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Article history:
Received 22 May 2015
Received in revised form 18 July 2015
Accepted 27 July 2015
Available online 29 July 2015
Keywords:
Carbon nanotubes
Carbon bers
Carbon/carbon composites
Mechanical properties
a b s t r a c t
We present an in-depth study of the effect of carbon nanotube (CNT) extending length on microstructural
and mechanical behavior of carbon/carbon (C/C) composite. High-purity CNTs with controlled extending
length were in situ grown on the surface of carbon cloths using injection chemical vapor deposition
(ICVD) by varying the reaction time. Microstructure analysis shows that compared with the CNTs of
short extending length which only change the pyrocarbon (PyC) close to ber surface, CNTs with long
extending length can strongly affect the deposition behavior of PyC during chemical vapor inltration
and modify the whole matrix PyC. Mechanical tests reveal that CNTs with long extending length are
more benecial to enhance the interlaminar shear strength and in-plane compressive strength of the
composites, while the reactive conditions during ICVD degrade the carbon bers and lead to the decrease
of exural strength. Our work demonstrates that it is necessary to make CNTs long enough as well as
to prevent strength degradation of bers, if we want to largely increase delamination resistance and
through-thickness properties without compromising in-plane performance of C/C composites.
2015 Elsevier B.V. All rights reserved.
1. Introduction
Carbon ber reinforced carbon matrix (C/C) composites have
been widely used in mechanical engineering, aeronautics and
astronautics [13]. Carbon bers are primarily preferred for conventional composite usage by virtue of their extraordinary intrinsic
properties (mechanical and physical). The chemical inertness of
carbon bers such as excessive smoothness, surface lipophobicity
and less adsorption characteristics always lead to poor adhesion with the matrix materials. Therefore, many researchers have
focused on modifying the carbon ber surface to execute strong
ber/matrix (F/M) interface bonding for effective stress transfer in composite materials, especially in resin matrix composites
[4,5]. Nevertheless, new study suggests that increasing cohesion
between ber and matrix is far from enough to obtain high performance C/C composite which is determined by not only the nature of
F/M interface bonding but also the microstructure of matrix pyrocarbon (PyC) [6].
Corresponding author.
E-mail addresses: fengleijinan@163.com (L. Feng), likezhi@nwpu.edu.cn (K. Li),
sunjiajia55@163.com (J. Sun), jiayujun2013@mail.nwpu.edu.cn (Y. Jia),
lihejun@nwpu.edu.cn (H. Li), zhangleilei@nwpu.edu.cn (L. Zhang).
http://dx.doi.org/10.1016/j.apsusc.2015.07.198
0169-4332/ 2015 Elsevier B.V. All rights reserved.
Composite
Vber (%)
VCNT (%)
C/C
CNT 15C/C
CNT 45C/C
44.5 0.6
43.6 0.8
42.3 1.1
0
0.6 0.2
1.9 0.6
1.60 0.2
1.61 0.1
1.62 0.1
2. Experimental
2.1. Growing CNTs on carbon cloths
Commercially available carbon cloth (1-kilo polyacrylonitrile
based carbon ber, Jilin Carbon Corporation, China) woven in a
0 /90 satin-weave was used as the preform materials of C/C
composites. CNTs were grown onto carbon cloth using ICVD
method at ambient pressure in a horizontal quartz reactor
equipped with an electrical furnace. At room temperature, the
reactor was rst purged with 300 sccm argon (Ar). After purging, the reactor was heated to 800 C under Ar ow. At the
growth temperature, the feeding solution of ferrocene (0.01 g/ml)
in ethanol/ethylenediamine mixture (volume ratio of 4/1) was
injected continuously into the reactor at a rate of 10 ml/h using
a syringe pump. The growth time was set to be either 15 min or
45 min.
2.2. Composite preparation
VCNT (%) =
Vfiber
fiber Vpreform
MCNT
CNT Vpreform
In order to explore the inuence of ICVD process on the properties of carbon bers, tensile tests of ber bundles taken from
carbon cloths with CNT grafting at different reaction time were carried out using tensile stress testing system on a universal testing
machine (CMT5304-30 kN). A ber bundle (consist of 1000 bers)
was glued at both ends onto two aluminum sheets (thickness less
than 1 mm). The gauge length was 20 mm. A typical crosshead
speed of 0.5 mm/min was applied for the test. A minimum of 20
measurements were recorded for each ber bundle sample. The
averaged values of tensile strength were obtained.
