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Advances in thermoplastic polyurethane composites reinforced with carbon

nanotubes and carbon nanofibers: A review
Rabia Sattar, Ayesha Kausar and Muhammad Siddiq
Journal of Plastic Film and Sheeting published online 20 May 2014
DOI: 10.1177/8756087914535126
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DOI: 10.1177/8756087914535126
polyurethane composites jpf.sagepub.com
reinforced with carbon

nanotubes and carbon
nanofibers: A review
Rabia Sattar1,2, Ayesha Kausar1 and

Muhammad Siddiq2
Abstract
Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest
man-made material known to date. Owing to high electrical conductivity, CNTs
have also gained interest in the area of electrical appliances and communication
related applications. Moreover, carbon nanofibers (CNFs) depict fine electrical
and mechanical profile. Due to their miniscule size, excellent mechanical, elec-
trical, and thermal properties, CNTs can only be beneficial if they are homoge-
neously dispersed and embedded into light-weight engineering polymer matrices.
Adding small amounts of CNTs strongly improve the electrical, thermal, and
mechanical properties of the composites. In order to enhance their chemical
affinity to polymer matrices, chemically modifying the graphitic sidewalls and
tips is necessary. This article reviews the processing technology and improvement
of various properties of carbon nanotube-reinforced thermoplastic polyurethane
(PU) composites. Initially, the structure, morphology, mechanical, thermal, and
electrical properties of nanotubes are described. Then various strategies for
fabricating PU/CNTs composites and their properties are discussed. To conclude,
recent developments in the field of mechanical, thermal, and electrical properties
of thermoplastic PU reinforced with nanotubes and nanofibers are reviewed.
1
Nanosciences and Catalysis Division, National Centre For Physics, Quaid-i-Azam University Campus,
Islamabad, Pakistan
2
Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan
Corresponding author:
Muhammad Siddiq, Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan.
Email: m_sidiq12@yahoo.com

2 Journal of Plastic Film & Sheeting 0(0)
A brief account regarding the toxicity and environmental safety aspects of carbon
nanomaterials is also included in this article.
Keywords
Carbon nanotubes, carbon nanofibers, polyurethane, composite, thermoplastic,
reinforced
Introduction
A polymer nanocomposite combines polymers loaded with high surface area
reinforcing fillers.1 Such systems have gained massive attention from the
materials community as even a very low filler loading is sufficient to improve
the desired material properties. Conventional fiber-reinforced composites can
be fabricated with a comparatively low tooling cost as nanocomposites are
compatible with conventional polymer processing.2 The role of carbon nano-
tubes (CNTs) in developing new advanced composite materials has been
focused due to superior mechanical, thermal, and electrical properties.3–7
The homogeneous dispersion of nanotubes in polymer matrix, without des-
troying their integrity, has been considered as an important factor for efficient
utilization of these nanofillers in nanocomposite applications.8
Since Iijima discovered CNTs in 1991, they have been exploited in many
areas of science and engineering due to their excellent properties. Their out-
standing properties render nanotubes as an excellent nano-size reinforcement
material in composites.9 The CNT structure is cylindrically curled graphene
sheets. The distinction between graphene and graphite is that graphene is a
single, one atom thick layer of the frequently found mineral graphite; graphite
is essentially made up of hundreds of thousands of graphene layers. Unlike
diamond, which is a 3-D carbon atom structure arranged in a tetrahedron
pattern, graphite is formed as a 2-D sheet of carbon atoms in a hexagonal
array. The CNT properties depend how the graphite sheets are rolled, i.e. the
structure, length, diameter, and morphology of the tubes.10 CNTs are mainly
categorized as single-walled carbon nanotube (SWCNT) and multi-walled
carbon nanotube (MWCNT). SWCNT consist of a single rolled graphene
sheet to form a cylinder having 1 nm diameter and up to a centimeter
length. On the other hand, MWCNTs consist of several concentric graphene
cylinders separated by 0.35 nm. These diameters may range from 2 to * 100 nm
and lengths around tens of microns.9 The tube chirality, or helicity, Ck and
the chiral angle, y are the key parameters used to describe the nanotube
atomic structure. The*chiral vector is frequently known as the roll-up
* *
vector and defined as Ck ¼ na1 þ ma2 . The integers (n, m) are the number
* *
of steps along the zig-zag carbon bonds of the hexagonal lattice and a1 and a2

Sattar et al. 3
are unit vectors as shown in Figure 1(A).10 The ‘twist’ in the tube is deter-
mined by the chiral angle. The chiral angle at 0 and 30 exists as the two
limiting cases. The 0 chiral angle is referred as zig-zag and the 30 chiral
angle as armchair based on the carbon bond geometry around the nanotube
circumference. The armchair and zig-zag nanotube structure is shown in
Figure 1(B). In terms of the roll-up vector (n, m), for the armchair nanotube
n ¼ m and for the zig-zag nanotube either n ¼ 0 or m ¼ 0. By knowing the
carbon atom inter-atomic spacing, the nanotube diameter can be identified by
the nanotube roll-up vector.10 The carbon nanotube chirality has major
effects on the material physico-mechanical properties. Meticulously, tube
chirality has been identified to possess strong impact on the electronic proper-
ties. While graphite is often regarded as a semi-metal, nanotubes can be either
metallic or semiconductors depending on tube chirality.11 Different tube
morphologies result from CNT defects, yet they can be single-walled or
multi-walled structures. MWCNT is fundamentally concentric single-walled
tubes and individual tubes can have different chirality. Weak van der Waals
forces are responsible for binding these concentric nanotubes. As the intra-
tube interactions complicate the nanotube properties, single walled CNTs are
more desired for basic tube structure/property relationship investigations. In
fact, both single and multi-walled nanotubes show distinctive properties that
can be exploited for use in composite materials.10
Figure 1. (A) Illustration for hexagonal graphite sheet ‘rolled’ to form carbon nano-
tube; (B) atomic structure of (a) an armchair and (b) a zig-zag nanotube.10
Table 1 summarizes the CNT unique mechanical, electrical, magnetic,

optical, and thermal properties.12 High-performance light weight structural
materials can be developed by adding nanotubes to the polymers or other

matrix materials which can be used in some particular applications such as

space exploration. The better CNT properties present exciting opportunities
for new composites. Recently, polymer/carbon nanotube composites have
gained much interest due to their exclusive mechanical, surface, and multi-
functional properties, and strong interaction with the matrix resulting from
the nano-scale microstructure and very large interfacial area. The nanocom-
posite performance depends on the nanotube dispersion in the matrix and
interfacial interaction between the filler and the polymer. However, the
carbon atoms in the nanotube walls are chemically stable due to the aromatic
nature of the bond. So, as a result, the reinforcing CNT is inert and interacts
with the surrounding matrix mainly through van der Waals interactions. They
do not offer an efficient load transfer across the matrix-nanotube interface.
Therefore, significant efforts have been directed toward developing methods
to modify their surface properties. There are several comprehensive review
papers that describe the chemistry of the functionalized carbon nanotube and
the reaction mechanisms between the CNT and functional groups.13–16 These
methods can be appropriately divided into chemical functionalization and
physical methods based on the interactions between the active molecules
and nanotube carbon atoms. Table 2 tabulates the major principles of the
mentioned methods along with the corresponding advantages and disadvan-
tages.17 There are many studies on modifying the CNT surface characteristics
based on the various techniques; however, there are many processes and
material variables that have not been fully optimized. In addition, the con-
cerns related to the structural changes resulting from chemically functionaliz-
ing CNTs, the damaging effects of ultrasonication and other dispersion and
mixing processes still exist because of the expected adverse effects.
Polyurethanes (PU) are important polymers with wide applications and
properties.1,18 The PU end product properties can be designed according to
user needs. Their properties range from liquid, soft, and rubbery solids to
rigid thermoplastic and thermoset materials. This polymer has diverse appli-
cations in coatings, structural foams, and composites due to their excellent
abrasion resistance, toughness, low temperature flexibility, chemical and cor-
rosion resistance, and a wide range of mechanical strength.19 Due to the
possibly greater applications and versatility of properties, these materials
entail a comprehensive understanding of the synthesis and properties. The
term ‘‘polyurethane’’ is given to polymers containing a noteworthy number of
urethane (ethyl carbamate) groups. The urethane linkage is formed by the
reaction of an isocyanate group with the hydroxyl group of polyol as shown
in general Scheme 1.

