Multi-scale Hybrid Composites-Based Carbon

Nanotubes

Yongkun Wang, Zhiwei Xu, Li Chen, Yanan Jiao, Xiaoqing Wu

Key Laboratory of Advanced Braided Composites, Ministry of Education, Tianjin Polytechnic University,
Tianjin 300160, China

Since the carbon nanotubes (CNTs) have been discov- polymer composites, which present tremendous strength-
ered, there has been a marked increase in the scientific ening effect for the composites [16–22]. Later, a number
literature dealing with multi-scale composites. The of research groups demonstrated that the tensile, shear,
multi-scale hybrid composites with CNTs could endow
the composites with some superior mechanical proper- flexural, fracture toughness, and thermal properties of
ties, such as improving the tensile performance, mod- polymer composites could be significantly improved,
est increasing compressive and flexural properties, and which contained loading CNTs between 0.1 and 5 wt%
significantly enhancing interlaminar, interfacial and [23–28].
fracture strength. In addition, composites with CNTs Because there is a much strong interfacial interaction,
can also develop the functional properties. A small
quantity of CNTs can significantly increase the electrical especially in the surface functionalized CNT/polymer
properties of composites and lower the coefficient of composite interphase, some investigations have been done
thermal expansion of composites. The purpose of this recently on the design and preparation of the CNT/fiber
work is to review the available literature in mechanical hybrid composites by growing CNTs on fibers [29–32].
and functional properties of multi-scale hybrid compo- The growth of CNTs offers potential for selective
sites manufactured using CNTs. POLYM. COMPOS.,
32:159–167, 2011. ª 2010 Society of Plastics Engineers reinforcement, improves through-thickness properties of
polymer composites or is used to stiffen the fiber/matrix
interface [29, 33]. The CNTs in the multi-scale hybrid
composites can not only grow directly on the fiber (see
INTRODUCTION Fig. 1) or fabric surface (see Fig. 2), but also be dispersed
Since the discovery of carbon nanotubes (CNTs) in in matrix. The CNTs in polymers hold a potential to
1991 by Iijima, CNTs have been used extensively by improve the mechanical, thermal and electrical properties
researchers in various fields such as nano-electronic com- in the host materials [19, 35]. It has been demonstrated
ponents, catalyst, electrode materials, hydrogen storage that adding only 1wt% of CNTs to matrix material, the
materials, and composites [1–9]. And new structural com- stiffness of the resulting composite can increase as high as
posite concepts harnessing the attractive properties of 36–42% and the tensile strength can raise 25% [36]. And
CNTs are being intensely researched around the world the presence of CNTs in the matrix may alleviate many
[10–14]. In recent years, CNTs have been the excellent drawbacks of conventional fiber composites, especially lon-
candidates for a new generation of high-strength, high- gitudinal compression and interlaminar properties [37–39].
stiffness materials. And CNTs have been shown to have
potential applications in composites due to their remark- PREPARATION OF MULTI-SCALE HYBRID
able mechanical, thermal, and electrical properties, and COMPOSITES
because of their high aspect rations and low densities
[15]. Therefore, there have been many attempts to use Because of high performance of CNTs, a lot of investi-
CNTs in reinforcement of composite materials for over- gations have been done recently on design and prepara-
coming the performance limits of conventional materials. tion of the CNT/fiber hybrid composites. And there are
However, most efforts in this area have dealt with CNT/ many methods to prepare the multi-scale hybrid compo-
sites, and several methods to fabricate the composite of
them have been developed, e.g., solution casting [40–43],
Correspondence to: L. Chen; e-mail: [email protected] melt-mixing and in situ process through polymerization of
Contract grant sponsor: Tianjin Natural Science Foundation; contract
monomers with the presence of the CNTs [37, 44, 45].
grant numbers: 08JCZDJC24400, 10JCYBJC02300.
DOI 10.1002/pc.21035
But in this study, four kinds of commonly used methods
Published online in Wiley Online Library (wileyonlinelibrary.com). are mainly introduced. Figure 3 shows the architectures of
V
C 2010 Society of Plastics Engineers CNT-carbon fiber hybrid composites. Figure 4 exhibits a

POLYMER COMPOSITES—-2011
 FIG. 1. SEM micrographs of carbon fibers (a) before and (b) after CNT growth [33].

