communications
Nanocomposites
High-Strength, High-Toughness Composite Fibers by
Swelling Kevlar in Nanotube Suspensions**
Ian OConnor, Hugh Hayden, Jonathan N. Coleman,* and Yurii K. Gunko*
Strong polymer fibers have a broad range of applications and
play a very important role in modern technology and everyday
life. Therefore, the development of new ultra-strong polymer
or composite fibers is of great interest both scientifically and
for industry. Carbon nanotubes have been envisaged as one of
the most promising additives for the fabrication of ultra-strong
polymer composite materials[1] due to their superior mechan-
ical properties. It is well-known that carbon nanotubes have
Youngs modulus and tensile strength above 1 TPa[2] and
60 GPa,[3,4] respectively, while their densities can be as low as

1.3 g cm1.[3,5] For these reasons, various polymernanotube
composites have become a subject of intensive research and
technological development over the last decade.[1] The most
common approaches for the fabrication of polymernanotube
composite fibers have been melt processing[69] and solution
coagulation spinning.[1015] In these techniques, nanotubes
must either be incorporated into a polymer solution or molten
polymer before the formation of corresponding polymer
nanotube composite fibers. However, these methods cannot be
applied in the case of insoluble or temperature-sensitive
polymers, which decompose without melting. Kevlar is a well-
known high-strength polymer with a variety of important
applications including bullet-proof vests, protective clothing,
and high-performance composites for aircraft and automotive
industries.[1618] However, Kevlar is not soluble in any
common solvent and has no melting point, decomposing
above 400 8C.[17] As a result, Kevlar fibers must be produced
by wet-spinning from sulfuric acid solutions.[19,20] While
single-walled nanotube (SWNT) fibers can be produced by
acid-spinning,[21] to the authors knowledge, no reports of
Kevlarnanotube fibers have appeared in the literature
(however, it should be noted that poly(paraphenylene-2,6-
benzobisoxazole) (PBO, also known as Zylon)nanotube
composite fibers have been produced by acid dry-jet wet-
[] Prof. J. N. Coleman
School of Physics and CRANN Institute
Trinity College, University of Dublin
Dublin 2 (Ireland)
E-mail: colemaj@tcd.ie
Prof. Y. K. Gunko, I. OConnor, H. Hayden
School of Chemistry and CRANN Institute
Trinity College, University of Dublin
Dublin 2 (Ireland)
E-mail: igounko@tcd.ie
[] The authors acknowledge Science Foundation Ireland (RFP pro-
gramme) for financial support, and staff members of the Electron
Microscopy Unit (TCD) for their help with SEM imaging.
DOI: 10.1002/smll.200801102
466 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
spinning).[22,23] Although it is probably possible to produce
KevlarSWNT fibers by acid-spinning, an alternative method,
which would allow proof-of-concept, would be to incorporate
nanotubes in commercially available, pre-existing Kevlar
fibers by a post-production method. Such a method is described
in this paper, where we report the preparation of new,
reinforced Kevlarnanotube composites. These are prepared
by swelling commercially available Kevlar 129TM fibers in
suspensions of nanotubes in the solvent N-methylpyrrolidone
(NMP). Nanotube uptake of up to 4 wt% has been observed,
resulting in significant mechanical enhancement of the
fibers.
Recently, it has been reported that nanotubes can be
efficiently dispersed in NMP.[24,25] It is known that NMP can
be used as a solvent for the synthesis (polymerization) and
processing of Kevlar.[26] We have also found that Kevlar fibers
can be swelled in NMP. This led us to hypothesize that
nanotubes could be incorporated into swelled Kevlar by
soaking Kevlar fibers in a dispersion of nanotubes in NMP. In
our experiments, commercially sourced Kevlar 129 yarns were
placed in stable suspensions of multiwalled carbon nanotubes
(MWNTs), containing various concentrations of nanotubes, in
NMP. These Kevlarnanotube mixtures in NMP were
sonicated using an ultrasonic bath for various periods of time
at ambient temperature. The Kevlar yarns were then retrieved
from the nanotube dispersions and washed several times. They
were then dried, weighed, and investigated by thermogravi-
metric analysis (TGA), scanning electron microscopy (SEM),
and mechanical testing.
