Materials and Design 92 (2016) 120–128

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Three-dimensional carbon/carbon composites with vertically aligned

carbon nanotubes: Providing direct and indirect reinforcements to the
pyrocarbon matrix
Lei Feng a, Kezhi Li a,⁎, Zhigang Zhao a, Hejun Li a, Leilei Zhang a, Jinhua Lu a, Qiang Song b,⁎
a
State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi'an 710072, China
b
Center for Nano Energy Materials, Northwestern Polytechnical University, Xi'an 710072, China

a r t i c l e i n f o a b s t r a c t

Article history: Vertically aligned carbon nanotubes (CNTs) were grown in situ on the surface of carbon cloths coated by a thin
Received 27 September 2015 SiO2 layer and then the hybrid cloths were stacked and densified by chemical vapor infiltration to obtain
Received in revised form 30 November 2015 three-dimensional (3D) C/C composites. Effects of the length (5.2–21.8 μm) of aligned CNTs on the microstruc-
Accepted 8 December 2015
tures and mechanical properties of the composites were investigated. Results showed that aligned CNTs not
Available online 9 December 2015
only directly stiffened the matrix within the reach of CNTs, but also gave indirect reinforcement to the matrix
Keywords:
out of the reach of CNTs by inducing the formation of small pyrocarbon grains that interlocked with each
Carbon nanotubes other. Both the direct and indirect reinforcements on the matrix could be dramatically increased by extending
Carbon/carbon composites CNT length. Therefore, 3D C/C composites with 21.8 μm-long CNTs showed the most notably improvements of
Reinforcements matrix-dominated mechanical properties: 63% and 275% improvements in out-of-plane and in-plane compres-
Mechanical properties sive strength; meanwhile, 13% improvements in fiber-dominated flexural strength. Compared with z-pinning
and stitching, the use of vertically aligned CNTs would pave a meaningful way for effectively improving the global
mechanical performance of woven-fabric C/C composites.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Carbon fiber (CF)-reinforced carbon (C/C) composites possess wide
structural applications in aeronautics and astronautics [1,2]. Although
excellent in-plane tensile properties have been achieved using various
configurations of fiber preforms, the relatively weak compression and
interlaminar properties of these composites remain major issues,
which are mainly dependent on the low-strength brittle carbon matrix.
Carbon nanotubes (CNTs) are regarded as the ideal secondary rein-
forcement, due to their excellent mechanical properties [3]. The use of
nano-level CNTs in the micro-level CF preforms can provide the oppor-
tunity to improve the bonding state of fiber/matrix (F/M) interface and
also to modify the microstructure of pyrocarbon (PyC) and then in-
crease the structural continuity of C/C composites [4,5], improving
their through-thickness mechanical properties. So far, CNTs with differ-
ent morphologies, including fluff-like CNTs, curved CNTs, CNT thin-
coating, randomly-oriented CNTs, and so on, have been applied to rein-
force the C/C composites [6–9]. Although some improvements in
matrix-dominated mechanical strengths are achieved, the increments
are always limited (30–115%), due to the poor dispersion morphologies
⁎ Corresponding authors.
E-mail addresses: likezhi@nwpu.edu.cn (K. Li), songqiang511@nwpu.edu.cn (Q. Song).
of CNTs and the resulting modest reinforcements. Recently, over 200%
improvements in out-of-plane compressive strength and interlaminar
shear strength are obtained for short CF felt-based C/C composites
after grafting radially straight CNTs, the key result of which was that
the radially straight CNTs provide substantial reinforcement to PyC
[10]. Undoubtedly, the significance of these results consists in the fact
that it is imperative to tailor the CNT morphology for maximizing the
performance of CNT doped C/C composites. However, the tailoring
CNT morphology should take the types and structures of CF preforms
into full consideration. As for two-dimensional (2D) carbon cloth-
based preforms, the weakest link in mechanical performance is the
gap between adjacent fiber plies due to the large width ranging from
10 μm to over 20 μm, and the macroscale surface that can be up to sev-
eral square meters dependent on the size of C/C specimen. To improve
the through-thickness mechanical properties of the composites, it is
necessary to provide efficient reinforcements to the interlaminar PyC
matrix. For that, the use of curved CNTs, CNT coating, or radially straight
CNTs would be undesirable, due to the undesirable morphologies such
as short length, curved body, low dispersion density and random
orientation.
Aligned CNTs with micron length prepared by catalytic chemical
vapor deposition (CVD) can be used as continuous reinforcements to
provide several times more enhancements to polymer composites
than randomly distributed CNTs [11,12]. Besides, due to the unique