schematic of the experimental set-up for the closed-mould mat scraped from nickel foil substrate. And as shown in
vacuum-assisted resin transfer moulding (VARTM) Fig. 5(b), the mat comprises of high purity nanotubes
process [46]. with different diameters.
Although the CVD process is an efficient technique for
the growth of CNTs on a variety of surfaces, the use of
Chemical Vapor Deposition(CVD) high temperatures and predeposited catalysts, taken to-
gether with the difficulties in processing large panels,
At present, some research groups are working on imposes serious limitations on the practical application of
growth of CNTs by chemical vapor deposition (CVD) this technique for the fabrication of CNT-reinforced struc-
directly onto a carbon fiber surface [29, 47]. And the tural composites [50]. CVD can produce well-aligned sin-
CVD route has been established as the most effective and gle wall carbon nanotube (SWNTs) or MWNTs but can
practical route to synthesize CNTs [36]. Matsuda et al. also yield entangled CNTs [51]. And many difficulties
[48] used direct current (DC) plasma CVD method on the need to be solved, such as homogeneous dispersion of
submicron-sized dot-catalyst array substrate which was CNTs in polymeric matrix and strong interfacial interac-
fabricated by electron beam lithography for the purpose tion so as to affect load transfer from polymeric matrix to
of developing nano-sized electron field emitters. Experi- CNTs [37]. Moreover, the properties of pristine fiber are
mental results showed that multi-walled carbon nanotubes seriously injured because of the catalyst and prophetic gas
(MWNTs) grown from Ni-C composite nanoclusters have environment.
become narrower than those from Ni evaporated thin film.
Their diameters were reduced from 50–100 nm to 5 nm
or less. Guo et al. [49] used CVD method to synthesize
Chemical Grafting
hybrid composites. Ni foil with thickness of 0.2 mm was
used as a catalyst for CNT growth. The Ni foil was He et al. [30] presented a new chemical method used
placed in a thermal CVD system using a gas mixture of for preparation of the CNT/carbon fiber multi-scale rein-
acetylene and hydrogen. The as-prepared CNTs were forcement, which combines micrometric fibers with nano-
processed to field emission emitter by screen-printing metric CNTs. MWNTs functionalized with hexamethylene
method. Figure 5a shows a photograph of typical CNTs diamine at the end caps were grafted onto the surfaces of
carbon fibers treated by acyl chloride using the fiber sur-
face grafting technique [30, 52–54]. Laachachi et al. [47]

FIG. 2. Illustration of the hybrid composite (a) Schematic illustration

of the architecture composed of a cloth containing fiber tows, covered
by CNTs, in a polymer matrix. The two different plies are shown in two
different colors; (b) Closer view of the interface cross-section between
the two composite plies [34]. FIG. 3. CNT-carbon hybrid composite architectures [11].

160 POLYMER COMPOSITES—-2011 DOI 10.1002/pc

 processes (see Fig. 7). He added a small amount of
SWNTs in nanocomposite to improve Z-axis properties,
particularly, interlaminar shear strength. The glass fiber
fabric was coated by CNTs and then was processed into
vinyl ester composite laminates. Figure 8 shows the glass
fiber coated with CNT-epoxy nanocomposite.
The advantage of this coating method is that it could
be implemented in a straightforward manner by conven-
tional composite processing like resin transfer molding.
The method can also be easily extended to other polymer
based composite systems. However, it is very difficult to
control the homogeneous dispersion of the CNTs by using
this method.

FIG. 4. Schematic view of the preparation of nanotube/fiber/epoxy

composites using VARTM [46].