Sattar et al. 5
Table 1. Theoretical and experimental properties of CNT compared with graphite.12
Property CNT Graphite
Specific gravity 0.8 g/cm3 for SWCNT; 2.26 g/cm3

1.8 g/cm3 for MWCNT
(theoretical)
Elastic modulus 1 TPa for SWCNT; 1 TPa (in-plane)
0.3–1 TPa for MWCNT (145 Million psi)
Strength 50–500 GPa for SWCNT;
10–60 GPa for MWCNT
Resistivity 5–50 m
cm 50 m
cm (in-plane)
Thermal conductivity 3000 W m1 K1 3000 W m1
(theoretical) K1(in-plane)
6 W m1 K1(c-axis)
Magnetic susceptibility 22 106 EMU/g (perpen- _
dicular with plane),
0.5 106 EMU/g (parallel
with plane)
Thermal expansion Negligible (theoretical) 1 106 K1 (in-plane),
29 106 K1(c-axis)
Thermal stability >700 C (in air); 450–650 C (in air)
2800 C (in vacuum)
Specific surface area 10–20 m2/g _
Table 2. Advantages and disadvantages of various nanotube functionalization methods.17

Interaction Re-
Possible Easy with agglomeration
damage to polymer of CNT
Method Principle to CNT use matrix in matrix
Chemical Side wall Hybridization of C ˇ S ˇ

method atoms from sp2 to
sp3
Defect Defect ˇ ˇ S ˇ
transformation
Physical Polymer Vander Waals force, ˇ V

method wrapping p–p stacking
Surfactant Physical adsorption ˇ W
adsorption
Endohedral Capillary effect W ˇ
method
S: strong; W: weak; V: variable according to the miscibility between matrix and polymer on CNT; ˇ:
Yes; : No.

N C O H O C
N O
H
Isocyanate group Hydroxyl group Urethane linkage
Scheme 1. Classical urethane linkage reaction.
Polyurethane/carbon nanotube (PU/CNT) composites are more functional

than basic PU.20–22 These composites are considered as ternary systems
formed by three components:
. nanofiller (carbon nanotube)

. hard segments (HS)
. soft segments (SS).
All of these components can be varied in ratio, chemical composition, and

physical properties. Generally, the PU SS consists of polyester or polyether
macrodiol and hard segment (HS) composed of diisocyanate and diol or
diamine.18 The study of variation in PU phase morphology with the inclusion
of CNT and its effects on the mechanical performance, along with the under-
standing of thermodynamics of favored alliance between nanotubes and PU
phases should be considered in order to develop tailored PU/CNT compos-
ites.23 Most PU/CNT nanocomposite application necessitates an even disper-
sion and distribution of separated nanotubes; therefore, debundling of CNT
samples is indispensable. As discussed above, huge aspect ratio of CNTs
usually result in extensive non-covalent attractive forces between nanotubes
causing them to aggregate together into bundles that are difficult to separate.
Aggregation/bundling of CNTs may cause poor nanofiller dispersion in PU
nanocomposite and cause adverse effects on the thermal, mechanical, and
other physical properties of the resulting materials. In these systems, nano-
scale and spectroscopic properties of macroscopic samples are also important
to understand the structure–property relationship between the components.
Fabrication of PU/CNT composites

Several methods for fabricating PU/CNT composites including solution
mixing, melt blending, in situ polymerization, etc. have been described here.
Better composite performance is observed when the CNTs are well dispersed,
without entangling and bundle formation. However, fine dispersion is not

Sattar et al. 7
easy to achieve by typical mixing methods. Various parameters for the fabri-
cation process, such as sonication time, stirring speed, dispersion solvent
selected, and reaction mixture temperature are essential to attain good nano-
tube dispersion in the polymer matrix. Among these, sonication is the most
popular one for including CNTs into the resin.24
Solution mixing
Solution mixing is a common way to prepare polymer/nanotube composites
due to low solution viscosity which assist the mixing and nanotube dispersion.
Many researchers have used this processing method to prepare both thermo-
set and thermoplastic polymer nanocomposites. The basic mixing scheme is
almost same as either the nanotubes are dispersed in solvent or polymer
solution by stirring or nanotubes are mixed with polymer in solution by agi-
tation and then followed by evaporating the solvent to form a dry composite
film.25 To achieve metastable nanotube dispersion, the agitation can be
achieved by magnetic shearing, mechanical stirring, reflux, or sonication
using sonication bath.26 Other ways such as heat or acid treatment27 of the
functionalized nanotubes28–30 can often be used to improve nanofiller disper-
sion. Solution mixing which often produces well-dispersed polymer nanocom-
posites31–35 has also been used by many researchers to mix nanotubes and
PUs. Vaia and coworkers20,36 used tetrahydrofuran (THF) solvent to mix
MWCNT into a commercially available PU with a polyester SS and aromatic
hard segment with achieving a percolation threshold of 0.5 vol.%. First, poly-
mer was dissolved in THF and then the nanotube was added to this solution
with continuous stirring. Sonication for 2 h was followed by subsequent cast-
ing and controlled solvent evaporation and finally composite films were
obtained by peeling them off the Teflon disk. THF solvent was also used
with another commercial PU, and through controlled evaporation, carbon
nanotube-reinforced composites were obtained37,38 In another study, several
mixtures of PU/CNT films were prepared by using various amounts of func-
tionalized and unfunctionalized nanotubes.39 In this method, a predetermined
amount of reinforcing filler was bath-sonicated for 2 h in dimethylformamide
(DMF). Afterwards, calculated amount of PU (pellets) were added to suspen-
sion under continuous sonication and left under sonication for further 1 h to
readily solubilize the PU. Subsequently, the mixture was poured over a Petri
dish containing a silicone bed, which provided smooth and uniform surface
and facilitated detaching the film at the end of the process. The infiltration of
MWCNT forests with a PU solution in DMF using a simple drop-casting
procedure has also been reported.40
Mixed THF and DMF solvents were also used to cast PU nanotube com-
posite films.21,41 Solvent-cast PU/MWCNT composites were prepared using a

1:1 DMF/THF ratio.42 The system was chosen because amide solvents are
good nanotube dispersants, while the THF has a low boiling point which
allows easier solvent evaporation from the cast composites. Jung and cow-
orkers have also prepared the PU nanocomposites using THF and DMF (1:1)
as a mixed solvent.43 Kim and coworkers reported dispersing CNTs in a
waterborne PU matrix.44,45 The MWCNT dispersion in the PU matrix was
done through non-covalent solution blending. Electrospinning is another
solution-based process to provide alignment to the nanotube which involves
the continuous production of one dimensional nanofibers. In an electrospin-
ning process, a high voltage is applied to a polymer solution which overcomes
surface tension and a fine jet stream ejected from the needle gets deposited on
the collector. DMF was also used with polyester based PU to produce elec-
trospun fibers filled with carbon nanotube.46 PU and PU/MWCNT 350 nm
nanocomposite nanofibers were also prepared by an electrospinning process
from PU DMF solutions.47
Melt blending
Melt blending/processing is a very valuable technique for fabricating thermo-
plastic polymer/carbon nanotube composites as they soften when heated
above their melting point. In addition, this method is suitable for polymers
that cannot be processed with solution techniques due to their insolubility in
common solvents.48,49 For polymer/CNT composites to be commercially
viable, the fact that these materials need to be manufactured on an industrial
scale by melt processing is significantly important. The complete dispersion of
primary CNT agglomerates in a polymer melt is difficult to achieve, making it
an important and exigent scientific dilemma. This method involves using
standard melt processing equipment such as an extruder or internal mixer.
In this process, CNTs are melt mixed in polymers using mechanical mixing
elements present in the processing equipment. For thermoplastic polymers,
single and twin-screw extruders are commonly employed for melt compound-
ing.50 For lab-scale experiments, batch micro-compounders are used. This
method is used to produce direct compounds or master batches with higher
CNT loadings which are later diluted. Generally, polymers and CNT are
added in a running extruder/compounder. Due to high temperature, the poly-
mer melts quickly and the shear forces present in the compounder help dis-
perse CNT agglomerates. The shear forces generated inside the compounder
depend on the melt viscosity and how fast the mixing elements rotate. Many
studies have reported producing composites either by direct mixing or by
master batch dilution in PUs.51–53 One common way to produce composites
by melt compounding is with master batch dilution. In this method, highly
loaded CNT composites are produced in the extruder. These are known as

