10 investigated fibre reinforced poly-
amide 6 (PA 6)zlayered silicate nanocomposite matrix
hybrid composites. The composites were prepared by
film stacking and fibre impregnation in a hot plate press.
The composites were built up by alternating layers of
matrix material films (which contained the dispersed
nanoparticles) and woven glass and carbon fibre
reinforcement. The results showed that the flexural
strength was enhanced by improving the matrix
modulus in case of several types of PA 6 nanocompo-
sites with glass and carbon fibres.
Shen et al.15 produced PA 6 hybrid composites by hot
pressing. In the first step, 100 mm thick films containing
0?5, 1, 2 and 4 mass-% multiwall carbon nanotube
(MWCNT) were prepared by extruder, and then they
were layered between woven glass fabrics and hot
pressed. Before the study of the hybrid systems, the
MWCNT-containing composites were examined. The
melt flow index (MFI) tests revealed that the addition of
0?5 and 1 mass-% MWCNT did not change the MFI
values of PA 6 significantly, but at higher MWCNT
contents, a strong decrease was observed. In the case of

Institute of Materials, Minerals and Mining 2011

Published by Maney on behalf of the Institute
Received 15 September 2010; accepted 26 September 2010
DOI 10.1179/1743289810Y.0000000015 Plastics, Rubber and Composites 2011 VOL 40 NO 6/7 289
Meszaros et al. Effect of nanotube content on BF reinforced polyamide 6
simple nanocomposites, both the flexural strength and
the flexural modulus increased by augmenting the
nanotube content, but in the case of the hybrid
composites, a positive hybrid effect was observed only
at 0?5 and 1 mass-% MWCNT content. Similar effects
were experienced at the tensile properties.
Besides the nanoparticles, the conventional fibres are
also developing; more perfect high strength materials are
now available to produce high performance composites.
One of these fibres is the continuous basalt fibre (BF).
The reinforcing effect of the BF is similar to that of the
glass fibre; a remarkable increase in static mechanical
properties was observed by several authors. The
differences between the two kinds of composites are
that the BF reinforced ones have better wear resistance
and thermal properties.1618
Deak et al.19 dealt with the effect of the type of
coupling agent on the mechanical properties of chopped
BF reinforced PA 6. It was proven that the silane
coupling agents developed for glass fibres are applicable
for BFs. The applied silane coupling agents influenced
all investigated properties of the composites favourably.
In case of 30 mass-% BF reinforced composites, the
tensile strength grew by 42%, the flexural strength grew
by 37% and the impact strength grew by 223% as
compared with unsized composite.
Based on these papers, it can be concluded that PA 6
is an often used matrix material for preparing thermo-
plastic matrix composites reinforced by conventional
microfibres or nanoparticles. The hybridisation of
micro- and nanofibres can lead to better mechanical
properties in the field of thermoplastic composites.
There are some recent investigations on manufacturing,
such hybrid composites, but most of them use the
pressing technique, which is a less efficient method, and
there can be problems with the proper impregnation. It
turned out that both MWCNT and BF can have a
strong reinforcing effect in the PA 6 matrix, so there is a
good chance to achieve high performance PA 6 matrix
hybrid composites for engineering purposes using these
two reinforcing materials together. The aims of this
study were to prepare MWCNT and BF reinforced PA 6
by continuous melt mixing and injection moulding and
to investigate the effect of the MWCNT content on the
mechanical properties of the composites.
Materials and methods
In the present investigations, PA 6 (Schulamid 6MV13F;
A. Schulman AG, Germany) was used as a matrix. For
the macroscopic reinforcement, BF (BCS 13?6.KV02;
Kamenny Vek Ltd, Russia) was used. The nanotubes
were produced by Bayer, and the type was Baytubes C
150 P. A Brabender Plasti-Corder PL2100 twin screw
extruder was used for continuous melt mixing. The screw
speed was 10 rev min21, and the extrusion temperature
was 240uC. For the composites, 30 mass-% BF and 0?5
2 mass-% nanoparticles were used. First, the granulates
of PA 6 and the MWCNT were mechanically mixed and
then extruded. Above the 2 mass-% MWCNT content,
the mixture was not processable with the applied
extrusion parameters. After extrusion, the samples were
injection moulded with constant parameters (pressure,
mould temperature, etc.) by an Arburg Allrounder 320C
600250 injection moulding machine.