Analysis of the samples showed that swelling of Kevlar
yarn in MWNT dispersions under ultrasound in a sonic bath
resulted in a measurable mass uptake after washing. This
suggests that soaking in NMP induces porosity in the Kevlar,
allowing nanotube infiltration. The nanotube mass uptake was
found to scale with the square root of soak time (Figure 1A),
suggesting that the intercalation of nanotubes into the Kevlar
fibers is diffusion limited.[27] For mass transport by diffusion
into porous thin films, the intercalated mass uptake as a
function of time is given by[28]

 s


mNT mNT 16D
t (1)
mKev mKev Sat b2 p
where (mNT/mKev)Sat is the saturated value of the mass uptake,
D is the diffusion coefficient, and b is the sample thickness.
While this equation is not strictly valid for diffusion into a
porous cylinder, we use it here in the expectation that it is
small 2009, 5, No. 4, 466469

Figure 1. A) Normalized nanotube mass uptake in Kevlar yarns against
swelling time. The dashed line shows square root behavior allowing
the estimation of the intercalative diffusion coefficient to be
<1.4  1017 m2 s1. B) Graph of nanotube mass uptake (expressed as
nanotube mass fraction) as a function of nanotube concentration in the
swelling suspension.
correct to within a constant factor. In addition, we approx-
imate b by the fiber radius, that is, the furthest the nanotube
can diffuse into the fiber. We did not observe saturation of the
mass uptake in our experiments. However, by normalizing the
mass uptake to the maximum observed value we can get an
upper limit to the diffusion coefficient. This allows Equation 1
to be fitted to the data in Figure 1A. The fit was reasonably
good, indicating the validity of Equation 1. The fit parameters
give an upper limit for the diffusion coefficient (taking
b 5 mm): D < 1.4  1017 m2 s1. This is significantly lower
than the value of 1.3  1012 m2 s1 that one can estimate using
the Broersmas equations[29] for a MWNT dispersed in the
liquid phase. This is unsurprising as diffusion in the restricted
environment of the swelled polymer would be expected to be
considerably slower then diffusion in the solvent.
Extensive tests involving soaking yarns in dispersions with
a nanotube concentration of 0.6 mg mL1 under different
conditions showed that the best mechanical properties were
obtained when soaking MWNTs in a sonic bath for 30 min.
Subsequently, a range of yarns were treated by soaking for
30 min in nanotube dispersions at a range of nanotube
concentrations. We accept that the true optimum soak time
may vary slightly with concentration, however, we chose to
treat all nanotube concentrations equally in terms of
small 2009, 5, No. 4, 466469 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
processing parameters. Thus, we chose 30 min as the soak
time for all samples, accepting that most of the samples may
not be perfectly optimized. In addition, a control sample was
prepared where the Kevlar yarn was soaked under identical
conditions in pure NMP. These yarns were washed, dried, and
weighed and the mass uptake calculated. The mass uptake as a
function of nanotube concentration in the NMP dispersion for
a 30 min soak time is shown in Figure 1B. The mass uptake was
found to vary from 0.3 to 4 wt%. It should be pointed out that
after a soak time of 30 min, the diffusion process had certainly
not reached steady state (Figure 1A). We reiterate that this
time was chosen in order to maximize the mechanical
properties rather than to represent equilibrium.
An image of a KevlarMWNT composite fiber that had
been cut using a blade for SEM cross-sectional analysis is
shown in Figure 2. This and other images of the surface of
individually treated Kevlar fibers show a web-like deposit of
nanotubes, even after washing. While the breaks do not tend to
be particularly clean, the presence of nanotubes in the interior
of the fibers can be seen as illustrated in the blow-up on the left
side of Figure 2. This demonstrates nanotube insertion as well
as surface coating.
The yarns treated for 30 min in nanotube dispersions of
varying concentrations were used for mechanical testing. The
mass fractions were those shown in Figure 1B. Mechanical
measurements were made on between 8 and 13 individual
fibers extracted from each of the treated yarns. These fibers
were typically
10 mm in diameter and were mounted in the
tensile tester with the aid of glue. In all cases the stressstrain
curves (not shown) were linear, demonstrating brittle failure.