http://dx.doi.org/10.1016/j.matdes.2015.12.036
0264-1275/© 2015 Elsevier Ltd. All rights reserved.
 L. Feng et al. / Materials and Design 92 (2016) 120–128
dispersion morphology, aligned CNTs can also be used as matched rein-
forcements in woven-fabric composites for great improvements of in-
terlaminar mechanical properties [13,14]. Unfortunately, the
carbonized photoresist surface of CFs cannot support the growth of
aligned CNTs due to the poor wettability of fibers within catalyst solu-
tions (Fe, Ni and Co) [15]. Moreover, the high temperature and reactive
conditions used for CNT growth can introduce defects on CF surface,
which can significantly degrade in-plane mechanical properties of C/C
composites.
Here, a thin inorganic SiO2 interface layer was pre-coated on CF sur-
face to facilitate the growth of vertically-aligned CNTs by injection CVD
(ICVD) with minimum degradation to the underlying CFs in a woven
cloth. And then, the CF cloths coated with aligned CNTs were stacked
and densified though chemical vapor infiltration (CVI) to obtain three-
dimensional (3D) C/C composites. The aim of growing vertically-
aligned CNTs on the surface of cloths is to provide enhanced mechanical
properties to woven-fabric C/C composites along the thickness direction
without altering the 2D stack design. Effect of the length of aligned CNTs
on their reinforcing role were evaluated under compression and bend-
ing stresses.
2. Experimental
2.1. Growth of vertically aligned CNTs on cloths
Polyacrylonitrile-based carbon cloths (T300, fiber diameter: 6–7 μm,
1000 fibers in a single bundle) with surface sizing removed were used
as the preform materials. CFs were coated with a SiO2 interface layer
by immersing cloths into toluene containing 5 vol.% silicon tetrachloride
(SiCl4) and 5 vol.% tetraethoxy silane (TEOS), and followed by the hy-
drolysis and pyrolysis processes. The growth of CNTs on the surface-
Fig. 1. Overview of preparing 3D C/C composites with aligned CNTs.
121
treated cloths was carried out using ICVD technique according to the
procedure described in our previous work [16]. Hybrid cloths with
CNTs of different lengths were obtained by controlling the growth
time (10, 20 and 40 min).
2.2. Composite preparation
Twenty-layers of CNT-coated cloths were stacked to build the multi-
layer 3D preforms and then were densified using isothermal CVI tech-
nique according to the procedure reported in Ref. [16]. C/C composites
without and with CNTs grown for 10, 20 and 40 min were denoted as
base, 3D-10, 3D-20 and 3D-40, respectively. The preparation procedure
of the 3D composites is depicted in Fig. 1.
2.3. Mechanical property tests
Tensile tests were carried out to investigate the effects of surface treat-
ment and CNT growth processes on the mechanical strength of CFs. Ten-
sile specimens were prepared by fixing both ends of fiber bundles onto
two aluminum sheets using resin with a gauge length of 20 mm. The
sizes of specimens for compression and bending tests were machined to
be 7 mm × 6 mm × 4 mm and 55 mm × 7 mm × 4 mm, respectively.
The support span for bending tests was 40 mm. The numbers of speci-
mens for tensile, compression and bending testing were not less than
20, 10 and 7. All the tests were carried out on a universal testing machine
(CMT5304) at a constant speed of 0.5 mm/min.
2.4. Characterization
The chemical composition of CFs before and after the surface treat-
ment was characterized by X-ray photoelectron spectroscopy (XPS),
122 L. Feng et al. / Materials and Design 92 (2016) 120–128
which was conducted on an ESCALAB 250Xi using AlKα radiation at a
power of 300 W. Scanning electron microscopy (SEM) and transmission
electron microscopy (TEM) were used to examine CNT growth morphol-
ogy, fracture surfaces of the failure specimens and CNT microstructure.
Microstructure of the PyC matrix was analyzed using polarized light mi-
croscopy (PLM).
3. Results and discussion
3.1. XPS analysis of the surface treatments of CFs
Fig. 2 presents the XPS results of the CFs before and after the surface
treatment. As seen, XPS survey spectrum of the CFs presents a strong C
1 s peak at 284.5 eV, along with a much weaker O 1 s peak at 532.5 eV
ascribed to physically absorbed oxygen species. The distinguishing fea-
ture of the XPS spectra of the surface-treated CFs is the appearance of Si
2p (103.5 eV, seen inset) and Si 2 s (155.5 eV) peaks, together with con-
comitant increase in the O 1 s and decrease in the C 1 s peaks. The Si 2p
(103.5 eV) is signal from SiO2 [17]. In addition, the C 1 s peak in the XPS
spectra of the surface-treated CFs arises from the carbon substrate, indi-
cating that the SiO2 interface layer is thinner than the XPS probe depth
(b10 nm). Insets of Fig. 2 present the SEM images of CFs before (down)
and after (up) the surface treatment. Similar to the CFs, the SiO2-coated
CFs still show smooth with evenly distributing shallow folds along the
direction of fiber axis. The thin nature of the SiO2 interface layer can en-
sure the efficient stress transfer from matrix to the underlying CFs [18].
3.2. Characterization of CNTs grown on cloths
The surface-treated cloths after growing CNTs on its surface by ICVD
process are presented in Fig. 3a, c and e. Aligned CNTs grow uniformly