Electrophoresis
developed a simple method for grafting CNTs onto a car- Electrophoresis is a simple and versatile technique that
bon fiber surface. CNTs and carbon fiber underwent an can be readily automated and utilized for industrial appli-
oxidation treatment. Oxidation generated oxygen, like car- cation. On the basis of the ability of CNTs to respond to
boxyl, carbonyl, or hydroxyl groups on nanotube and car- an electric field, Bekyarova et al. [50] developed the
bon fiber surface. Functionalized CNTs were dispersed in method for the deposition of CNTs on the surface of car-
a solvent and deposited on carbon fibers. The bonds bon fibers by using of electrophoresis. It was found that
between CNTs and carbon fibers were operated by esteri- CNTs were deposited uniformly on the surface of a car-
fication or anhydridation of the chemical surface groups bon fiber from aqueous nanotube dispersions upon apply-
(see Fig. 6). ing a DC potential between the carbon fibers and the
The grafted MWNTs stuck to the carbon fiber surface counter electrode. Because of their negative charge, CNTs
at different angles and were uniformly distributed along migrate toward the positive carbon fiber electrode and are
the outer edges of the grooves in the fiber surface. The subsequently deposited on the fiber surface (see Fig. 9).
grafting increased the weight of the carbon fiber by 1.2%, The negative charge is attributed to the carboxylic acid
and it was implied that a considerable amount of MWNTs groups introduced into the nanotubes during the nitric
were grafted onto carbon fiber surface [30]. But this acid treatment [57], and the adsorption of hydroxyl anions
method may damage the strength of the fiber during the from the dispersion may also contribute to the net nega-
fiber surface functionalization. tive charge [58]. Figure 10 shows the images of carbon
fibers with CNTs deposited by electrophoresis.
By using this method, the manufactured multi-scale
Surface Coating
hybrid composites reinforced with CNT-coated carbon
Zhu et al. [55] developed a coating method for distrib- fabric showed 30% enhancement of the interlaminar
uting a very small amount of CNTs on the woven fiber to shear strength, and importantly, they have preserved in-
facilitate the fabrication of large scale nanocomposites plane mechanical properties. However, this method
compatible with the traditional composite manufacturing required relatively harsh conditions and the CNTs can get

FIG. 5. (a) Photograph of CNTs mat by CVD on nickel foil, (b) SEM image of as-prepared CNTs by CVD on nickel foil [49].

DOI 10.1002/pc POLYMER COMPOSITES—-2011 161

 FIG. 6. Chemical bonding of fonctionnalized nanotubes or fibers by subsequent esterification, anhydridation,
or amidization of the carboxyl groups formed during oxidation treatment [47].

a homogeneous dispersion on the fiber/fabric surface but tests on these three samples showed that for pristine
can not disperse homogeneously in the inner-fabric. MWNT-reinforced composites, both tensile modulus and
shear modulus were improved by about 8%, but the ten-
sile strength and shear strength decreased. However, all
MECHANICAL PERFORMANCE OF MULTI-SCALE
the properties of multi-scale composites using functional-
HYBRID COMPOSITES
ized MWNTs showed significant enhancement. Modulus
Adding the CNTs in the composite can significantly along fiber orientation was enhanced by 27.2%, while ten-
improve the composite mechanical properties and the sile strength was enhanced by 15.9%. Siddiqui et al. [56]
improvement in mechanical properties can be mainly showed that the 0.3 wt% CNT-epoxy nanocomposite coat-
attributed to the following characteristics of this new type ing gave rise to a significant increase in tensile strength
of interface structure. First, stress can be efficiently trans- of the single fiber for all gauge lengths, which was better
ferred from the matrix to the reinforcements. Second, the than the neat epoxy coating. The results on glass fiber
matrix surrounding the reinforcement particles is rein- roving also indicated a clear beneficial effect of compos-
forced by CNTs. Finally, CNTs may promote formation ite impregnation on tensile strength.
of microcracks in the interface [15]. Figure 11 shows me- However, adding the CNTs in the carbon fiber/epoxy
chanical property improvement of carbon fiber reinforced composites can’t improve the tensile properties signifi-
plastic (CFRP) by incorporation of CNTs. cantly. Bekyarova et al. [50] had carried out some tensile
tests on the carbon fiber/epoxy and multi-scale MWNT/
carbon fiber/epoxy composites and found that the tensile
Tensile Strength and Modulus strength and tensile modulus of the composites prepared
The tensile properties are some of the most important with MWNT deposited carbon fiber are similar to those
indicators to reflect the composite mechanical properties. of the composites made with carbon fiber alone. Kim
In the composites, different reinforcement may cause dif- et al. [61] showed that the longitudinal tensile modulus
ferent tensile properties. Adding the CNTs in the glass and transverse tensile modulus of epoxy/carbon fiber com-
fiber/epoxy composites can improve the tensile properties. posite were 221.3 and 13.08 GPa, however, after adding
Qiu et al. [60] fabricated three different composite the CNT in the epoxy/carbon fiber composite the longitu-
samples based upon conventional epoxy/glass-fiber com- dinal tensile modulus and transverse tensile modulus were
posites: (1) 1 wt% functionalized MWNT-reinforced
multi-scale composites; (2) 1 wt% pristine MWNT-rein-
forced multi-scale composites; (3) conventional epoxy/
glass fiber composites without adding MWNT. The tensile

FIG. 7. Illustration of the overcoating method for distributing nano- FIG. 8. Schematic illustration of a fiber with CNT-epoxy nanocompo-
tubes onto woven fiber [55]. site coating [56].