290 Plastics, Rubber and Composites 2011 VOL 40 NO
1 Tensile strength as function of nanotube content in PA
6 matrix conventional and hybrid composites
Before the mechanical tests, the specimens were
conditioned under 50% relative humidity and 20uC for
48 h. Tensile tests were performed on a Zwick Z020
universal testing machine according to EN ISO 527. The
tensile modulus was determined in the strain range of
0?10?5% with a crosshead speed of 5 mm min21. Over
the strain rate range of 0?5%, the crosshead speed was
increased to 50 mm min21. The flexural tests were
carried out also on this machine according to EN ISO
178 with the following parameters: crosshead speed of
1 mm min21 and gauge length of 64 mm. The ultimate
flexural stresses were measured at the maximum deflec-
tion of 6 mm.
The fracture surfaces of the tensile specimens were
investigated by a scanning electron microscope (JEOL
6380 LA, Japan) after coating with AuPd alloy.
Transmission electron microscopy (TEM) images were
taken from thin section of the composites using a Leo
912 Omega microscope (Oberkochen, Germany) with an
accelerator voltage of 120 kV. The thin sections
(y100 nm) were cryocut with a diamond knife at about
2120uC and used without staining.
Results and discussion
Tensile properties
The presence of the nanotubes reduced the tensile
strength of the matrix (Fig. 1), indicating that the
nanotubes are not well dispersed. The increment of the
tensile strength of the 30 mass-% BF-containing com-
posite was significant. If there were also nanotubes in the
system, a synergetic effect was observable: if only
MWCNT was given to the system, the strength
decreased, but with the basalt, a small increase in
strength was experienced. Significant effects were
observable only in the case of the composites containing
0?5 mass-% MWCNT. Further addition of the nano-
tubes did not cause any considerable change in the
strength values even if there was also BF in the
composite.
In contrast to the tensile strength, the tensile modulus
(Fig. 2) showed some increment by adding nanotubes to
the matrix. This phenomenon is explained by the
calculation of the modulus: it is calculated from the
beginning of the tensile curve, where the negative effects
of aggregates are still not observable. The effect of the
BF is similar to its influence on the tensile strength: it
increases the tensile modulus considerably. The effect of
6/7

2 Tensile modulus as function of nanotube content in PA
6 matrix conventional and hybrid composites
the MWCNT in BF reinforced composites is a bit
different: it increases the tensile modulus until 1 mass-%
MWCNT content, but then, it begins to decrease
significantly. This can be explained by the fact that if
there is a high amount of nanotubes in the composite,
they impede each other in utilising their total strength-
ening effect.
In thermoplastic nanocomposites, the tensile elonga-
tion at break e shows the quality of the dispersion
(Fig. 3). In PA 6zMWCNT composites, the e decreases
greatly compared to the pure matrix (ePA 658024%).
This can be explained by the remaining MWCNT
aggregates. On the other hand, the presence of the BF
also decreases the elongation at break, but if there are
also nanotubes in the system, the elongation at break
does not decrease any further. It indicates that the
starting points of the fractures are not the nanotubes or
their aggregates, but the characteristic failure form is
fibre breaking; consequently, the dispersion state of the
nanotubes is good.
Flexural properties
The bending tests showed that the presence of the
nanotubes had a positive effect on both the flexural
strength (Fig. 4) and the flexural modulus (Fig. 5). The
presence of 0?5 mass-% nanotubes in the system almost
doubled the flexural strength, and further addition of
nanotubes caused slightly higher values; however, those
changes are not significant. The flexural modulus also
showed an increment of up to 1 mass-% nanotube content.
