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Reinforcement of Polymers with Carbon

Nanotubes: The Role of Nanotube


Surface Area
M. Cadek,

J. N. Coleman,*
,
K. P. Ryan,

V. Nicolosi,

G. Bister,

A. Fonseca,

J. B. Nagy,

K. Szostak,

F. Be guin,

and W. J. Blau

Materials Ireland Polymer Research Centre, Department of Physics,


Trinity College Dublin, Dublin 2, Ireland, Laboratoire de Resonance Magnetique
Nucleaire, Fac. UniVersite N.D. de la Paix, rue de Bruxelles 61,
5000 Namur, Belgium, and Centre de Recherche sur la Matie`re DiVisee,
1B, rue de la Ferollerie, 45071 Orleans, France
Received November 11, 2003; Revised Manuscript Received December 17, 2003
ABSTRACT
Tensile tests were carried out on free-standing composite films of poly(vinyl alcohol) and six different types of carbon nanotubes for different
nanotube loading levels. Significant increases in Youngs modulus by up to a factor of 2 were observed in all cases. Theories such as the
rule-of-mixtures or the Halpin-Tsai-theory could not explain the relative differences between composites made from different tube types.
However, it is possible to show that the reinforcement scales linearly with the total nanotube surface area in the films, indicating that low
diameter multiwall nanotubes are the best tube type for reinforcement. In addition, in all cases crystalline coatings around the nanotubes were
detected by calorimetry, suggesting comparible polymernanotube interfaces. Thus, the reinforcement appears to be critically dependent on
the polymernanotube interfacial interaction as previously suggested.
Carbon nanotubes have generated a great deal of interest
since their discovery
1
due to their unique physical properties.
2
Much research has focused on nanotubes as fillers in polymer
or epoxy matrix composite materials with enhanced mechani-
cal,
3-5
electrical,
6,7
and thermal
8,9
properties. Most signifi-
cantly, they are considered to be ideal candidates for
mechanical reinforcement of polymers.
2
CNTs are known
to have an extremely high Youngs modulus of up to 1
TPa
10,11
and tensile strength approaching 60 GPa.
11
However,
to access these extraordinary properties, a number of issues
must be addressed. Of these issues, identifying the optimal
properties of the polymer-nanotube interface is considered
the most pressing. Specifically, the polymer-nanotube
interfacial stress transfer must be maximized in order to
achieve the best possible reinforcement. This topic has been
the basis of several studies to date.
12-16
Another important
issue is the type of nanotubes to use for the highest level of
reinforcement. It is generally thought that high quality
SWNT
13
are the best due to their high modulus and small
size. Alternatively, arc produced MWNTs are considered
promising due to their high modulus and rigidity. Catalytic
MWNTs, however, are generally viewed less favorably as
their high defect level results in a modulus a factor of 10
lower than the more perfect nanotubes.
17
In this paper, we will address these issues by studying
the mechanical properties of a range of different types of
nanotubes dispersed in one type of polymer matrix. We find
that the reinforcement scales with inverse nanotube diameter
for MWNT. Relative to MWNTs, SWNTs display poorer
reinforcement, probably due to bundle formation. This
strongly suggests that low-diameter MWNTs are the opti-
mum material for polymer reinforcement.
For this study poly(vinyl alcohol) (PVA) was used as the
polymeric matrix as it is known to provide good stress
transfer to carbon nanotubes.
4
The nanotubes used were
purified HipCO-SWNTs supplied by CNI Ltd. (U.S.A.),
18
double-walled nanotubes (DWNT) from Nanocyl S. A.
(Belgium),
19
arc grown MWNT
20
produced in our own
laboratory (AMWNT), catalytic MWNT from Nanocyl S.
A. (NMWNT),
21
catalytic MWNT produced in Orleans
22
(France) (OMWNT), and nanotubes with hydroxyl groups
covalently bonded at the tips using ball milling
23
under
constant hydrogen flow (OHMWNT). In all cases except the
AMWNT, the nanotubes were pure when received. For the
AMWNT the NT were purified during the composite
formation process.
4
A range of composite dispersions were prepared for each
nanotube type by adding the nanotube material to 30 g/L
* Corresponding author. E-mail: colemaj@tcd.ie, Tel ++353 1 6083859.