and vertically on all of the exposed fibers on the surface of cloth. Anoth-
er finding from the SEM images is that the CNTs become denser and lon-
ger with the increase of growth time. Side views (Fig. 3b, d and f) of the
CNT forests provide accurate information of the CNT lengths which are
5.2, 13.1 and 21.8 μm, corresponding to the growth time of 10, 20 and
40 min (Table 1), respectively. Apparently, the length of the CNTs is in-
creased with the increasing growth time. We define the yield of CNTs as
weight gain of the cloth during the growth process. CNTs add 1.5% to the
specimen weight with 10 min growth, and up to 3.6% and 5.4% (aver-
aged over 10 specimens) with 20 and 40 min growth, respectively.
From enlarged view of the CNTs with 40 min growth shown in inset
of Fig. 3f, we can also get the spacing between nanotubes (from centre
to centre) are 40–120 nm, and thus the area density of the CNTs on
Fig. 2. XPS spectra and SEM images of the CFs before (down) and after (up) the surface
treatment.
the CF surface is estimated to be ~1.56 × 1010 tubes/cm2. This value is
roughly equal to those of CNTs grown on silica by the ICVD process
[19]. In contrast, to prior work where CNTs are grown on the surface
of CFs without SiO2 coating [16,20], the CNTs here obtained at the
same growth time are extremely long, dense and aligned. Typical TEM
image shown in Fig. 3g reveals a typical structure of bamboo-like
CNTs [21]. The CNTs have high quality with no by-products
(e.g., amorphous carbon and catalyst particles). Statistics from over 50
CNTs suggest that the inner and outer diameters of CNTs range from 8
to 12 nm and 15–25 nm, respectively. Higher-resolution TEM image
(Fig. 3h) shows clear graphene lattices in the tube wall, indicating a
high crystallinity of the produced CNTs.
3.3. Tensile strength of fiber bundles
Fig. 4 shows the tensile results of fiber bundles before and after the
surface treatment and CNT growth processes. It can be seen that the
surface-treated fiber bundles exhibit a small relative decrease in tensile
strength compared with pristine CFs, probably attributed to the thermal
degradation during high-temperature pyrolysis process. However, the
most encouraging result is the large strength retention rate of CFs
after growing CNTs. For the surface-treated fiber bundles after 40 min
CNT growth, the strength retention rate is 88.5%. This value is much
higher than those of fiber bundles (69.1% of strength retention rate)
without surface treatment after the CNT growth with low growth tem-
perature and roughly same growth time [20]. The large strength reten-
tion rate of CFs can be attributed to the SiO2 protection which may
prevent the Fe catalyst diffusing into the carbon substrates and the
trace oxygen attack [22]. It is expected that these 3D fabric reinforce-
ments with less damaging to the CFs can result in excellent mechanical
improvement in 3D C/C composites.
3.4. Characterization of 3D composites
To investigate the effect of vertically aligned CNTs on the microstruc-
ture of PyC matrix, images of cross-sections for the base and 3D compos-
ites are captured using PLM (Fig. 5a–d) and SEM (Fig. 5e–h). From
Fig. 5a, much large PyC grain size, long straight grain boundaries and ev-
ident matrix annular cracks can be clearly observed in the base compos-
ites. By contrast, the PyC matrix in 3D composites is highly integrated
with no annular cracks, as shown in Fig. 5b–d. Another interesting ob-
servation from PLM images of 3D composites is that the matrix exhibits
sandwich-like structures. The bottom and top layers next to fiber plies
are PyC with CNTs (defined as PyC/CNT) having no optical activity due
to the densely packed nanotubes [7], and the intermediate layer is
pure PyC containing no CNTs. Note that the intermediate PyC has small-
er grain size and short curved grain boundaries, largely different from
those in base composites. The PyC matrix at its electron microscopy is
shown in SEM images of Fig. 5e–h, where PyC next to ply surface ex-
hibits rough containing CNTs and aloof from fibers is smooth without
CNTs but with interlocked grain boundaries. These characteristics ob-
served in PLM and SEM images become much more distinct and clearer
with the prolonged CNT length.
Based on the PLM and SEM observations, corresponding models re-
garding the microstructure of PyC matrix of the base and 3D composites
are established, as shown in Fig. 6. In the case of base composite
(Fig. 6a), large PyC grains both in size and thickness are rather suscepti-
ble to cracking caused by thermal stress during the fabrication process,
leading to the occurrence of matrix annular cracks [23]. Moreover, long
straight grain boundaries preferentially aligned roughly either along or
parallel to the fiber plies are more likely to form among these large PyC
grains. After introducing aligned CNTs, two conclusions can be drawn
from the change of matrix microstructure. Firstly, the vertically aligned
nanotubes extending into the surrounding matrix as continuous rein-
forcers significantly stiffen the matrix. With the increase in CNT length,
this direct reinforcement on PyC matrix can extend to the area aloof
 L. Feng et al. / Materials and Design 92 (2016) 120–128 123