Sattar et al. 9
master batches and are diluted with the neat polymer in the extruder to obtain
lower filler composites. As the CNT agglomerates are wetted with the poly-
mer during master batch production, they get well dispersed during dilution.
Further, the agglomerates are subjected to shear twice achieving good disper-
sion. Slight modifications to the melt processing equipment are also used to
enhance CNT dispersion.54,55 The higher mechanical properties of the com-
posites processed at a high-shear rate than those processed at a low shear rate
were attributed to better CNT dispersion. The biggest advantage of the melt
compounding approach is that existing melt processing technology can be
used to produce the composite. The method is fast and economical. It is an
environment-friendly method as compared to those in which large quantities
of solvents might be needed. Further, this approach is flexible as the CNT
loading can be varied easily and the same equipment can be used to produce
composites of different polymers. However, at very high filler loadings, there
might be some limitation in using extruders due to very high torque values.
This approach has successfully prepared many other polymers, including
polyolefins,56–59 polyamides,60,61 polyesters,62,63 and PU.64 Electrically con-
ducting adhesive nanocomposites with different nanotube loading were
obtained by dispersing MWCNT in polyester-based thermoplastic PU by
melt mixing.64 Prior to the melt mixing process, polymer powder was pre-
pared and the nanotube and polymer powders were stirred in order to obtain
a homogeneous mixture. Afterward, this mixture was blended in twin-screw
extruder. Chen and coworkers have also fabricated carbon nanotube rein-
forced PU composite fibers via twin-screw extrusion.65 Conductive thermo-
plastic PU/MWCNT composites with an extremely low percolation threshold
of 0.13 wt.% via melt blending process have been synthesized.66 Percolation
threshold is actually a mathematical idiom related to percolation theory (pat-
terning of long-range connectivity in random systems). Below the threshold, a
giant connected component does not exist; while above it, there is a giant
system-sized component. Research regarding percolation threshold of CNTs
in polymer composites has shown dependence on CNT type, dispersion, syn-
thesis method, dispersion method, as well as polymer type. Usually, low per-
colation threshold results from homogeneous dispersion and a high CNT
aspect ratio in the matrix. Consequently, low percolation threshold for the
aligned nanotubes has been observed in polymer/carbon nanotube compos-
ites.67 Low percolation threshold is beneficial in the composite system. These
nanocomposites were also prepared by two-step melt mixing strategy in order
to improve the filler dispersion. A 15 wt.% MWCNT master batch in thermo-
plastic PU was prepared and then diluted to 3 wt.% filler. A twin-screw
extruder running at 80 rpm was used to do the mixing. Thermoplastic PU
filled with carbon nanotube prepared through a two-step melt blending pro-
cess for electrical dissipative and conductive applications has been reported.68

Injection molding has also been commonly used in combination with extru-
sion to fabricate nanocomposites samples for further testing. Abdullah et al.
have reported preparing PU nanofiller composites by mixing and injection
molding.69 The mixing was done in two steps to get better mixing quality.
First, the manual mixing of filler and polymer at different composition was
carried out before being fed into extruder. Then, an extruder was used for
further mixing the pre-blend at 210 C and the 260 rpm screw speed to opti-
mize the mixing properties. After mixing, injection molding was used to make
dog bone and round-shaped samples. Based on an intensive literature search
on mechanisms and influencing factors on dispersion of agglomerated nanos-
tructured fillers, the main dispersion steps were evaluated and investigated
concerning the agglomerated CNT.53–55 Consequently, systematic investiga-
tions have been performed to study the effect of the melt infiltration on CNT
agglomerate dispersion and to analyze the corresponding main dispersion
mechanisms, namely rupture and erosion. The states of CNT agglomerate
dispersion were assessed by quantifying the agglomerate area ratio and par-
ticle size distribution using image analysis of optical transmission micro-
graphs.54–59 Melt infiltration into the primary nanotube agglomerates plays
a crucial role for their dispersion in the melt. During melt mixing when low
shear rates were applied, better CNT dispersion was obtained in high viscosity
matrices because applied shear stresses were high. On the contrary, if high
shear rates were applied, similar CNT dispersion was obtained in low and
high viscosity matrices although significantly lower shear stresses were applied
in the low viscosity matrix versus the high viscosity matrix.55,60–64
In situ polymerization
In recent years, in situ polymerization has been widely used to prepare poly-
mer-grafted nanotubes and process related to polymer composite mater-
ials.70–80 The chief advantage is to facilitate grafting polymer
macromolecules onto the walls of MWCNT. In situ polymerization permits
fabricating nanocomposites with high carbon nanotube loading and miscibil-
ity with polymer matrices. This processing method is mainly important for
fabricating insoluble and thermally unstable polymers that cannot be pro-
cessed via solution or melt processing. PU/MWCNT elastomeric nanocom-
posites have been prepared via in situ polymerization in the presence of
sonication. The chemical route for functionalizing nanotubes and preparing
composites is shown in Figure 2.81

Sattar et al. 11
HNO3 SOCl2 EDA

COOH COCl COEDA
H2SO4 n n n
CNT
TDI
H2NCH2CH2NH2
(EDA)
PTMO
H O CH2 OH COEDA-PU COEDA-TDI
4 n n n
(PTMO)
O
NCO
HNCO CH2 O
O 4
NCO CH3
C N CH3
H n
(TDI)
(PU)
Figure 2. Chemical routes for functionalization of MWCNT and preparation of

composites.81
First, the carboxylic acid groups on the MWCNT surface were converted
into amide in a two-step chemical reaction. These amide-terminated nano-
tubes were reacted with polyoxytetramethylene glycol (PTMO) and toluene
diisocyanate (TDI) to produce the composites. The grafted amide groups on
the nanotube surfaces can easily react with TDI and the functionalized
MWCNTs are inserted into the hard PU segments as shown in Figure 3.
Ryszkowska et al. reported the synthesizing carbon nanotube-reinforced
nanocomposite by in situ polymerization using poly(ethylene adipate)
(PEA) under sonication.82 A high intensity ultrasound had been applied to
fabricate the composites. First, nanofillers were dispersed with acetone, and
then the PEA and acetone were mixed. Finally, the PEA and MWCNT mix-
ture was used to produce PU nanocomposites under ultrasonic agitation.

(a)
PTMO
TDI
(PTMO)
(b)
MWCNT inserted in hard segment
Figure 3. Model of carbon nanotube inserted in hard segment of PU: (a) carbon nano-
tube and (b) hard segment (TDI).81
Chen et al. also prepared PU/MWCNT nanocomposites by an in situ

polycondensation approach.83 Polyester-based PU and carbon nanotube con-
ductive composites had also been prepared via in situ polymerization
process.84 A series of conducting nanocomposite films comprising different
soft–hard segments and various MWCNT loading were prepared by in situ
coupling reaction among linear hydroxyl-terminated polymer diols, 1,6-hex-
amethylene diisocyanate (HDI), and different chain extenders.85
Hyperbranched PU nanocomposites reinforced with nanotubes were fabri-
cated by in situ polymerization with poly("-caprolactone)diol (PCL) as the
SS, 4,40 -methylene bis(phenylisocyanate) (MDI) as the HS, and castor oil as
the multifunctional group for the hyper branched structure.86 These hyper-
branched PU with different HS were prepared by a two-step procedure. First,
the prepolymer was prepared by reacting polyol and diisocyanate. After com-
pletion, the required castor oil and chain extender were added. The chemically
modified MWCNT dispersed in DMF were then added to reaction mixture
and reacted to obtain PU composite films.
Loos et al. have synthesized the PU/MWCNT composites by dispersing the
carbon nanotube in polyol as the dispersing agent using a high shear Ross
mixer.87 The MWCNT suspension was degassed and mixed with the isocyan-
ate by stirring, and the mixture was allowed to cure at room temperature
overnight and then finally post-cured. The preparation of in situ covalent