162 POLYMER COMPOSITES—-2011 DOI 10.1002/pc

 pressive properties. Yokozeki et al. [66] showed that in
composite laminates, the compressive strength of compo-
sites with 5% CNTs increased to 501 MPa, and the com-
pressive strength of composites with 10% CNTs is 539
MPa.

Flexural Properties
Although the conventional composites have been
widely used in many industries, the flexural properties
always blocked its development. However, the conven-
tional composites with CNTs can make up for this
deflects. Song [68] tested the flexuous properties of ara-
mid fiber/epoxy composite and CNT/aramid fiber/epoxy
composite. It was found that the flexuous properties of
the aramid/epoxy composites with CNTs were slightly
improved. Zhou et al. [69] showed that the carbon fabric/
epoxy composites with 0.3% CNTs can slightly improve
FIG. 9. Deposition of carbon nanotubes on a carbon fiber surface by the composites flexuous properties. Yokozeki et al. [66]
electrophoresis [50]. added the cup-stacked carbon nanotubes (CSCNTs) in the
CFRP laminates composites, and he found that adding 5
wt% CSCNTs in the composites can improve the compo-
221.4 and14.15 GPa, respectively. It is indicated that the
sites flexural properties, and the flexural strength is 912
CNTs can’t significantly improve the composites tensile
MPa. At the same time, adding the CNTs in the matrix
properties.
can also improve the properties of the matrix. When 0.3
wt% reactive CNTs were added in the matrix, the flexural
strength, modulus and breaking strain of the epoxy sys-
Compressive Properties
tems increased by 32, 9, and 70%, respectively [70]. Yan
There are a large volume of works concentrating on [71] tested five specimens of glass fiber reinforced epoxy
buckling of CNTs by themselves, but there have been rel- composites, and found that glass fiber/epoxy composites
atively few studies on the compressive behavior of CNTs with or without SWNTs had no obvious change on the
when embedded in composites. However, adding some flexural properties of composites. However, the SWNTs/
CNTs in the composites affects not only the tensile prop- glass fiber/epoxy composites containing SWNTs treated
erties but also the compressive properties [62–67]. Cho by Volan or by both Volan and BYK-9076, the flexural
and Daniel [65] showed that adding 0.5 wt and 1.0 wt% strength of composite improved dramatically by 2.64 or
CNTs in carbon fiber/epoxy composites, the in-plane 16.11%. The reasons of these results can be separated
compressive strength increased by 39 and 26%, respec- into two factors, one is that the dispersing agents can
tively. Zhu et al. [55] indicated that in glass fiber rein- improve the dispersion of SWNTs and the other one is
forced vinyl ester composites, the compressive strength is that the Volan can improve the interface property between
27 MPa. The addition of 0.1 wt% SWNTs and 0.2% SWNTs or glass fiber and epoxy resin. Kepple et al. [8]
SWNTs in the composites, the compressive strength is found that after woven carbon fiber laminates were func-
about 39 and 33 MPa, respectively. So, it is proper to add tionalized in situ with CNTs, the flexural modulus of car-
right amount of CNTs in the composites to improve com- bon/epoxy composites actually increased by a slight 5%

FIG. 10. SEM images of carbon fibers with (a) SWNTs and (b,c) MWNTs deposited by electrophoresis [50].

DOI 10.1002/pc POLYMER COMPOSITES—-2011 163

due to the addition of the CNT on the surface of the car-
bon fiber. The flexural properties of different composites
are shown in Table 1.