Fig. 3. SEM images (a–f) of SiO2-coated CFs grafted by aligned CNTs with different lengths controlled by the growth time: (a, b) 10 min; (c, d) 20 min; (e, f) 40 min. Inset of (f) is an enlarged
view of the CNT forests. TEM images (g, h) of the produced CNTs.
124 L. Feng et al. / Materials and Design 92 (2016) 120–128
Table 1
Comparison of CNT length (L), volume fractions (V) of CFs and CNTs, density and open po-
rosity of base, 3D-10, 3D-20 and 3D-40 composites.
Composites LCNT (μm) VCF (%) VCNT (%) Density (g/cm3) Open porosity (%)
Base – 38.1 – 1.62 12.8
3D-10 5.2 34.7 1.2 1.63 12.6
3D-20 13.1 33.8 3.0 1.60 14.1
3D-40 21.8 32.2 4.2 1.59 14.9
from plies because of the expansion of 3D CNT forests into distant space.
Secondly, CNTs also play an indirect reinforcing role in reinforcing the
PyC matrix out of the reach of nanotubes (here, it is called as “indirect
reinforcement”). Concretely, the top surface of CNT forests provides
abundant nano nucleation sites, which can induce the formation of
spherical or cone-shaped PyC on the surface of PyC/CNT [24]. With the
proceeding of CVI process, these PyC grains contact with each other
forming interlocked grain boundaries. Furthermore, the expansion of
3D CNT forests can efficiently reduce the growth space for the single
PyC both in thickness and size, resulting in smaller PyC grains with
shorter grain boundaries among them. These refined PyC have high co-
hesion and fracture resistance, which are expected to inhibit the growth
and propagation of cracks under loading. Therefore, compared with
CNTs reinforced polymer or ceramic composites wherein the CNTs can
only modify the matrix within the reach of nanotubes, the great signif-
icance of aligned CNTs used in C/C composites is their ability to not only
directly reinforce the matrix within the reach of nanotubes, but also to
give indirect reinforcement to the matrix aloof from nanotubes. The mi-
crostructure models of 3D composites with CNTs of different lengths are
clearly described in Fig. 6b–d. Clearly, both the direct and indirect rein-
forcements on the PyC matrix can be significantly increased by extend-
ing the CNT length.
3.5. Mechanical properties of 3D composites
Fig. 7 shows the compressive stress–strain curves obtained for all the
composite specimens. It is apparent that the out-of-plane compressive
strength (OCS, Fig. 7a) and in-plane compressive strength (ICS,
Fig. 7b) of the C/C composites are significantly increased after the
growth of vertically aligned CNTs on cloths, especially for the compos-
ites containing long nanotubes. The curves also display a clear behavior
in the specimens' response as seen by the difference in slope: specimens
from 3D specimens containing long CNTs show a higher slope than the
base specimen and 3D specimens containing short CNTs. This observa-
tion suggests that the former composites are stiffer than the latter com-
posites, i.e., higher out-of-plane compressive modulus (OCM) and in-
plane compressive modulus (ICM). The results listed in Table 2 show
that 3D-10, 3D-20 and 3D-40 have improvements in OCS of 33%, 42%
Fig. 4. Tensile stress–strain curves (a) and corresponding strengths (b) of fiber bundles before and after surface treatment (STCF) and CNT growth processes (STCF-X, X represents the