Sattar et al. 13
encapsulation of MWCNT by PU via condensation polymerization of MDI

and butane diol (BD) in the presence of HO-poly(acryloyl chloride) (PACl) P-
MWCNT was reported by Wang et al.88 To make the nanocomposites, HO-
PACl-MWCNT and DMF were mixed and sonicated. With stirring, MDI
was added followed by adding catalyst and chain extender and the reaction
continued overnight. Afterwards, the solution was vacuum filtered, washed
with solvent, re-dispersed in DMF, and precipitated by adding THF to obtain
the final product. The MWCNT composite fabrication with soluble cross-
linked PU was reported by Liu and coworkers.89 Initially, MDI and hydro-
xyterminatedpolybutadine (HTPB) polyol was mixed with stirring. DMF
solvent was then added to generate a dilute homogeneous solution followed
by the drop wise addition of BD chain extender with stirring. After some time,
DMF/toluene (1:4) mixed solvent was added gradually to reduce the mixture
viscosity and the temperature was raised in order to complete the cross-link-
ing reaction. The dispersed nanotube suspension in DMF/toluene was then
gradually added into solution with stirring to yield a homogeneous composite
solution/suspension. Wang et al. incorporated hydroxyl groups into the PU
backbone and then used the ‘‘grafting to’’ approach to functionalize the
carbon nanotube via esterification reaction between MWCNT and segmented
PU as depicted in Figure 4.90 According to a model proposed for the chain
conformation and packing of MDI-HS in PU elastomers, MDI had non-
planar zig-zag conformation.7
H2 H2 DMF
2 OCN C NCO HO C O H OCN NCO
4 85-90 oC, 3 hr 1
x
Et O O Et
H2 H2 DMF H H2 H2
1 HO C C C OH C N N C O C C C O
H
85-90 oC, 3 hr
CH2OH CH2OH
PU n
TMP
O O
H2 H H2 H2
: Ph C Ph N C O C O C NH Ph C Ph
4
x
O O
*
100 oC, 24 hr
C * C PU
Cl -HCl
CH2OH
m
PU m
Figure 4. ‘‘Grafting to’’ approach for the functionalization of MWCNT with segmented
PU prepared from MDI, i.e. is a bent molecule not planar.

The non-planar structure in the hard PU segments enhances the interaction

of PU chains with the nano-filler surface, thus sustaining the properties of the
resulting composites. The conventional prepolymer method was employed to
prepare the segmented PU with side-chain hydroxyl groups on the chain
extender. Prepared acylated MWCNT was allowed to react with segmented
PU at 100 C for 24 h to obtain PU-grafted CNTs. Films were prepared by
dissolving the PU matrix in DMF and then adding this solution to PU-grafted
MWCNT.
Multi-walled CNTs containing carboxyl, lactone, or phenol groups on the
surface were introduced into the PU matrix using various MWCNT load-
ing.91 The PU-based on poly(oxypropylene)glycol (PPG) with trimethylol
propane (TMP) and TDI was used as matrix for nanocomposites synthesis.
Jung et al. had proposed a novel concept to prepare PU/MWCNT nanocom-
posites via in situ prepolymer polymerization in the presence of modified
nanotube.92 In another attempt, they first synthesized the prepolymer by
reacting MDI and PCL followed by chain-extension step for the PU prepar-
ation. After the chain extension with TMP, this solution was treated with
carboxyl-functionalized MWCNT at 100 C for 1 h to obtain the composites.
Synthetic route for the fabricating composites is shown in Figure 5.93 Carbon
nanotube grafted with poly("-caprolactone)diol (PCL) has also been used to
make PU nanocomposites.94 The functionalized MWCNT was first reacted
with the desired amount of polyol and PU prepolymer was synthesized by the
reacting MDI with PCL grafted MWCNT followed by the adding chain
extender to the prepolymer. Afterwards, the solution mixture was diluted
and PU composites were washed with water and vacuum-dried overnight.
Fabricating PU/MWCNT nanocomposites with MWCNT up to 1 wt.% load-
ing via addition polymerization reaction has also been reported.95
The electroactive shape memory of MWCNT-filled PU composites pre-
pared by in situ polymerization was studied by Jung et al.43 For the in situ
polymerization, the specified weight fractions of the acid-treated nanotube
were dispersed in polyol followed by the adding MDI to obtain prepolymers
by the reaction between the polyol–OH groups and the MDI–NCO groups.
Then, BD was added to the prepolymer to get MWCNT filled PU composites
by in situ polymerization. In another study, PU/MWCNT composites pre-
pared by a sol–gel process have been reported.96 MWCNT were first modified
with coupling agents and introduced into PU-urea system by chemical link-
ages. Transparent membranes with self-crosslinkable PU/MWCNT nano-
composites were fabricated.

Sattar et al. 15
O O
H2 H2 H2 H2
HO C C O C O C C OH OCN C NCO
5 6 5
n n
80 oC, 90 min
O O
O O
H2 H2 H2 H2 H H2
OCN C NH C O C C O C O C C O C N C NCO
5 6 5
n n
TMP
80 oC, 1hr
Carboxylic MWCNT
100 oC, 1hr
O O Et
H2 H2
C N N C O C C C O
H H
O CH2
n
MWCNT C O
Figure 5. Synthetic routes for the fabrication of PU/MWCNT nanocomposites.
Broadly speaking, in situ polymerization method involves the polymeriza-

tion on the nanotube surface. However, this approach is not generally applic-
able to all the polymer types and polymerization is often incomplete. Solution
dispersion is a comparatively better technique involving dispersing a filler
suspension in a polymer solution via high agitation. Although both the in
situ polymerization and solution methods are rather simple, there is a prob-
ability of nanotube stacking during processing due to their intrinsic strong
attraction and large surface area. Melt blending under high shear is a rela-
tively better method primarily applicable to thermoplastic polymers.
Other methodologies employed

Aıssa et al. proposed the fabricating field effect transistor (FET)-based nano-
composite microfibers of PU and MWCNT directly on a silicon substrate by
using developed UV-assisted direct-writing technology.97 Nanocomposite
microfibers, consisting of cylindrical microrods having different diameters
with various nanotube loads, were used as a transistor active channel in the
FET scheme. In another study, PU/MWCNT composites had been prepared
by spray-coating and bucky paper infiltration techniques.98 Spray-coating
was used to produce samples with 1 mass % MWCNT, and impregnation
methods were used to produce buckypaper-based materials with

approximately 50 mass % nanotubes. To fabricate PU/MWCNT nanocom-

posites by spray-coating, different amounts of MWCNT were first suspended
in DMF solvent and then sonicated, centrifuged, and filtered. Afterward, PU
was also dissolved in DMF and the resultant solution was added to the
MWCNT suspension using long-term stirring and sonication. The PU solu-
tion and nanotubes were sprayed on stainless steel substrates and solvent
evaporation was carried out to obtain the final films. In bucky paper infiltra-
tion technique, initially single/multi-walled CNTs are used to form solvent-
based suspension with the aid of surfactant and sonication. Through filtration
process, CNTs are fabricated into thin membranes called bucky papers to
form networks of CNT ropes. In the bucky paper resin infiltration technique,
the resin impregnation of the produced bucky paper is usually achieved by
infiltrating solvent diluted resin (polymer). For fabricating PU/MWCNT
nanocomposites using bucky paper, first functionalized nanotube materials
were dispersed in DMF solvent by treatment in a low ultrasonic bath. Then
the homogeneous suspension was filtered and dried. PU solution was allowed
to pass through the nanotube mat placed on the membrane for several hours
to allow impregnation. After infiltration, a bucky paper was soaked in the PU
solution system overnight to assure complete impregnation and the compos-
ites were maintained in a vacuum oven to remove solvent and stored in a
vacuum chamber. Arlas et al. had also adopted the bucky paper infiltration
processing route to fabricate PU/MWCNT nanocomposites.42
Morphology and structure of PU/CNT composites

The microstructure of PU/MWCNT composites have been investigated and
characterized using various techniques such as optical microscopes, scanning
electron microscopy (SEM), transmission electron microscopy (TEM), atomic
force microscopy (AFM), and X-ray diffraction (XRD). Electron microscopy
is a popular technique to study nanotube structure and their dispersion in
nanocomposites.99–102 In a study regarding thermoplastic PU/carbon nano-
tube composites, SEM micrographs revealed dispersed bundles or agglomer-
ates of approximately 6–10 nanotubes in PU matrix.64 Chen et al. investigated
MWCNT and PU composite fiber morphology by a field emission SEM and
TEM.65 They observed SEM transverse direction fracture surface images of
pure PU fiber and the PU composite fibers containing different weight %
loading of MWCNT as illustrated in Figure 6. Bright dots and lines
showed the embedded nanotubes in the polymer matrix. Better dispersion
was found for the samples with up to 9.3 wt.% nanofiller loading, while
localized aggregation was observed for 17.7 wt.% MWCNT concentration.
A 3-D arrangement and state of nanotube dispersion in the PU matrix were
also observed via TEM. In other studies, the reinforced nanotube dispersion

Sattar et al. 17
in the nanocomposite was also analyzed from its surface morphology using
TEM and SEM.86,88 TEM images showed well-dispersed individual MWCNT
in the PU matrix.86
Figure 6. SEM images of PU nanocomposites: (a) pure PU; (b) 5.6 wt.% filler; (c) 9.3
wt.%; filler; and (d) 17.7 wt.% filler.65
The uniform dispersion, microstructure analysis and crystalline properties

of PU/MWCNT nanocomposites were studied using SEM, TEM images, and
XRD pattern.41,85 PU molecular backbone had significant polar groups, such
as –CONH– and –CH2-O–, compatible with nanotube and responsible for the
uniform nanotube dispersion in PU matrix. The fine nanostructures of as
prepared PU/MWCNT nanocomposites and the MWCNT dispersion in the
thermoplastic PU nanocomposites were also studied through SEM.8,67
Ryszkowska et al.82 analyzed carbon nanotube dispersion in PU matrix
and its surface morphology by optical microscopy, SEM, and AFM. The
nanocomposite thin film microstructure was investigated using an optical
microscope and the micro-section nanocomposite morphology was character-
ized by SEM and AFM. MWCNT dispersion in PU matrix had shown to be a
function of the mixing process sonication time. Comparing composite AFM
topographies suggested that the MWCNT dispersion during composite

preparation played a dynamic role in determining the surface morphology.