Interlaminar Shear Strength and Interface Adhesion

The composite interlaminar adhesion is one of the
most important mechanical properties. So, there are con-
siderable amount of research groups devoting to improve
it. The interlaminar strength of the conventional compo-
sites is very weak; however, adding some CNTs in the
composites can remove this defect. On the basis of the FIG. 11. Scenario of mechanical properties improvement of CFRP by
concept that inter-laminar carbon-nanotube forests would incorporation of CNTs [59].
provide enhanced multifunctional properties along the
thickness direction [72], the hybrid laminate showed an tion tests and demonstrated that it was possible, in the
improvement of 69% with respect to the unreinforced best case, to obtain an improvement of over 4.75 times in
laminate [69]. Zhu et al. [55] showed that interlaminar the interfacial shear strength. In similar tests, Thostenson
shear strength is one of the most interesting Z-axis prop- et al. [29] found an improvement of interfacial load trans-
erties for composite laminates, and made the conclusion fer, which was attributed to local stiffening of the poly-
that adding 0.1% SWNTs in the glass fiber reinforced mer matrix near the interface. Bekyarova et al. [50]
vinyl ester composites can improve the interlaminar prop- showed that the addition of MWNTs played a significant
erties significantly. For the fabricated 3D composites with role in the reinforcement of the polymer matrix. The
MWNT forests (Fig. 12), remarkable improvement was introduction of 0.25% of MWNTs in the carbon fiber/
found in the interlaminar fracture toughness, hardness, epoxy composites resulted in an enhancement of the
delamination resistance and in-plane mechanical proper- interlaminar shear strength by 27%. This finding was con-
ties. The flexural modulus, strength, and toughness of 3D sistent with the earlier report of enhanced fiber/matrix
composites were increased by 5, 140, and 424%, respec- interfacial bonding through selective reinforcement with
tively [73]. nanotubes [29]. Frankland predicted that a functionaliza-
Because the mechanical properties of composites tion of CNTs of less than 1% would improve the interac-
depend on not only the properties of the constituent mate- tion between CNTs and the polymer without significant
rials but also the nature of the interfacial bond and the decrease in their strength [79].
mechanism of load transfer, the topic of the fiber/matrix
interface, or ‘‘interphase’’ has been the subject of consid-
erable research [74]. And efforts have been made to
Fracture Toughness
improve the interfacial adhesion using various methods,
by either enhancing the chemical activity of the fiber sur- The dispersion of CSCNT resulted in the enhancement
face or increasing the surface area [75–78]. For carbon of 908 stiffness and strength and the decrease of residual
fibers, a number of surface treatments have been used to thermal strain in composite laminates. Fracture toughness
improve adhesion at the fiber/matrix interface, and it was associated with the matrix crack onset was evaluated
found that the presence of CNTs at the fiber/matrix inter- using the analytical models and experimental results, and
face can improve the interfacial shear strength of the about 40% increase of the fracture toughness in CFRP
composites [29]. Downs and Baker [77] investigated the filled with CSCNT was indicated [80]. Godara et al. [50]
interfacial properties of the composites with carbon nano- demonstrated the influence of CNTs on the fracture
fiber-grafted carbon fibers through single fiber fragmenta- toughness of the UD composite laminates and showed

TABLE 1. The flexural properties of different composites.

Composite samples Flexural modulus (GPa) Flexural strength (MPa) References

Carbon fiber/epoxy 39.5 6 2.1 626.4 6 78.2 [61]

Carbon fiber/CNT/epoxy 44.1 6 1.6 740.6 6 73.2
Carbon fabric/epoxy 63.0 (6 5.5%) 608 (6 4.7%) [69]
Carbon fabric/0.3 wt%CNT/epoxy 66.1 (6 5.6%) 626 (6 5.7%)
Aramid fiber/epoxy 31.2 1,450 [68]
Aramid fiber/CNT/epoxy 31.8 1,470
CFRP laminates 53.0 875 [66]
CFRP laminates with 5%CSCNT 55.1 912
CFRP laminates with 10%CSCNT 55.8 888