growth time).
and 63%, respectively. Compared with the base composites, 3D-10,
3D-20 and 3D-40 composites also have 13%, 19% and 24% improve-
ments in OCM, respectively. The measured ICS of the 3D-10, 3D-20
and 3D-40 composites show 152%, 206% and 275% enhancements com-
pared with base composites, respectively. The percentage improve-
ments in the ICM of the 3D-10, 3D-20 and 3D-40 composites
compared with those for the base specimens are 90%, 110% and 151%,
respectively.
For the base composites, upon 90° loading of specimen, massive de-
structive cracks are formed which propagate along the length and
height of specimen and then break the base specimens into small
pieces, whereas for the 3D composites the fracture only penetrates
the height of specimens forming roughly 45° angle with the thickness
direction resulting in fewer and bigger fragments. Further investigation
is performed based on SEM observations into the failure specimen to ac-
quire the information regarding reinforcement mechanism. The obser-
vation from the low-magnification SEM images of out-of-plane
compressive fracture surface shows that compared with the completely
disintegrated base specimens (Fig. 8a), the crushed PyC is significantly
decreased and even absent in the fragments of 3D specimens (for illus-
trative purpose, only image for representative specimen of 3D-20 is pre-
sented, as shown in Fig. 8c). Examination of the fracture surface at
higher magnification provides detailed information regarding the mor-
phology of the fractured PyC. As stated in Fig. 8b, the surface of fractured
PyC in base specimens looks flat and exhibits brittle fracture character.
Thus, it can be speculated that, when the base specimens are subjected
to out-of-plane stress, the matrix annular cracks and straight grain
boundaries (labeled by arrows in Fig. 8b) provide the main channels
for the destructive crack propagation along the length and height of
the composites, respectively. But comparatively, the fractured PyC of
3D composites appears very integrated and rugged (Fig. 8d). These ob-
servations indicate that a strongly-enhanced PyC matrix change the
mode of failure of the composites to a higher level of reinforcement.
Furthermore, sidewalls and ends of CNTs exposed to the fractured PyC
of 3D composites can be clearly observed, as shown in Fig. 8e and f,
which can be considered as another important factor for the increase
of OCS and OCM. On the one hand, the existence of CNT forests sharply
increase the interface area between PyC matrix and reinforcements, and
thus damage is more difficult to occur in 3D composites by virtue of ad-
ditional surface energy and friction work because of the newly formed
surface area [25]. On the other hand, the fracture of densely-packed
CNTs also dissipates great energy, which can further endow the high
fracture strength of the 3D composites.
Fig. 9 presents the SEM images of failed composite specimens after
the in-plane compression tests. When the base specimens are subjected
to 0° loading stress, overall shear failure occurs characterized by delam-
ination failures, as displayed in Fig. 9a. Enlarged SEM images reveal that
the destructive cracks spread in the PyC matrix (Fig. 9b) or along the
 L. Feng et al. / Materials and Design 92 (2016) 120–128 125