SEM has been employed to investigate morphology and to analyze the PU/
MWCNT nanocomposite fracture surface.23,87,90,98 It was observed that con-
tinuous and distributed networks had been formed in the composites with a
high nanotube loading. The quantitative fatigue results and the SEM images
certainly verified that MWCNT enhance the fatigue performance of PU sys-
tems. CNTs retard the fatigue failure by preventing large, shattering cracks
due to the interfaces provided by nanotubes.103 The nanotubes can also
bridge the cracks and reduce the plastic deformation experienced by the
matrix while their pull-out from the matrix and the separation processes at
the crack front scatters the stored strain energy that would otherwise result in
damage buildup and subsequent fatigue damage. It was observed via SEM
analysis that with in situ polymerization, MWCNTs were well-distributed in
PU matrix along with slight aggregation.84,104 Upon failure, the CNTs were
broken rather than pulled out from the matrix, demonstrating a strong inter-
facial interaction between the reinforcing filler and the matrix.
The PU/MWCNT composite microstructure containing 2 wt.% nanotubes
was investigated by FESEM and TEM.81 Figure 7 shows SEM images of
these nanocomposites. The nanotube dispersion in the polymer matrix was
clearly observed from SEM image with low magnification (Figure 7a).
Greyish areas about several hundred nanometer scale showed that a few
clusters formed with a relatively high MWCNT concentration in the PU
matrix. Besides the clusters, individual nanotubes were also clearly discerned
and uniformly dispersed in the polymer matrix. From the high magnification
SEM image (Figure 7b), it was clearly observed that the functionalized
MWCNT have a good compatibility with the matrix. In addition, it was
found that most CNTs prefer an ordered orientation compared to a
random distribution. TEM composite images showed presence of both aggre-
gates and individual nanotubes dispersed in the polymer composite
(Figure 8). Individual nanotubes were clearly seen in the low nanofiller con-
centration region and were well dispersed (Figure 8a). However, nanotube
agglomeration was observed in the relatively high reinforcing filler concen-
tration region (Figure 8b). In another study,95 the MWCNT morphology and
dispersion in a PU matrix was studied using a combination of SEM, high
resolution transmission electron microscopy (HRTEM), and wide angle X-
ray diffraction (WAXD) and revealed that nanotubes were highly dispersed in
the PU matrix. The TEM images from in situ, cross-linking and blended
polymerized PU nanocomposites were analyzed.43 More black dots and
lines in the TEM images of in situ and cross-linked polymerization methods
indicated the homogeneous dispersion of MWCNT, while the conventionally
blended composite had poor dispersion with the tube aggregates.
The enhanced dispersion for tubes in cross-link polymerized composites

Sattar et al. 19
was confirmed based on the bright spots in the topographical AFM mapping
images.
Figure 7. PU/MWCNT composite FESEM cross section images: (a) low magnification
and (b) high magnification.81
Figure 8. PU/MWCNT nanocomposite TEM images: (a) lower MWCNT concentration

region and (b) higher MWCNT concentration region.81
Mechanical properties of PU/CNT composites

Fiber reinforced composites have been widely used in many areas from auto-
motive to aerospace and military applications due to their light weight and
improved mechanical properties. Using filler as a reinforcing agent is obvi-
ously not a new idea and has been considered for years. Carbon fibers have
been known to greatly improve the polymer mechanical properties (stiffness,

strength, modulus, etc.). Recently, MWCNTs have been used as nanofiller to

reinforce the polymers because they have exceptional mechanical properties.
A carbon nanotube has very high Young’s modulus (1 TPa/145 Mpsi) and
strength (100 GPa/14.5 Mpsi) relative to other carbon fibers. Due to such
exceptional mechanical properties along with their light weight, they have
proven to be better than all conventional fiber-reinforced composites.
Mechanically enhancing different polymers with nanotubes has been dis-
cussed in many literature reviews.105–108 For any effective reinforcement,
there are mainly four system requirements:
. high aspect ratio

. good dispersion
. interfacial stress transfer
. nanofiller alignment.
The most challenging issue is to finely disperse the MWCNTs in the matrix
in order to enhance the load transfer capacity of the composite to the nano-
tube network. Adjusting parameters such as type, growth method, chemical
pre-treatment, and nanotube processing strategy have given some encoura-
ging results for preparing comparatively strong polymer nanocomposites.
From earlier results we can extract general conclusions about the dependence
of the aforementioned parameters on the mechanical behavior of PU/
MWCNT nanocomposites.
Typical stress–strain curves for unfilled PU and nanocomposite fibers con-
taining various MWCNT wt.% loadings were investigated (Figure 9).65 They
showed that the PU nanocomposites have a non-linear elastic behavior in the
low stress region and plastic deformation at higher stress. This work showed65
that the tensile modulus, tensile strength, and elongation at break depend on
the filler content. Increasing the nanotube concentration from 0.0 to
17.7 wt.% resulted in a non-monotonic trend. At 9.3 wt.% concentration,
the tensile strength was nearly 2.4 times greater than that of unfilled PU
fiber. The decrease in strength for high concentrations (17.7 wt.%) can be
ascribed to the increased frequency of localized clusters or aggregations.
Xiong et al. prepared a series of self-crosslinkable PU/MWCNT nanocompo-
sites using the sol-gel process.81 They concluded that adding a small amount
of amide-functionalized MWCNT in the samples increased the Young’s
modulus and tensile strength significantly with no loss in elongation at
break. Similar results have been reported for carbon nanotube-reinforced
PU composites.37,46,84,104

Sattar et al. 21
Figure 9. PU nanocomposite stress–strain curves versus CNTs loading.65
Wang and coworkers had synthesized PU-grafted nanotubes and made

from PU composites with different nanotube loading.8 The nanocomposite
film tensile strength was enhanced from 59 to 275% with 1–10 wt.% loading
compared to the unfilled PU. However, the elongation at break decreased
from 192 to 116%. The increased nanocomposite tensile strength might be
due to the nanotube filler reinforcing the PU matrix. Koerner reported that
incorporating 2.9 vol.% MWCNT into the thermoplastic PU increases yield
stress, stress at break, and modulus.20 These properties influenced by a strain-
induced crystallization of the soft-segments of the polymer, which led to a
complex synergism in the mechanically reinforcing PU nanocomposites. Jiang
et al. had also studied the thermoplastic PU/MWCNT nanocomposite mech-
anical properties with different nanotube content at room temperature and
120 C41 They found that increasing MWCNT content increased the Shore A
hardness and stress at 100% strain of the nanocomposites. The nanocompo-
site tear strength was substantially increased at first and then leveled off with
increasing nanotube content. The tensile strength increased quickly at the
beginning and then slight increase was observed with the increasing nanotube
content while the elongation at break tended to decline all the time with
nanotube loading. At 120 C, the thermoplastic PU hard phase started to
dissociate so that the polymer tensile strength dramatically decreased due
to losing the self-reinforcing effect.
The enhanced mechanical properties of the hyperbranched PU due to
added MWCNTs was also observed.86 Composites had shown better

mechanical properties due to the synergistic effect of the combined hard seg-
ment content and the carbon nanotube addition. Chen et al. had prepared
PU/MWCNT composites by in situ polycondensation and reported that the
tensile strength and elongation at break of the composites increased with
reinforcing agent concentrations below 1 wt.% and then decreased with con-
centrations above 1 wt.%.83 The maximum increase in tensile strength and
elongation at break were 900% and 741%, respectively, at 1 wt.% MWCNT
loading. At high nanotube content, the improvement in the mechanical prop-
erties might be limited by the composite high viscosity and resulting void
defects. Studies by Karabanova et al.91 revealed that the covalently bonded
functional groups to the MWCNT lattice in PU matrix provided better mech-
anical properties relative to those functional groups that had physically linked
to nanotube via van der Waals forces. Similar results on tensile properties
revealed that functionalized nanotubes were effective nanofillers for PU
matrix as compared to the neat nanotube and responsible for the improved
mechanical performance.88,90–93
Thermal properties of PU/CNT composites