164 POLYMER COMPOSITES—-2011 DOI 10.1002/pc

 Electrical Conductivity
Composite electrical properties have received much
attention due to their potential applications in some spe-
cial environment. The addition of CNTs can improve the
electrical properties of the composites. Bekyarova et al.
[50] measured the in-plane and out-of-plane electrical
conductivities by the four-probe configuration for two sets
of composites prepared with SWNT/carbon fabric and
MWNT/carbon fiber reinforced epoxy. The MWNT/car-
bon fiber/epoxy composites showed an enhancement of
the out-of-plane electrical conductivity of 30% as com-
pared with that of the reference carbon fiber composites.
Gojny et al. [89] showed that the GFRP containing 0.3
wt% amino-functionalized double-wall carbon nanotubes
exhibited an anisotropic electrical conductivity, whereas
the conductivity in plane was one order of magnitude
higher than out of plane. Wichmann et al. [90] illustrated
FIG. 12. Schematic diagram of hierarchical MWNTs reinforced 3D that only the glass-fiber-reinforced composites containing
composite [73].
0.3 wt% unfunctionalised double-wall carbon nanotubes
and MWNTs exceeded the percolation threshold. A con-
that even at relatively low CNT concentration (0.5 wt%) ductivity of up to 1.6 3 1022 S
m21 was achieved with
in the epoxy matrix (0.2–0.25 wt% in the final three the laminate containing 0.3 wt% MWNTs. And the con-
phase composite) there was a significant improvement in ductivity of the double-wall carbon nanotubes modified
the fracture toughness. He et al. [81] added 1.5 wt% composite was measured to 3 3 1023 S
m21.
CNTs and 0.3 wt% Ni in the CNT(Ni)-Al2O3 composite, Ounaies et al. [91] tested DC volume and surface con-
and found that the toughness of the composites increased ductivities and alternating current (AC) conductivity of the
67% over pure alumina, and the introduction of 1.5 wt% composites, respectively. The DC results showed that a
CNTs into alumina matrix improved the hardness from sharp increase of the conductivity value was observed
17.1 to 20.1 GPa. He characterized that the improvement between 0.02 and 0.1 vol%, where the conductivity changed
of the fracture toughness and hardness was attributed to from 3 3 10217 to 1.6 3 1028 S
cm21. At 0.5 vol%, the
the network structure of CNT(Ni)-Al2O3, which ensured conductivity was 3 3 1027 S
cm21. The AC test confirms
homogenously dispersed CNTs in the matrix and tight the percolation behavior. At concentration levels below the
interfacial bonding between CNTs and alumina matrix, percolation threshold, a strong frequency dependence of the
and thus led to a good stress transfer between the nano- conductivity was observed, but as the concentration ratio
tube and alumina matrix. Kepple et al. [8] found that the increased, the frequency dependence disappeared. At 0 and
CNTs as-grown on the woven carbon fiber were shown to 0.02 vol%, the specific admittance increased linearly with
substantially improve the fracture toughness of the cured the frequency in a logarithmic scale, exhibiting a typical ca-
composite on the order of 50%. pacitor behavior. At loadings in excess of 0.1 vol%, the
Fiedler et al. [82] reviewed the fracture properties of composites exhibited a conductive behavior. This result is
the CNT/epoxy composites with CNT volume contents in excellent agreement with the findings from the DC con-
below 1%. It was shown that the fracture toughness KIC ductivity measurements, and further confirms that the criti-
can be increased by 45% by adding only 0.3% of amino- cal volume fraction is between 0.02 and 0.1 vol%.
functionalized double-walled carbon nanotubes. This illus-
trated the huge potential of CNTs for improving the frac- Coefficient of Thermal Expansion
ture performance of polymer composites. Therefore, it is
The thermal properties of the composites are difficult
possible to add CNTs into the matrix of a laminated com-
to control, however, their thermal properties can be
posite to improve its poor interlaminar properties [73].
improved and become easy to control by adding some
CNTs. CNTs themselves have a negative coefficient of
thermal expansion [92], so, adding the CNTs in the com-
posites will reduce the coefficient of thermal expansion
FUNCTIONAL PROPERTIES OF MULTI-SCALE
(CTE) of composites. Godara [80] tested the CTE of car-
HYBRID COMPOSITES
bon fiber/epoxy composites with various CNTs, and found
Composites with CNTs can not only offer extraordi- that the MWNTs do not seem to be effective probably
nary theoretical mechanical properties [83–88], but also because of their low level of interaction or any physical/
offer functional properties such as electrical conductivity chemical affinity with the matrix and higher possibility of
and thermal properties. undergoing the agglomeration. For the composites with

DOI 10.1002/pc POLYMER COMPOSITES—-2011 165

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