Trinity College Dublin.

Fac. Universite N.D. de la Paix.

Centre de Recherche sur la Matie`re Divisee.


NANO
LETTERS
2004
Vol. 4, No. 2
353-356
10.1021/nl035009o CCC: $27.50 2004 American Chemical Society
Published on Web 01/07/2004
solutions of PVA in water. PVA (M
w
) 30 000-70 000
g/mol) used in this investigation was purchased from Sigma-
Aldrich [product code: 9002-89-5] and used as supplied.
In the case of AMWNT a mass fraction of 25% soot relative
to the polymer content was added to the polymer solution.
This solution was mixed and purified as described previ-
ously
24,25
and the true nanotube mass fraction measured by
thermal gravimetric analysis. For all other nanotube types,
the mass fraction added to the polymer solution was 1 wt
%. These samples were sonicated for 5 min using a high-
power sonic tip followed by a mild sonification for 2 h
followed by further high-power sonification for additional
5 min.
To fabricate free-standing composite films, 1 mL of each
solution was pipetted onto a polished Teflon disk and placed
in a 60 C heated oven to allow evaporation of the solvent.
This procedure was repeated four times on each disk in order
to obtain films with thicknesses of up to 0.5 mm. The films
were peeled off the substrates and cut into strips of 10
mm 4 mm 0.3 mm to perform mechanical testing. Prior
to testing, all specimens underwent an additional drying
procedure for 1 h at 60 C to evaporate any remaining water.
The width and thickness of each strip were measured using
a low torque digital micrometer. The volume fraction of NT
in each film was calculated from the mass fraction using
the densities, F ) 1300kg/m
3
for PVA, F ) 1500kg/m
3
for
DWNT and SWNT, and F ) 2150kg/m
3
for all MWNT.
To measure the average diameter and length for each
nanotube type, transmission electron microscopy was per-
formed (Hitachi H-7000). Formvar-coated copper grids (mesh
size 300) were dipped into composite solutions and allowed
to dry in ambient conditions. The average diameter, D, and
length, l, of each type of nanotube were found to be: DWNT,
D ) 2.5 nm, l ) 2.2 m; SWNT (bundles), D ) 9 nm, l >
10 m; NMWNT D ) 14 nm, l ) 2.1 m; OHMWNT D )
15 nm, l ) 1.6 m; OMWNT D ) 16 nm, l ) 3.8 m;
AMWNT D ) 24 nm, l ) 0.8 m.
Tensile testing was carried out using a Zwick Z100 tensile
tester. A 100N load cell and a cross head speed of 0.5 mm/
min were used to obtain the tensile modulus, Y. In all cases,
four strips were measured and the mean and standard
deviation calculated. Furthermore, morphology and thermal
properties of the composites were studied by differential
scanning calorimetry (DSC) using a Perkin-Elmer Diamond
DSC power compensation instrument. Scanning rate was 40
K/min where approximately 10 mg of each sample was
measured and analyzed.
Shown in Figure 1 are the normalized tensile moduli for
composite films containing all six nanotube types plotted
versus the volume fraction of CNT. An increase in tensile
modulus of up to a factor of 2 was observed at very low
loading levels. In all cases straight lines can be fit. In the
case of the DWNT the curve is linear only at low volume
fractions. This is probably due to bundle formation for higher
volume fractions.
Two of the most common theories used to analyze these
type of curves are the rule-of-mixtures
26
and the Halpin-
Tsai theory.
27
Analysis using the rule-of-mixtures gives the
nanotube tensile modulus while if the NT modulus and
diameter are known, analysis using Halpin-Tsai-theory gives
the NT length. These parameters have been calculated in all
cases and are presented in Table 1 along with the expected
or measured values and the slopes, m, of the fit curves shown
in Figure 1. None of these calculated values match well to
the expected or measured values. This suggests that neither
of these theories apply well for these samples.
Empirically, it can be seen from Table 1 that the slopes,
m, do not scale with the expected modulus or length.
However, as the NT diameter increases the slope tends to
decrease. To study this in more detail we plot the rate of
increase of the normalized modulus with volume fraction
(m) versus the NT diameter on a log-log scale in Figure 2.
A straight line of slope close to -1 could be fitted to these
data, indicating that the rate of increase is inversely
proportional to NT diameter. It can be shown as follows that
this indicates that the increase in normalized modulus is
proportional to the total NT surface area per unit volume of
composite film, SA/V. We can define the reinforcement as
the increase in modulus on addition of nanotubes relative to
the polymer modulus. If the reinforcement is proportional
to the total nanotube surface area per volume then we can
write
where Y
C
and Y
P
are the Youngs moduli of the composite
and polymer, respectively, k is a proportionality constant,
N/V is the number of nanotubes per unit volume, and (DL)
is the surface area per nanotube (D and L are the nanotube
diameter and length, respectively). By definition, the volume
fraction can be written as
Substituting N/V from eq 2 into eq 1 and rearranging gives
Figure 1. Normalized tensile modulus plot versus volume fraction
of nanotubes for each composite film.
Y
C
- Y
P
Y
P
) k
N
V
(DL) (1)
V
f
)
N
V