High nanotube thermal conductivity about 3000 W/mK render them as
attractive filler to enhance thermal properties.109 The nanocomposite material
thermal behavior can be predicted by knowing the heat dissipation from their
surfaces. It was reported in various studies that introducing nanotubes in a
polymer matrix increased glass transition, melting and thermal decomposition
temperatures due to hindered chain and segmental mobility of poly-
mers.110–115 It was observed that the glass transition temperature (Tg) of
PU/amide-functionalized MWCNT elastomer composite had increased by
10 C and thermal stability was also improved relative to the unfilled PU
properties.81 In a study, DSC curves of the thermoplastic PU/MWCNT nano-
composites with different mass ratios were recorded.41 The thermoplastic PU
had two glass transition temperatures around 56 C and 54 C corresponding
to their soft and hard segments, respectively. The composite DSC curves
showed an irregular and slight Tg increase of hard segment with adding
MWCNT. However, the soft phase Tg did not change. It was also found
that the nanocomposite thermal conductivity increased with increasing
carbon nanotube volume fraction. It was also reported that the nanocompo-
site thermal conductivity was nearly three times the unfilled PU as the
MWCNT volume fraction was about 20%.41
In another study,83 the thermal properties of unfilled PU polymer and
carbon nanotube-reinforced polymer nanocomposites were measured by
DSC. The effects of different nanotube content on the glass transition were
also discussed. The DSC measurements revealed that new peaks near 54 C

Sattar et al. 23
had appeared and soft nanocomposites Tg was changed due to the microphase
separation structure and that PU hard and SS alteration occurred with nano-
tube addition. It was also noted that the Tg of SS was first decreased up to 1
wt. % nanofiller content, and above 1 wt.% nanotube addition Tg was found
to increase with nanotubes content. This can be due to confined polymer
chains between MWCNT, which would lower Tg,soft and improve the segmen-
tal dynamics of the polymer chains. Likely some other mechanisms might
transform PU microphase morphology (i.e., hard domain rotation, inter
chain slippage, fibrillation, and SS crystallization) and abundant polymer-
filler interaction. In related studies,84,92 DSC results also suggested that
adding nanotubes into PU increased the rate of crystallization, and this out-
come existed more significantly in nanocomposites prepared by in situ poly-
merization. Enhanced rate of crystallization of some polymer/nanotube
composites with nanofiller incorporation has also been reported.116,117
Several studies8,81,88,90,93,104 observed that with increased functionalized
nanofiller content over unfilled PU, the thermal stability increased.
Thermogravimetric analysis (TGA) was used to test hyperbranched PU/
MWCNT nanocomposites.86 Two-step thermal degradation was observed
for all samples due to the soft and hard PU segments. The pristine nanotubes
showed no weight loss below 600 C and the neat PU showed a large weight
loss around 435 C. The nanocomposites degradation temperature shifted to a
considerably higher temperature than the unfilled hyperbranched PU. This
effect is due to the nanoscale filler barrier properties which enhance the nano-
composite thermal stability. Jana and Cho94 compared the difference in ther-
mal stability of PU nanocomposites prepared via conventional and in situ
methods. The thermal degradation temperature for in situ nanocomposites
was found to be higher than that of the conventional nanocomposites with the
similar nanotube loading. Increased values of activation energy and half-life
period at 10% degradation were also obtained for in situ nanocomposites.
The improved thermal stability was attributed to covalent linkage between
nanotube and polymer matrix and to the fine nanofiller dispersion in the
matrix for in situ PU nanocomposites. Abdullah and coworkers69 reported
that carbon nanotube showed better thermal stability and conductivity com-
pared with carbon fiber (CF) in PU because MWCNTs have a higher thermal
conductivity.
Electrical properties of PU/CNT composites

CNTs have clearly proven their competency as attractive fillers in various
multifunctional nanocomposites. Nanotubes with their very low percolation
thresholds (<0.1 wt.%) in polymer matrices have demonstrated improved
electrical conductivity by several orders of magnitude without compromising

other polymer performance features such as their low density, optical clarity,
low melt viscosity, etc. which has prompted much activity in this field.
MWCNT filled polymers5,105,118–123 could potentially be used for:
. transparent conductive coatings

. electrostatic dissipation
. electrostatic painting
. electromagnetic interference shielding applications.
These composites showed percolation behavior where the interconnected

nanotube network resulted in a large increase in electrical conductivity.
Physical parameters of composite materials such as the electrical conductivity,
percolation threshold (c), and the critical exponent (t) have been studied to
attain conductive nanotube-reinforced polymer composites at low filler con-
centrations. In the context of percolation theory, a percolation transition is
characterized by critical exponent that describes the fractal properties of the
percolating medium at large scales and depends on the percolation model.
Electrical conductivity is directly related to critical exponent. An increased
critical exponent means that there exists a conductive nanotube network in
CNT-filled nanocomposites which allows direct macroscopic electron
transport.
Koerner et al.20 reported that the additing small amounts of nanotube to
thermoplastic PU elastomer resulted in nanocomposites with high electrical
conductivity and low electrical percolation. According to this study, max-
imum electrical conductivity value of 2000 Sm1 has been observed for PU
filled with 27 wt.% MWCNT using the solution casting technique. Yoo
et al.’s84 study revealed that the electrical conductivity of PU nanocomposites
also depends on the filler dispersion. The electrical conductivity of the com-
posite filled with the well-dispersed nanotube was found to be one order of
magnitude higher than that of the PU nanocomposites filled with the poorly
dispersed nanotubes as it was easier to form conductive path for the fairly
homogeneous dispersed nanoparticles relative to the poorly dispersed nano-
filler in composites. In another study,97 the fabrication and transport proper-
ties of PU nanocomposite microfiber-based FET s was reported. The room
temperature dc electrical conductivity measurement of these microfibers
increased with respect to the nanofiller concentration (0.1 to 2.5 wt.%) in
the nanocomposite, and were about ten orders of magnitude higher than
the pure polymer. Jiang et al.41 reported that the electrical conductivity of
the nanocomposites with about 20 vol.% nanotube was 1.1 S.m1, which was
12 orders of magnitude higher than the unfilled thermoplastic polymer. The
nanocomposite electrical conductivity increased significantly when the
MWCNT volume fraction was 5%, and continued to increase up to

Sattar et al. 25
15 vol.%. The percolation threshold value in electricity of the carbon nano-

tube-reinforced PU nanocomposites was found to be higher. It was generally
known that the percolation threshold is related to aspect ratio, orientation,
and dispersion of the conductive nanofiller. When the filler aspect ratio was
smaller and filler dispersion was not optimum, the percolation threshold value
was relatively higher. The dynamic percolation behavior of thermoplastic
PU/MWCNT composite was also studied.66 The conductivity of hot pressed
films was compared with extruded strands. A statistic percolation behavior
was observed in hot-pressed film samples with a percolation threshold as low
as 0.13 wt.%. Lima et al.98 observed that the electrical conductivity of the PU
elastomer increased from 1012 to 105 S cm1 in the 1 mass % nanotube
composite and increased up to 7 S cm1 for the amine functionalized
MWCNT-based bucky paper (50 mass % nanotube). The electrical conduct-
ivity of nanocomposite films (5 wt.% modified MWCNT) measured using the
4-probe method was in the order of 103 S cm1 which was enough to heat the
sample above 35 C, the glass transition temperature of PU.21 As the modified
MWCNT content increased, the electrical conductivity also increased, and the
effect of nanotube surface modification on the composites electrical conduct-
ivity was similarly large. The electrical conductivity of the surface-modified
carbon nanotube composites was found to be less than the unmodified
MWCNT composites having the same nanotube content. The modification
assigned the increased defects in the lattice structure of carbon–carbon bonds
formed on the nanotube surface as a result of the acid treatment. Actually, the
severe nanotube modification significantly lowered the conductivity. As a
result, both the mechanical and conducting properties were found to be
dependent on the degree of nanofilled surface modification, and the acid
treatment at 90 C gave properties desired for various applications.
Significance of PU/carbon nanofiber composites