From these stressstrain curves, we can obtain four mechanical
parameters: Youngs modulus, Y; tensile strength, s B; strain at
break, eB; and toughness, T. These data are shown as a function
of nanotube mass fraction in Figure 3AD. In all cases, the
0 wt% curve is for Kevlar fibers treated in NMP in a fashion
analogous to the composite preparation treatment. This
treatment resulted in very little change in the Kevlars
mechanical properties. For each mechanical property, both
mean values, with standard deviations (closed squares), and
maximum observed values (open squares) are plotted. No
significant change in the mean values of either the Youngs
modulus or the strain at break is observed. In fact, hypothesis
testing shows that the data sets for both Youngs modulus and
strain at break are statistically indistinguishable (significance
level 0.01) for all mass fractions. However, an increase in mean
strength from 4 GPa for the Kevlar fiber to 5 GPa for the
1 wt% composite fiber is observed. In addition, despite the
Figure 2. SEM images of cross sections of a blade-cut Kevlar fiber after
treatment in 1 mg mL1 MWNT suspension in NMP.
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 communications
Figure 3. A) Youngs modulus, B) strength, C) strain at break, and
D) toughness as functions of mass fraction for nanotubes in Kevlar
fibers. The toughness is shown on a per mass basis on the right axis of
the lowest panel. This is as converted from the per volume toughness
assuming a density of 1500 kg m3.
substantial error bars, there is a real increase in mean
toughness from 40 to 70 J g1 for the 1.75 wt% sample.
Hypothesis testing shows that for both strength and toughness,
both the 1 and 1.75 wt% data are statistically distinguishable
from the pure Kevlar data (significance level 0.01).
However, it is the maximum observed values that are of
most interest as these represent the ultimate mechanical
properties that are potentially achievable. In all cases the
maximum observed value increases from the Kevlar-only
fibers with increasing mass fraction, peaking at either 1 or
1.75 wt%. The observed increases compared to the Kevlar-
only fibers, were (maximum values only): Youngs modulus,
115207 GPa; strength, 4.75.9 GPa; strain at break, 4.05.4%;
and toughness, 6399 J g1.
We have demonstrated that significant mechanical
enhancement of Kevlar fibers is possible by the incorporation
of carbon nanotubes. However, it is important to put these
results in the context of the properties of other polymer-based,
high-strength, low-ductility fibers. Shown in Figure 4 is a plot
468 www.small-journal.com 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 4. Comparison of fibers prepared in this work with literature
values for various fibers including a PBOnanotube composite fiber. [22]
Selected fibers are labeled. (For full details, see Chae and Kumar, [18]
Table II).
of published data for mechanical properties of various high-
performance fibers (the data have been adapted from Chae
and Kumar, Table II[18]). We have plotted these data in the
form of Youngs modulus versus tensile strength (Figure 4A)
and toughness versus strain at break (Figure 4B). Our data
have been incorporated into this graph as both the set of best
mean values we have observed and the absolute best results
observed for single fibers. (Nota bene: the best results for
single fibers do not necessarily refer to the same fiber. For
example, the best modulus and best toughness were observed
for different fibers.) It is clear that the best mean strength and
toughness values observed for our fibers are better than most
of the fibers reported to date. However, our best observed
results are comparable in terms of strength and modulus and
superior in terms of toughness (albeit at higher strain)
compared to the very best fibers reported. In particular, we
obtain strength and modulus comparable to recent results for
experimental PBO fibers.[30,31] In addition, our best mean
strength and modulus values are comparable to SWNTPBO
fibers prepared at significantly higher nanotube content (open
triangles).[22] Furthermore, our best mean values for tough-
ness and strain at break are significantly higher than those for
SWNTPBO fibers.
