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J. N. Coleman,*
,
K. P. Ryan,
V. Nicolosi,
G. Bister,
A. Fonseca,
J. B. Nagy,
K. Szostak,
F. Be guin,
and W. J. Blau
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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