Hughes and Chambers124 in 1889 explored another type of carbon nanoma-
terial known as carbon nanofibers (CNFs), and in the early 1950s
Radushkevich and Lukyanovich125 first exposed their hollow graphitic struc-
ture. CNFs diameter is hundreds of nanometers and length is a few tens of
microns which gives them high aspect ratios (l/d > 100). Their dimension
places them between CNTs and commercially available carbon fibers,
although the distinction between CNFs and MWCNTs is not clearly
defined.126 However, the two-dimensional (2-D) disordered morphology of
graphitic layers describes the key difference between carbon nanotube and
CNF. The nanofiber reveals stacked cone morphology defined by a finite cone
angle (a), while an ideal nanotube has a zero degrees cone angle.127 CNFs can
be synthesized by catalytic chemical vapor deposition of hydrocarbons (such

as natural gas, propane, acetylene, benzene, and ethylene) or carbon monox-

ide using metal (Fe, Ni, Co, Au) or metal alloy (Ni-Cu, Fe-Ni) catalysts at a
temperature of 500–1500 C128–134 The CNF morphology and dimensions are
highly dependent on the manufacturing and operational conditions.135 CNFs
as polymer fillers has received less research effort compared to the CNTs
because they have microstructural defects136 and therefore lower mechanical
and electrical properties than nanotubes. They also have larger diameters,
higher density, and lower aspect ratios compared to the nanotubes. Besides
all these, CNFs can be an excellent alternative for CNTs owing to their avail-
ability and relatively low price and in addition, CNFs could also be used for
research intentions in order to build knowledge that might be applicable to
the more costly nanotubes. MWCNTs were considered to be 2–3 times more
expensive than CNFs, and SWCNTs were even more expensive.137 It is
expected that as production efficiencies improve, CNFs price might drop
significantly.138 Within these contexts, CNFs have received increased atten-
tion as polymer composites reinforcements, especially for the widely applied
thermoplastic polymers in the last few decades. Due to their lower cost than
CNTs and their admirable electrical, thermal, and mechanical characteristics,
several research groups have studied them as promising fillers for thermoplas-
tic polymers.139–142
Barick and Tripathy made thermoplastic PU nanocomposites with differ-
ent weight percent CNF loadings using a melt intercalation technique by
mixing the nanofibers with the polymer matrix in an internal batch mixer
at 185 C followed by compression molding.143,144 They used commercial ali-
phatic polyether-based thermoplastic PU with about 35% HS consisting of
MDI and BD as the matrix in their work. Tsang et al.145 synthesized the
PU/CNFs composites via solution mixing using THF and 1,2-dichloroethane
as the solvents. Composite solutions of varying weight ratios were ultra-soni-
cated for 30 min in order to evenly disperse CNFs in solution. Pure PU, pure
CNF, and nanocomposite solutions were placed onto glass discs followed by
the vacuum drying for 72 h to allow the solvent to evaporate. In related
studies, the PU with CNFs and oxidized CNFs (ox-CNFs) nanocomposites
were fabricated in a low shear chaotic mixer.146,147 These studies showed that
a low mixing shear rate helped preserve nanofiber length and also the chaotic
fluid path in the mixer improved both dispersive and distributive mixing. As a
result, composites prepared in a chaotic mixer had better mechanical, ther-
mal, and electrical properties compared to materials produced in commercial
internal mixers under similar shear rates. Thermoplastic PU was synthesized
using polyether-based PPG SS and a hard segment based on MDI and chain
extender BD. The ox-CNFs were produced by the controlled oxidation of
CNFs under air atmosphere at 400–500 C. The shape-memory properties of
thermoplastic PU composites synthesized from MDI, BD, and PCL-diol and

Sattar et al. 27
CNFs were studied by Jimenez and Jana.148 These composites were synthe-
sized by bulk polymerization in a chaotic mixer. Shape-memory polymers
(SMPs) have the ability to change shape when an external stimulus, such as
heat, electrical voltage, pH, moisture change, and light, is applied.149,150 The
PU/CNFs composites prepared by melt mixing an extended chain polymer
with the filler were also reported elsewhere.151 The prepolymer was first
synthesized by reacting MDI and PCL diol at 80 C for 2.5 h under nitrogen.
Then chain extension was carried out using a stoichiometric BD at 110 C for
2 min before adding the CNF. The filler was mixed with the polymer for
another 5 min at 165 C. Lastly, composites were compression molded to pro-
duce 0.5 mm thick specimens for further testing. The CNF dispersion and
distribution in the thermoplastic PU matrix can be investigated and charac-
terized through X-ray diffraction, SEM, TEM, AFM, and optical micro-
scopes. In a study it was concluded through XRD studies that the PU
microstructure was not sufficiently affected by including CNFs as almost all
the peaks appeared at the same location in the PU/CNFs nanocompo-
sites.143,144 To assess the nanofiber dispersion and alignment in the polymer
matrix, the nanocomposites were examined via SEM and TEM. The studies
revealed the homogeneous dispersion of CNFs within the thermoplastic PU
matrix at low nanofiber loading. The uniform distribution resulted from the
strong interfacial adhesion between the nanofibers and the PU matrix.
However, small randomly distributed aggregates as well as interconnected
nanofiber conductive network structure were visualized within the matrix at
high CNF loading content.143,144 AFM and optical microscopy probed the
morphology and nanofiber dispersion embedded in the thermoplastic
PU/CNFs composites and revealed the effective nanofiber dispersion via
either covalent or ionic bond formation between CNFs and PU.143,144
Other studies145–147 have shown that oxygen-rich polar functional groups
on the surfaces of ox-CNFs had better dispersion in PU matrix compared
to the virgin CNFs.
Incorporating small amounts of CNFs in thermoplastic PU matrix could
result in enhanced mechanical properties. The tensile strength, tear strength,
and hardness of the nanocomposites were found to be appreciably improved
by adding nanofibers.143,144 However, high nanofiber loading reduced mech-
anical properties due to small clusters in the matrix. Better tensile properties
were observed for 5 and 1 wt.% loading of CNFs and ox-CNFs respectively,
compared to unfilled thermoplastic PU.146,147 At higher ox-CNF loading, the
phase mixing of soft and hard segment domains resulted in reduced tensile
properties. It was also reported that CNFs did not significantly boost tensile
modulus and decreased SS crystallinity due to adding nanofibers in the poly-
mer. Thermoplastic PU matrix has shown significantly improved thermal
properties with the added CNFs. Better PU/CNFs composite thermal

stability was observed via TGA experiment with the added nanofiber.143,144
DSC measurement revealed that Tg and crystallization melting temperature of
the PU matrix SSs was not greatly influenced by the addition of CNFs. The
thermoplastic PU nanocomposites storage and loss modulus increased with
increased CNF content. Significantly improved thermal stability was also
observed for the PU nanocomposites at low nanofiller (CNFs and ox-
CNFs) concentration.151 It was indicated that thermoplastic PU/ox-CNFs
nanocomposites show better thermal-oxidative stability, higher storage
modulus, and glass transition temperature than the unmodified CNFs.146,147
Polar groups on the ox-CNF surface promoted the fine nanofiller dispersion
in the polymer matrix and resulted in improved thermal properties.
Moreover, CNFs with their graphitic character show higher electrical con-
ductivity in nanocomposites. The electrical conductivity measurements indi-
cate that the dielectric constant and dissipation factor was more significant for
PU/CNFs composites and the electrical conductivity was enhanced with the
applied frequency as well as the high weight fraction nanofiller loading.143,144
It was inferred that higher ox-CNF content was needed versus CNF in order
to acquire electrically conductive thermoplastic PU composite materials.147
As fine dispersion and the lower ox-CNF aspect ratio did not permit fiber
overlapping, consequently failure in conductive networks formation occurred.
Hence, these improved thermoplastic PU/CNFs composite properties render
them useful in several technical applications.
Toxicity and environmental safety aspect of CNTs

While CNT toxicity is the subject of much discussion and experimentation,
this section does not aim to consider or analyze this literature in detail. The
potential risks from exposure to CNTs have been highlighted in several stu-
dies regarding the toxicology and health hazards associated with nanomater-
ials.152 Research regarding the carbon nanotube toxicity has demonstrated
that one of the most important factors leading to toxicity is impurities, espe-
cially catalyst metal contaminants, such as transitional metals Fe, Y, Ni, Mo,
and Co, introduced during preparation and purification procedures. Other
impurities, such as amorphous carbon and other carbon nanomaterials, may
also contribute to the CNT toxicity. CNT contamination by catalyst residues
is unavoidable during large-scale production. Moreover, it is impossible to
entirely remove the metal impurities without destroying the CNT structural
integrity because some metal particles are protected by graphitic shells.153
However, in cell culture and human or animal bodies, the metal impurities
may be released from the CNT structure to enhance their toxicity. A thorough
understanding of the toxicology kinetics of CNTs is necessary for risk assess-
ment and for minimizing any unwanted impact on human health and the

