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Dispersion of pristine CNTs in UHMWPE
solution to prepare CNT/UHMWPE composite
fibre
X. Y. Hao*
1,2
, A.-T. Chien
2
, X. Y. Hua
3
, J. Lu
4
and Y. D. Liu
2
Carbon nanotubes (CNTs) dispersion in polymer matrices uniformly remains a challenge. Uniform
dispersion of CNTs within ultra high molecular weight polyethylene (UHMWPE) solution is the first
step to achieve CNT/UHMWPE fibres with excellent properties. Several approaches have been
tried. Composite powder was acquired by coating CNTs on UHMWPE powder, then, dissolved in
decalin, through gel spinning, higher stronger composite fibre is fabricated.
Keywords: CNT, UHMWPE, Composite fibre
Introduction
Ultra high molecular weight polyethylene (UHMWPE)
bre has been used in a wide and ever increasing range of
applications such as personal and vehicle ballistic protec-
tion, cut-resistant gloves, apparel and ropes. However, the
highest strength of the commercial UHMWPE bre only
reaches 10% of its theoretical value.
CNTs are excellent candidates for producing compo-
site bres due to unique combination of properties:
high modulus, high tensile strength, large aspect ratio,
exibility and resilience, and chemical stability. CNT/
polymer composite bers have potential applications in
structural composites used in civil, automobile and
aerospace industry. UHMWPE is non-polar polymer,
which is difcult to be combined with pristine CNTs. In
order to enable themto combine, chemically or physically
modied CNTs have been used to reinforce various bers,
and shows property improvements. But these methods
can not give full play to the reinforcing effect of CNTs.
Compared with CNTs modied by acid, a graft modi-
cation and coupling agent etc, better result can be
expected by using un-modied CNTs, since grafted
functional groups or usage of third agent are detrimental
to CNTs template effect which induce highly aligned
molecular chains in its vicinity. Our strategy is to use
pristine CNTs to template the orientation of UHMWPE
chains to achieve better tensile properties.
112
The
research activities mainly focus on approaches that are
practically feasible to disperse CNTs.
Experimental procedure
Materials
The CNTs used in this study were multiwall carbon
nanotubes with diameter of 2030 nm and length of 30
40 mm, which were kindly provided by Professor Fei
Weis group of Department of Chemical Engineering,
Tsinghua University. UHMWPE with diameter of
80 mm, was purchased from Beijing No.2 Assistant Plant.
Solution
CNTs were added to o-dichlorobenzene (DCB). Ultraso-
nic treatment was applied to obtain a homogeneous
distribution of CNTs with concentration of CNTs 80
mg/1 L DCB.
In a three-necked ask equipped with an overhead
mechanical stirrer and Liebig condenser assembled for
reux and heated to 130170uCto obtain a 2%UHMWPE-
0?5%antioxidant (di-butyl-p-cresol)-decalin solution. (All
blend ratios described in the text relate to weight ratios of
gross weight.) To prevent degradation of UHMWPE, the
solution was carried out under nitrogen. CNTs-DCB
solution was subsequently added to the UHMWPE-
decalin solution. The excess amount of solvent was
evaporated by vacuum distillation at 120uC, while
stirring, to obtain the desired solution concentration of
2%UHMWPE.
Gel spinning
As soon as the UHMWPE solution was transferred into
an extruder, which was preheated to 135uC, the spinn-
ing process started. The extruded UHMWPE passed
through an air gap, then, entered an ice water pool for
gel spinning. Then the spun bre was passed through
hexane bath to remove decalin at room temperature.
The spun bre was hot drawn by passing through silicon
oil with 130 and 140uC respectively.
Coating
UHMWPE particles and CNTs were mixed by triple
abrader for 8 h to form CNT/UHMWPE composite
1
School of Materials Sciences and Technology, China University of
Geosciences, Beijing 100083, China
2
School of Materials Science and Engineering, Georgia Institute of
Technology, Atlanta, GA30332-0295, USA
3
Key Laboratory of Coordination Chemistry and Functional Materials in
Universities of Shandong, Dezhou University, Dezhou 253023, China
4
Indian River Research and Education Center, University of Florida, Fort
Pierce, FL 34945-3138, USA
*Corresponding author, email xy1864@126.com
W. S. Maney & Son Ltd. 2013
Received 16 October 2012; accepted 25 March 2013
DOI 10.1179/1432891713Z.000000000201 Materials Research Innovations 2013 VOL 17 SUPPL 1 S1-123
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particles. Then were dissolved in decalin, gel spun, and
hot drawn as above.