Finally, we note that while our best results are comparable
to the best polymer-based fibers, they are inferior to the best
nanotube-only fibers. Recently, Windle et al. reported a
method to spin MWNT-only fibers directly from the chemical
vapor deposition (CVD) furnace. This resulted in fibers whose
best values for strength, modulus, strain at break, and
small 2009, 5, No. 4, 466469
toughness were
9 GPa,
360 GPa, 6%, and 300 J g1,
respectively.[32] However, while we have prepared Kevlar
nanotube composite fibers by a post-treatment technique, we
feel confident that similar results could be obtained by acid-
spinning from Kevlarnanotube dopes as has been achieved
for PBO-based fibers.[22] In that case, high-strength, high-
toughness Kevlarnanotube fibers could be potentially
produced using existing production techniques and possibly
even facilities.
In conclusion, we have developed a new approach for the
preparation of polymernanotube composite fibers. This
method is based on the ultrasonic-assisted swelling of the
polymeric fiber in a nanotube suspension with the use of an
appropriate organic solvent. The swelling of Kevlar in a
carbon nanotube suspension in NMP resulted in new Kevlar
nanotube composites with improved mechanical properties.
Our new approach of incorporating nanomaterials into
polymer macromaterials by swelling could be expanded and
utilized for other nanosystems and polymer materials. We
believe there will be many possible important applications for
this new technique.
Experimental Section
MWNTs grown by CVD were purchased from Nanocyl (product
NC3100) and used as supplied. Kevlar 129 yarn was kindly
provided by du Pont. The MWNTs were dispersed in NMP using an
ultrasonic processor (Model GEX600; 750 W, 20%, 60 kHz) for
5 min followed by 2 h in a sonic bath (grant XB6, 300 W). A
weighed amount of Kevlar 129 yarn was then placed in the
nanotube dispersion in NMP. This yarn consists of a parallel array
of Kevlar fibers, each with diameters of
10 mm. The mixture was
treated using the ultrasonic processor for 5 min followed by
30 min in the ultrasonic bath. The Kevlar yarn was then removed
from the solution and washed by sonication in ethanol for 20 s.
The yarn was then washed twice in ethanol without sonication to
remove any residual NMP. The fibers were then straightened and
allowed to dry in a vacuum oven at 60 8C for 1 week. Following this
the Kevlar fibers were weighed again and a net weight change was
calculated. Mechanical measurements were made on individual
fibers using a Zwick 100 tensile tester at a cross-head speed of
15 mm min1. Eight to thirteen samples were analyzed for each
point on the graph.
Keywords:
carbon nanotubes . fibers . kevlar . nanocomposites .
polymers
[1] J. N. Coleman, U. Khan, W. J. Blau, Y. K. Gunko, Carbon 2006, 44,
1624.
[2] E. W. Wong, P. E. Sheehan, C. M. Lieber, Science 1997, 277, 1971.
[3] M. Yu, O. Lourie, M. J. Dyer, T. F. Kelly, R. S. Ruoff, Science 2000,
287, 637.
[4] M. F. Yu, B. S. Files, S. Arepalli, R. S. Ruoff, Phys. Rev. Lett. 2000,
84, 5552.
small 2009, 5, No. 4, 466469 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[5] J. N. Coleman, W. J. Blau, A. B. Dalton, E. Munoz, S. Collins, B. G.
Kim, J. Razal, M. Selvidge, G. Vieiro, R. H. Baughman, Appl. Phys.
Lett. 2003, 82, 1682.
[6] R. Haggenmueller, H. H. Gommans, A. G. Rinzler, J. E. Fischer, K. I.
Winey, Chem. Phys. Lett. 2000, 330, 219.
[7] J. C. Kearns, R. L. Shambaugh, J. Appl. Polym. Sci. 2002, 86, 2079.
[8] E. M. Moore, D. L. Ortiz, V. T. Marla, R. L. Shambaugh, B. P. Grady, J.
Appl. Polym. Sci. 2004, 93, 2926.
[9] J. K. W. Sandler, S. Pegel, M. Cadek, F. Gojny, M. van Es, J. Lohmar,
W. J. Blau, K. Schulte, A. H. Windle, M. S. P. Shaffer, Polymer 2004,
45, 2001.
[10] A. B. Dalton, S. Collins, E. Munoz, J. M. Razal, V. H. Ebron, J. P.
Ferraris, J. N. Coleman, B. G. Kim, R. H. Baughman, Nature 2003,
423, 703.