Sattar et al. 29
environment. With the rapid nanotechnology development, humans will be

exposed to nanoparticles through inhalation, ingestion, skin uptake, and vein
injection. Although CNTs are highly promising nanomaterials, their health
impact on humans is poorly understood. Moreover, conflicting results have
been noticed because of the different CNTs used, different evaluation meth-
ods, and even different exposure conditions. After CNTs enter the body via
inhalation or dermal or oral routes, the underlying mechanisms of CNT tox-
icity are manifested as oxidative stress, inflammatory responses, malignant
transformation, DNA damage and mutation, formation of granuloma, and
interstitial fibrosis. CNT-induced oxidative stress has been regarded as the
most acceptable mechanism. Increased intracellular reactive oxygen species
(ROS) can react with cellular macromolecules including DNA, proteins, and
lipids and disturb the homeostasis of the intracellular milieu. Because of the
low solubility, CNTs usually deposit on the cell surface without proper dis-
persion in the culture medium, which makes that the exact CNT concentra-
tion interacting with the biological system difficult to know. Therefore, it is of
profound significance to establish appropriate dosimetry for CNTs in toxicity
research. Numerous studies have documented that transition metals released
from CNTs have the potential to cause the conversion of cellular oxygen
metabolic products such as H2O2 and superoxide anions to hydroxyl radicals.
Commercial SWCNTs and MWCNTs (with high Fe, Co, Mo, and Ni con-
tent), as well as acid-treated SWCNTs with reduced metal impurities, have
been reported to cross the cell membrane.154 Moreover, respiratory exposure
to SWCNTs containing different metals could induce acute pulmonary and
cardiovascular responses. The coexistence of metal residues in SWCNTs
aggravated the adverse effects. Inflammation, oxidative stress, and cell
damage in the bronco alveolar lavage fluid were increased significantly 24 h
post exposures to SWCNTs. The major controls/precautions suggested for
the environmental safety aspects and handling of CNTs are as follow:
Inhalation controls include

. Negative pressure work area
. Fume cupboard
. Exhaust air ventilation to external environment
. Half face respirator reusable or disposable
. Clean-up and maintenance of the work place
Dermal Controls include
. Nitrile gloves—change regularly
. Lab coat
. Close fitting safety glasses
Environmental Controls such as
. Bunds and drain covers readily accessible

. Emergency clean-up and appropriately sized spill kit and containment

equipment readily available
Conclusion
In this article, we have reviewed the fabrication, morphology, and other impera-
tive properties of carbon nanotube-reinforced PU composites. PU/MWCNT
composites have been fabricated by melt blending, solution mixing, in situ
polymerization and various other methodologies. Homogeneous dispersion
of the CNTs in the PU matrix has been the key factor to enhance the composite
properties. The homogeneous dispersion of the reinforcing agent in polymer
matrix can be achieved through physical/chemical functionalization of nano-
tube lattice. Introduction of the nanotube in the PU matrix can slightly affect
the microphase separation of composites due to interaction of the functional
groups present on side walls of the nanotube with either the hard or soft poly-
mer segment. The PU composite mechanical, thermal, and electrical properties
of the thermoplastic can considerably increase with adding a small amount of
functionalized nanotube. Carbon nanotube-reinforced thermoplastic compos-
ites exhibited significantly increased thermal and mechanical stability plus elec-
trical conductivity rendering them multifunctional high performance materials.
Preparation and properties of another important carbon nanomaterial known
as CNFs and their reinforced PU composites have also been reviewed in this
article. Furthermore, the researchers must be aware of the potential risks and
deterrence from exposure to carbon nanomaterials.
Funding
This research received no specific grant from any funding agency in the public, com-
mercial, or not-for-profit sectors.
Conflict of interest
None declared.
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Biographies
Rabia Sattar obtained her MPhil from Quaid-i-Azam University, Islamabad,
Pakistan. She is currently a PhD student in National Centre for Physics,
Quaid-i-Azam University, Islamabad. Her research interests include the prep-
aration and properties of polyurethane-based materials.
Ayesha Kausar is an assistant professor at the National Centre for Physics,

Quaid-i-Azam University, Islamabad, Pakistan. She obtained her PhD from

Quaid-i-Azam University, Islamabad/KAIST (Korea Advanced Institute of

Science & Technology), Graduate School of EEWS, Daejeon, Republic of
Korea. Her research interests include synthesis, characterization and struc-
ture–property relationship of new types of polymeric materials; synthesis of
nanomaterials including organic–inorganic nanocomposites/hybrid materials;
polymeric blends via incorporation of nanoparticles into thin polymer films;
exploration of practical and potential prospects of the novel synthesized
materials (new polymers and nanomaterials) counting morphological, mech-
anical, thermal, electrical, conducting, etc.; flame retardant materials; proton
conducting fuel cell membranes; nanocomposites for polymer Li-ion battery
electrodes; composites based on electrospun nanofibers; production of vari-
ous types of polymeric nanoparticles and their composites for solar cells;
polymer/carbon nanotube/nanoparticle composites for water treatment;
potential of polymer/graphite nanocomposites; polymer/graphene hybrids;
polymer/fullerene nanomaterials; fabrication of epoxy-based nanocomposite
for various applications; radar absorbing materials; aerospace relevance, and
so on.
Muhammad Siddiq is presently the head of physical chemistry department in

Quaid-i-Azam University, Islamabad, Pakistan. He obtained his PhD poly-
mer chemistry from The Chinese University of Hong Kong. His research
expertise is in the synthesis and characterization of linear/block copolymers
and hybrid polymeric materials.

2014 Advances in

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Journal of Plastic Film and

Advances in thermoplastic polyurethane composites reinforced with carbon

The online version of this article can be found at:

Email Alerts: http://jpf.sagepub.com/cgi/alerts

>> OnlineFirst Version of Record - Jul 7, 2014

OnlineFirst Version of Record - May 20, 2014

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reinforced with carbon

Rabia Sattar1,2, Ayesha Kausar1 and

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Table 1 summarizes the CNT unique mechanical, electrical, magnetic,

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matrix materials which can be used in some particular applications such as

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Table 1. Theoretical and experimental properties of CNT compared with graphite.12

Property CNT Graphite

Specific gravity 0.8 g/cm3 for SWCNT; 2.26 g/cm3

Table 2. Advantages and disadvantages of various nanotube functionalization methods.17

Chemical Side wall Hybridization of C ˇ  S ˇ

Physical Polymer Vander Waals force,  ˇ V 

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Isocyanate group Hydroxyl group Urethane linkage

Scheme 1. Classical urethane linkage reaction.

Polyurethane/carbon nanotube (PU/CNT) composites are more functional

. nanoﬁller (carbon nanotube)

All of these components can be varied in ratio, chemical composition, and

Fabrication of PU/CNT composites

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HNO3 SOCl2 EDA

Figure 2. Chemical routes for functionalization of MWCNT and preparation of

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MWCNT inserted in hard segment

Chen et al. also prepared PU/MWCNT nanocomposites by an in situ

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encapsulation of MWCNT by PU via condensation polymerization of MDI

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The non-planar structure in the hard PU segments enhances the interaction

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100 oC, 1hr

Figure 5. Synthetic routes for the fabrication of PU/MWCNT nanocomposites.

Broadly speaking, in situ polymerization method involves the polymeriza-

Other methodologies employed

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approximately 50 mass % nanotubes. To fabricate PU/MWCNT nanocom-

Morphology and structure of PU/CNT composites

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The uniform dispersion, microstructure analysis and crystalline properties

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preparation played a dynamic role in determining the surface morphology.

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Figure 8. PU/MWCNT nanocomposite TEM images: (a) lower MWCNT concentration

Mechanical properties of PU/CNT composites

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strength, modulus, etc.). Recently, MWCNTs have been used as nanoﬁller to

. high aspect ratio

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Figure 9. PU nanocomposite stress–strain curves versus CNTs loading.65

Wang and coworkers had synthesized PU-grafted nanotubes and made

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Chemical Side wall Hybridization of C ˇ S ˇ

Physical Polymer Vander Waals force, ˇ V