D
2
4
L (2)
Y
C
Y
P
) 4k
V
f
D
+ 1 ) mV
f
+ 1 (3)
354 Nano Lett., Vol. 4, No. 2, 2004
confirming the relationship mentioned above. To test this
hypothesis the x-axis of Figure 1 was transformed to
represent the total surface area per volume (SA/V) as shown
in Figure 3.
It can be observed that, within experimental error, all data
points apart from the HipCO-SWNT fall on the same
universal curve. This clearly shows a dependency of the
reinforcement of polymer composites using CNT on the total
NT surface area per volume. In case of the HipCO-SWNT
composite, reinforcement is slightly lower than the rest of
the materials. This can be explained by the fact that bundle
formation is known to occur for these materials. This means
that the reinforcing entities are not individual SWNTs but
bundles. This results in a lower level of reinforcement in
these materials due to SWNT slippage in the bundles.
28,29
As the surface area appears to play a fundamental role in
the reinforcement mechanism it is important to understand
the nature of the interface for each composite type. To do
this, DSC measurements were carried out on all films. In all
cases a large melt peak was observed at approximately 160-
200 C, indicating a degree of polymer crystallinity in all
composites. This crystallinity was calculated and was
observed to increase with nanotube content. Shown in Figure
4 is the linear increase of crystallinity for all PVA/CNT
samples plotted versus the volume fraction of CNT present.
This linear increase in crystallinity suggests that each CNT
has a crystal coating with an average thickness that is
constant for each nanotube type. This shows that all samples
used in this study had a similar (crystalline) polymer
nanotube interface. It should be pointed out that for the
DWNT samples, the crystallinity is linear with V
f
, only at
low V
f
. This is consistent with the bundling of DWNT at
higher V
f
suggested above.
It is possible to derive a simple equation relating the
thickness of the crystal coating to the rate of increase of
crystallinity with volume fraction:
Table 1. Tube Analysis by Rule-of-Mixtures and the Halpin-Tsai Theory
a
Rul e of mi xtures Hal pi n-Tsai
tubes
di ameter d
(nm) sl ope m
coati ng b
(nm)
uni versal sl ope k
(nm)
Yc
(cal c)
Yc
(pred)
l ength, m
(cal c)
l ength, m
(measured)
DWNT 2.8 622 12 435 5.1 TPa 1TPa 200 2.2
NMWNT 14 188 16 658 1.4 TPa <0.1TPa 500 2.1
OMWNT 16 120 12 480 0.9 TPa <0.1TPa 500 3.8
OHMWNT 15 102 35 382 0.8 TPa <0.1TPa 500 1.6
AMWNT 24 64 10 384 0.5 TPa 1TPa 3 0.8
SWNT 9 (bundl es) 56 0.4 TPa
a
Shown in columns 2-5 are the measured NT diameters, D, slopes of the normalized modulus versus volume fraction curves, m, crystalline coating
thickness, b, and universal slope, k. Presented in columns 6-7 are the Youngs moduli calculated from the rule of mixtures and those predicted by the
literature. Presented in columns 8-9 are the nanotube lengths calculated using the Halpin-Tsai equation and those measured by TEM. Modulus for PVA
is 1.9 GPa. The measured values for diameter (column 2) and the predicted values for NT modulus (column 7) were used to calculate the NT length from
Halpin-Tsai theory. In all cases the calculated and predicted values do not match well.
Figure 2. Composite reinforcement (slope, m) versus nanotube
diameter on a log-log scale.
Figure 3. Normalized tensile modulus for all polymer/nanotube
samples plotted versus the total surface area per volume of all
composite films. Linear dependency of total surface area is shown
for all samples apart from HipCo-SWNT. This is most likely due
to SWNT bundle formation.
Figure 4. Crystallinity increase for all composites versus volume
fraction of carbon nanotubes.
(
b
R
)
2
+ 2
(
b
R
)
-
d
dV
f
) 0 (4)
Nano Lett., Vol. 4, No. 2, 2004 355