[11] A. B. Dalton, S. Collins, J. Razal, E. Munoz, V. H. Ebron, B. G. Kim, J.
N. Coleman, J. P. Ferraris, R. H. Baughman, J. Mater. Chem. 2004,
14, 1.
[12] P. Miaudet, S. Badaire, M. Maugey, A. Derre, V. Pichot, P. Launois,
P. Poulin, C. Zakri, Nano Lett. 2005, 5, 2212.
[13] J. M. Razal, J. N. Coleman, E. Munoz, B. Lund, Y. Gogotsi, H. Ye, S.
Collins, A. B. Dalton, R. H. Baughman, Adv. Funct. Mater. 2007, 17,
2918.
[14] B. Vigolo, A. Penicaud, C. Coulon, C. Sauder, R. Pailler, C. Journet,
P. Bernier, P. Poulin, Science 2000, 290, 1331.
[15] B. Vigolo, P. Poulin, M. Lucas, P. Launois, P. Bernier, Appl. Phys.
Lett. 2002, 81, 1210.
[16] http://www2.dupont.com/Kevlar/en_US/index.html (accessed
November 2008).
[17] D. Tanner, J. A. Fitzgerald, B. R. Phillips, Angew. Chem. Int. Ed.
1989, 28, 649.
[18] H. G. Chae, S. Kumar, J. Appl. Polym. Sci. 2006, 100, 791.
[19] H. Blades, US Patent 3767756, 1973.
[20] H. Blades, US Patent 3869429, 1975.
[21] L. M. Ericson, H. Fan, H. Q. Peng, V. A. Davis, W. Zhou, J. Sulpizio, Y.
H. Wang, R. Booker, J. Vavro, C. Guthy, A. N. G. Parra-Vasquez, M. J.
Kim, S. Ramesh, R. K. Saini, C. Kittrell, G. Lavin, H. Schmidt, W. W.
Adams, W. E. Billups, M. Pasquali, W. F. Hwang, R. H. Hauge, J. E.
Fischer, R. E. Smalley, Science 2004, 305, 1447.
[22] S. Kumar, T. D. Dang, F. E. Arnold, A. R. Bhattacharyya, B. G. Min, X.
Zhang, R. A. Vaia, C. Park, W. W. Adams, R. H. Hauge, R. E. Smalley,
S. Ramesh, P. A. Willis, Macromolecules 2002, 35, 9039.
[23] C. J. Zhou, S. F. Wang, Y. Zhang, Q. X. Zhuang, Z. W. Han, Polymer
2008, 49, 2520.
[24] S. D. Bergin, V. Nicolosi, P. V. Streich, S. Giordani, Z. Sun, A. H.
Windle, P. Ryan, N. P. P. Niraj, Z.-T. Wang, L. Carpenter, W. J. Blau, J.
J. Boland, J. P. Hamilton, J. N. Coleman, Adv. Mater. 2008, 20,
1876.
[25] S. Giordani, S. D. Bergin, V. Nicolosi, S. Lebedkin, M. M. Kappes,
W. J. Blau, J. N. Coleman, J. Phys. Chem. B 2006, 110, 15708.
[26] W. B. Black, J. Preston, in Science and Technology, Vol. 2(Eds: H. F.
Mark, S. M. Atlas, E. Cernia), Interscience, New York 1968,
pp. 297301.
[27] A. T. Fiory, S. Martin, L. F. Schneemeyer, R. M. Fleming, A. E. White,
J. V. Waszczak, Phys. Rev. B: Condens. Matter 1988, 38, 7129.
[28] N. Vahdat, V. D. Sullivan, J. Appl. Polym. Sci. 2001, 79, 1265.
[29] S. Badaire, P. Poulin, M. Maugey, C. Zakri, Langmuir 2004, 20,
10367.
[30] T. Kitagawa, K. Yabuki, R. J. Young, Polymer 2001, 42, 2101.
[31] Y. H. So, Prog. Polym. Sci. 2000, 25, 137.
[32] K. Koziol, J. Vilatela, A. Moisala, M. Motta, P. Cunniff, M. Sennett, A.
Windle, Science 2007, 318, 1892.
Received: July 29, 2008
Revised: November 25, 2008
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