Fig. 5. PLM (a–d) and SEM (e–h) images of the base and 3D composites: (a, e) base; (b, f) 3D-10; (c, g) 3D-20; (d, h) 3D-40.

Fig. 6. Structure models of the base and 3D composites: (a) base; (b) 3D-10; (c) 3D-20; (d) 3D-40.

interface between matrix and outer surface of fiber bundles (Fig. 9c) annular cracks provide the main channels for the destructive crack
until they absolutely open the plies. For the spreading of destructive growth and subsequent long-distance propagation. After grafting CNT
cracks in PyC matrix of base composites, long straight PyC grain bound- forests on the CFs, the delamination failures of 3D composites under
aries orientated roughly parallel to the fiber plies and the matrix in-plane stress are alleviated and even inhibited, especially for the

Fig. 7. Compressive stress–strain curves of the base and 3D composites: (a) out-of-plane compression and (b) in-plane compression.
126 L. Feng et al. / Materials and Design 92 (2016) 120–128

Table 2
Compressive and flexural properties of the base, 3D-10, 3D-20 and 3D-40 composites (± values represent standard deviation).

Out-of-plane compression In-plane compression Flexure

Composites
Strength (MPa) Modulus (GPa) Strength (MPa) Modulus (GPa) Strength (MPa) Modulus (GPa)

Base 158 ± 8 3.12 ± 0.18 48 ± 10 5.12 ± 0.65 135 ± 9 22.1 ± 1.4

3D-10 210 ± 11 3.54 ± 0.11 121 ± 9 9.72 ± 0.54 143 ± 13 24.6 ± 1.2
3D-20 225 ± 14 3.72 ± 0.16 147 ± 11 10.75 ± 0.87 148 ± 11 25.4 ± 1.1
3D-40 258 ± 16 3.86 ± 0.21 180 ± 18 12.86 ± 0.81 153 ± 9 26.6 ± 1.6

composites containing long CNTs. As illustrated in Fig. 9d selected from
3D-20 specimens, where the failure initiates from the top edge of the
composite and develops roughly along the diagonal of test specimen.
Enlarged SEM images demonstrate that the stiffer matrix impedes the
extending of cracks which want to develop along straight path
(Fig. 9e), and the resultant crack deflection leads to the fracture of
fiber bundles (Fig. 9f). Great energy can be consumed during crack de-
flection thus resulting in the remarkable enhancement in in-plane com-
pressive performance [26]. It is difficult to find the CNT ends and
sidewalls that are observed in the out-of-plane compressive fracture