where b is the crystal coating thickness, R the radius of the
CNT, V
f
is the volume fraction of CNT, and the crystal-
linity. This equation can then be used to calculate the
thickness of this coating from the data in Figure 4. This
model gives crystal coating thickness ranging from 10 nm
for AMWNT to 29 nm for OHMWNT. The calculated values
are given in Table 1. This result is interesting as it shows
that PVA can crystallize on the surface of both well
graphitized NTs such as AMWNT and poorly graphitized
NTs such as those that are catalytically grown. This suggests
that the crystallinity is not templated by the hexagonal lattice
of the nanotube but can occur on any cylindrical NT surface.
This is in good agreement with predictions by Coleman and
Ferreira.
30
This work is important for two reasons. Of the nanotubes
studied, the SWNT, DWNT, and AMWNT are expected to
be well graphitized and relatively defect free. However, the
NMWNT and OMWNT were produced catalytically and are
known to contain large quantities of defects. In addition, the
OHMWNT have -OH functionalities covalently attached.
Thus the defect level appears not to play a role in the stress
transfer. Furthermore, it shows that even poorly graphitized
and hence low modulus nanotubes can be effective as
reinforcement agents. This is probably due to the fact that
for most polymers the polymer-nanotube interfacial stress
transfer is low with values typically less than 50 MPa.
14
This
means that the full potential of the nanotubes can never be
addressed. This results in virtually no difference between
nanotubes with Y1 TPa and Y0.1 TPa in terms of polymer
reinforcement. As the interface appears to be the same in
all cases it seems clear that the PVA-nanotube interfacial
stress transfer determines the slope of the universal curve
shown in Figure 4. This slope, k, was found to be 457 ( 35
nm. Additionally, this slope can be found from eq 3 to be k
) mD/4. This was calculated for each nanotube type and
the results shown in Table 1. As expected, the average value
was determined to be k ) 468 ( 114 nm, in good agreement
with the previous value. This demonstrates the critical
importance of the interfacial stress transfer.
In addition, this work allows us to predict the optimal type
of nanotubes for reinforcement. As SWNTs tend to bundle
they result in poor reinforcement. The same is true for
DWNTs as the volume fraction is increased beyond 0.1%
(see Figure 1). Therefore, to maximize total surface area,
small diameter MWNTs are required. This is fortunate as
these materials can be produced in relatively large quantities
by catalytic processes.
19
In summary, we have showed an increase of mechanical
properties such as Youngs modulus by a factor of 2 while
adding only 0.6 vol % of CNT to poly(vinyl alcohol).
Furthermore, the mechanical property increase depends on
the average diameter of the carbon nanotubes and therefore
on the total surface area per unit volume. Polymer crystal-
linity increases linearly in all cases with increasing volume
fraction of nanotube indicating a crystalline polymer coating
at the nanotube surface. This shows that PVA can crystallize
on the surface of both well and poorly graphitized NT. In
addition, the best candidates for polymer reinforcement are
small diameter MWNTs.
Acknowledgment. The financial support of the Higher
Education Authority, Science Foundation Ireland and the
European Union NANOCOMP-Network Program, under
contract no. HPRN-CT-2000-00037 is gratefully acknowl-
edged. Furthermore, William Brennan of the National Centre
for Biomedical Engineering Science at the National Univer-
sity of Ireland, Galway is kindly acknowledged for providing
mechanical test equipment.
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356 Nano Lett., Vol. 4, No. 2, 2004