Results and discussion
The best solvent for CNTs is DCB, with solubility of
95mg CNTs per litre DCB. CNTs do not dissolve in
decalin, which is best solvent for UHMWPE gel
spinning. DCB dissolves mutually with decalin. But
aggregation of CNTs appears, when CNT/DCB solution
is drop-wisely added into UHMWPE/decalin solution
with temperature ranging from 90 to 180uC (Fig. 1). It is
hard to disperse CNTs in UHMWPE without acid or a
graft modication methods, because, at high tempera-
ture (above 80uC), CNTs separates out from DCB, or
N,N-Dimethylformamide (DMF) solution, etc. While
UHMWPE gels from decalin or DCB below 100uC.
In order to solve phase separation, DCB was used
instead of decalin. DCB, antioxidant and UHMWPE
powder were mixed together in a reactor at 150uC, with
nitrogen (N
2
) protection to get UHMWPE/DCB solu-
tion with concentration of 2% UHMWPE. CNT-DCB
solution was added drop by drop into UHMWPE/DCB
solution, along an insertion horn of sonication below the
upper level of UHMWPE/DCB solution. The process
lasted about 1030 min until the solution became
homogeneous. But the viscosity of the solution was
too low to draw ber. The reason is that the sonication
or DCB leads to degradation of UHMWPE.
From our previous study, DCB is not a good solvent
for gel spinning. Therefore, we try to avoid using DCB.
UHMWPE particle and CNTs were mixed by triple
abrader with a treatment time of 6 h to form CNT/
UHMWPE composite particles. CNTs disperse uniformly
on surface of UHMWPE powder without being cut short.
After the composite particle is dissolved in decalin, we can
see that CNTs disperse optically uniformly (Fig. 2). We
can see CNTs disperse well under microscope (Fig. 3) as
well. From reactor, composite ber can be drawn out
directly, with higher strength (Fig. 4).
By gel spinning and hot drawing, composite bre with
diameter of 18?8 mm is gotten (Fig. 5). By regulating
epitaxial growth of UHMWPE on pristine CNTs
surface, nano-hybrid shish-kebab (NHSK) with CNTs
shish and UHMWPE kebab can be grown. This type of
nanostructure can signicantly improve interfacial inter-
action between llers and polymer matrix. So reinforce-
ment potential of nanollers with high aspect ratio (L/D)
can be realised. Under further stretching, kebab of
1 Phase separation of CNT/UHMWPE solution
2 Uniform solution of CNT/UHMWPE
3 Solution of CNT/UHMWPE under microscope
4 Composite bre drawn from reactor
5 Composite bre under magnifying glass
Hao et al. Dispersion of pristine CNTs in UHMWPE solution
S1-124 Materials Research Innovations 2013 VOL 17 SUPPL 1
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UHMWPE will be transformed into highly extended
chains along with ber axis. Post-spinning hot drawing
process enhances orientation, exfoliation and the
mechanical properties of the CNT/UHMPE composite
bre. We will take further steps to improve the exfoliation
of CNTs in UHMWPE and carry out tensile strength test
of composite bre later.
Based on our research, we believe that coating
approach can be used for CNT/Kevlar and other
composite bres as well. The research results can be
further expanded to achieve industrialisation.
Conclusions
By triple abrader process, composite particles with core
(UHMWPE)-shell (CNTs) structure is produced. The
coating method is an effective way to achieve uniform
dispersion of pristine CNTs in solution of UHMWPE.
CNTs initiate UHMWPE crystallisation to form nano-
hybrid shish-kebab structure. Pristine CNT/UHMWPE
composite bre is fabricated by gel-spinning and hot
draw process.
Acknowledgements
This work was financially supported by Fundamental
Research Funds for Central Universities, China
(2011YXL002). Authors thank Professor S. Kumar
and Dr H. Chae at School of Materials Science and
Engineering, Georgia Institute of Technology, Atlanta,
USA.
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