Fig. 8. Different-magnification SEM images of the out-of-plane compressive fracture surfaces of the base (a and b) and 3D-20 (c–f) composites.
 L. Feng et al. / Materials and Design 92 (2016) 120–128
Fig. 9. SEM images of the representative failure specimens from the base (a–c) and 3D-20 (d–f) composites after the in-plane compression test (red dotted arrows represent the extending
paths of the destructive cracks).
surface of the 3D composites. Actually, compared with the strongly-
stiffened PyC/CNT, the destructive cracks are more likely to spread in in-
termediate PyC layer. For the 3D-10 composites containing short CNTs,
the absence of annular cracks in intermediate PyC layer is the main rea-
son for the improvements of ICS and ICM. With the extending of CNT
forests in 3D composites, the intermediate PyC is significantly decreased
in width and meanwhile has more convoluted and interlocking grain
boundaries, as a result, the growth and propagation of destructive
cracks in the PyC matrix of long CNT-reinforced 3D composites becomes
increasingly difficult such that crack deflection occurs, resulting in the
higher ICS and ICM. However, the stiffer carbon matrix may not be the
only contributor to ICS and ICM enhancements, since they can also be
attributed to the increased lateral support for the load-bearing plies
provided by vertically aligned CNTs that may prevent the CFs from
microbuckling, a critical composite failure mode associated with fibers
under in-plane compressive stress [27]. The percentage enhancements
in ICS and ICM obtained for 3D-40 composites are much higher than
those obtained by grafting curved and radially CNTs on CFs [10,16,20].
Therefore, from the above analysis, one can comprehend that high-
density CNT forests with long extending length which not only signifi-
cantly stiffen the surrounding matrix at greater depth (i.e., direct rein-
forcement), but also influence the peripheral matrix at higher level
(i.e., indirect reinforcement), and thus largely increase the compressive
properties.
Fig. 10. Flexural stress–strain curves of the base and 3D composites.
127
More surprisingly, the dramatic enhancement of the matrix-
dominated mechanical performance does not compromise the in-
plane properties. The flexural stress–strain curves for the test speci-
mens are presented in Fig. 10, in which all the 3D composites show
high failure flexural strength (FS) and modulus (FM) compared
with the base specimens. From Table 2, the FS of 3D-10, 3D-20 and
3D-40 are improved by 6%, 10% and 13%, although the fiber volume
fractions are decreased by 8.9%, 11.3% and 15.5% (Table 1),
respectively. Compared with the base composites, 3D-10, 3D-20
and 3D-40 also have 11%, 15%, and 20% enhancements in FM.
Another observation in Fig. 10 is that all the composite specimens
show typical brittle fracture, evidenced by the sudden failure as the
stress goes up to the peak of curves, which suggests that, the
introduction of CNT forests increases the mechanical properties of
C/C composites but not significantly changes their fracture behavior.
Besides, it needs to be emphasized that the little damage to the CFs
attributed to the SiO 2 protection is an important factor for the
improvement of FS and FM, since the direct growth of CNTs on the
CF surface leads to a serious decrease in flexural properties of C/C
composites due to the excessive strength loss of CFs by iron etching
and thermal degradation reported in our previous work [20].
4. Conclusions
The 3D composites introduced here is the first real instance
where the CNTs are used in high density, vertically aligned
orientation and controllable length to effectively improve the
mechanical performance of C/C composite. Vertically aligned
CNTs grown on the surface-treated carbon cloths not only directly
stiffen the matrix within the CNT reach, but also give indirect rein-
forcement to the matrix out of the CNT reach by inducing the for-
mation of small PyC gains that interlock with each other. Both the
direct and indirect reinforcements on the PyC matrix can be signif-
icantly increased by extending the CNT length. Our work demon-
strates that introducing vertically aligned CNTs in the thickness
direction of woven-fabric C/C composites is an effective strategy
to largely increase longitudinal and transverse compressive
properties without sacrificing the in-plane performance. To
further understand this new type composite and to enlarge its
application, further research should be done on the multifunction-
al properties, such as thermal conductivity, thermal diffusivity
and thermal expansion behaviors.
128 L. Feng et al. / Materials and Design 92 (2016) 120–128
Acknowledgments
This work has been supported by the Key Grant Project of the Chi-
nese Ministry of Education (Grant No. 313047), the FP7-International
Research Staff Exchange Scheme—Advanced Biomaterials for Regenera-
tive Medicine, the Global Innovation Initiative—Nanostructured Mate-
rials for the Control of Contaminants Detrimental to Health, the
Fundamental Research Funds for the Central universities under Grant
No. 3102014JCQ01030 and “111” Project of China (B08040), the Re-
search Fund for the Doctoral Program of Higher Education of China
(Grant No. 20126102110013) and the Natural Science Foundation of
China (Grant Nos. 51432008, 51202194, 51272212 and 51272213).
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