At the hybrid composites, the results of the bending
tests reflect a stronger synergetic effect of nanoparticles
3 Elongation at break as function of nanotube content in
PA 6 matrix conventional and hybrid composites
Meszaros et al. Effect of nanotube content on BF reinforced polyamide 6
4 Flexural strength as function of nanotube content in
PA 6 matrix conventional and hybrid composites
and BFs. The BF reinforcement was more effective if
nanoparticles were also in the system. In this case, the
flexural strength reached 170 MPa, which is more than
five times higher than the pure matrix. The same effect
was observable at the flexural modulus. The effect of the
nanotube content is similar to the tensile properties: the
modulus increases until 1 mass-% nanotube content and
than begins to decrease.
Electron microscopic study
Figure 6 shows the fracture surface of PA 6z1 mass-%
composite after tensile test. It can be seen that large
aggregates remained in the system (Fig. 6a). It can also
be concluded that these aggregates are the starting
points of the break. This result is in concordance with
the conclusion deducted from the elongation at break.
At a higher magnification, the nanotubes are visible
within the aggregate. The nanotubes are not impreg-
nated by the PA 6 at all; the shear forces were not
enough to break up the aggregates.
In the case of hybrid systems, a different fracture
behaviour was observable. Figure 7a shows the tensile
fracture surface of a hybrid specimen containing 1
mass-% MWCNT. There are no observable nanotube
aggregates, and the starting points of the break are
around the BFs. This refers to a well dispersed system,
which can be confirmed by the TEM image (Fig. 7b).
The nanotubes are dispersed very well: the matrix
contains individual fibrous structures. The large black
areas are pieces of broken BFs. Smaller spherical spots
can also be observed. These spots can even be the
remaining catalyst from the production of nanotubes or
5 Flexural modulus as function of nanotube content in
PA 6 matrix conventional and hybrid composites
Plastics, Rubber and Composites 2011 VOL 40 NO 6/7 291
Meszaros et al. Effect of nanotube content on BF reinforced polyamide 6
a 6250; b 650 000 (from centre of a)
6 Images (SEM) of fracture surface of PA 6z1 mass-% MWCNT after tensile test under different magnications
7 a SEM and b TEM images of PA 6zBFz1 mass-% MWCNT
other amorphous carbonic structures. Note that the
purity of the applied MWCNT was y95%.
Conclusions
Hybrid composites were succesfully prepared from PA 6
matrix, BF and MWCNTs. It turned out that the
conventional BFs can help in the dispersion of the
nanotubes. It has been demonstrated that hybrid
nanocomposites with advantageous properties can be
created by a combined application of short BFs and a
small amount of nanoparticles. With respect to tensile
strength, flexural strength and flexural modulus, the
joint increase caused by combining short BFs and
nanoreinforcements surpasses the sum of increments
caused by fibre reinforcement and by nanoadditives
applied alone, i.e. a positive synergistic effect has been
achieved. The maximimum increment in the properties
was measured at 1 mass-% nanotube content. The SEM
and TEM images show that large nanoparticle aggre-
gates disintegrated in the hybrid composite.
Acknowledgements
The authors would like to express their thanks to
ARBURG Hungary Ltd for the Arburg Allrounder
292 Plastics, Rubber and Composites 2011 VOL 40
320C 600250 injection moulding machine. This
research was supported by the Hungarian Research
Fund (grant no. OTKA F 67897), the Mexican
Hungarian intergovernmental intergovermental S&T
cooperation programme (grant no. MX-6/2007), the
HungarianSouth African intergovermental S&T coop-
eration programme (grant no. ZA-12/2008) and the
HungarianChinese intergovernmental intergovermen-
tal S&T cooperation programme (grant no. CN-1/2007).
This work is connected to the scientific programme of
the Development of quality-oriented and harmonized
RzDzI strategy and functional model at BME
project. This project is supported by the New Hungary
Development Plan (project no. TAMOP-4?2?1/B-09/1/
KMR-2010-0002).
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