2.5. Tests of mechanical properties
The composite specimens used for interlaminar shear test and
in-plane compression test were all machined into the size of
5 mm 4 mm 3 mm, and then polished to ensure perfect at and
parallel cross-sections. All the tests were carried out at a constant
speed of 0.5 mm/min on the universal testing machine at room temperature. Both the interlaminar shear strength (ILSS) and in-plane
compressive strength (ICS) were calculated by the following Eq. (3):
=
1021
(1)
(2)
where Vber (%) and VCNT (%) are the volume fractions of carbon
bers and CNTs, respectively. Mber and MCNT are the total masses
of carbon cloths (seventeen layers) and CNTs, respectively; ber
and CNT are the densities of carbon bers (1.75 g/cm3 ) and CNTs
(0.8 g/cm3 ), respectively; Vpreform is the volume of multilayered preform.
2.3. Morphology and structure characterization
The morphological features of grafted CNTs and PyC in
three kinds of composites were examined by scanning electron
microscopy (SEM, JSM-6700) operated at 15 kV. The microstructure
of CNTs was also investigated by transmission electron microscopy
(TEM, Tecnai F30G2 ) operated at 200 kV. The composite samples
were mounted in epoxy resin and ground by silicon carbide paper
with different grades (400, 600, 800 and 1200 grits) in turns, and
then polished with 0.1 m alumina powder on polishing cloth.
Finally, the polished section was observed by leica DMLP optical
microscope to identify the polarization microstructure (PLM) of
PyC. The graphitization degree and microcrystalline planar size of
PyC were obtained by Raman spectroscopy (Renishaw) using an
P
S
(3)
where means calculated mechanical strength; P means compressive force and S signies forced area.
The exural strength was tested using a three-point bending test on specimens with dimensions 40 mm 7 mm 3 mm, a
0.5 mm/min crosshead speed and a 30 mm support ban. The exural
strength was calculated according to the Eq. (4):
f =
3FL
2bh2
(4)
1022
Fig. 3. Tensile strength of ber bundles before and after grafting CNTs with different
reaction time (CNT 15CF and CNT 45CF present ber bundles with CNT growth
for 15 and 45 min, respectively).
Fig. 1. Optical photos (left column) and SEM images (right column) of carbon cloth:
(a) before and after (b) 15 min, (c) 45 min growth reaction using the ICVD method.
is decreased with the CNT length extending. Fig. 2 presents typical TEM images of CNTs collected from 45 min growth of hybrid
bers. From Fig. 2(a), it can be seen that CNTs are very uniform with
the outer diameter of 2040 nm and the nanotubes appear high
purity without by-products (e.g., amorphous carbon and encapsulated catalyst particles). High-magnication TEM image (Fig. 2(b))
reveals that the CNTs are multi-walled with the clear lattice fringes
parallel to the nanotube axis, indicating a very high degree of crystallinity.
Fig. 3 shows the tensile results of ber bundles before and after
the growth of CNTs with different reaction time. After grating CNTs
for 15 min, the ber bundles lose approximately 17.6% of their pristine strength; as the reaction time increases to 45 min, the strength
loss reaches nearly 30.9%. The degradation is ascribed to the surface
damage of the bers by the iron (catalyst) etching, which is believed
to induce defects on the ber surface and leads to a decrease in
ber strength [1517]. In addition, the high temperature may be
the other contributor to the strength degradation of carbon bers,
since trace amounts of oxygen may be present in the continuous
Ar ow, which can lead to the ber oxidation. The growth of long
CNTs needs a prolonged exposure of carbon bers to the reactive
conditions, i.e., more iron etching and oxygen attack, thus leading
to a more decrease in tensile strength.
1023
Fig. 4. PLM images of the cross-section of composites: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C (red points are the Raman detection positions). (For interpretation of the
references to color in the text, the reader is referred to the web version of this article.)
cracks and shows better adhesion with carbon bers. Enlarged SEM
image (inset of Fig. 5(b)) of the F/M interface illustrates that the PyC
closed to bers are porous and disordered in orientation, which are
the typical characteristic morphology of ISO PyC [21]. By contrast,
in CNT 45C/C composite, the microstructure of whole matrix PyC
is not homogeneous at all (Fig. 5(c)). It is observable that next to
the ISO area, PyC layers of rolled akes have been found. These
regular lamella structures arise from the orderliness deposition of
PyC around single CNT (see inset of Fig. 5(c)), which can be considered as medium-textured (MT) PyC [18]. It should be noted that
the interface between MT PyC is not straight (two examples are
labeled by red dotted lines marked in Fig. 5(c)), which is related
to the various nanotube orientation. In addition, the zone of ISO
PyC is obvious wider than those in CNT 15C/C composites (as presented in Fig. 5(c), the width of the isotropic area is over 5 m), in
agreement with PLM observation. The change of microstructure in
CNTC/C composites should be ascribed to the existence of CNTs,
i.e., CNTs have affected the deposition behavior of PyC during CVI.
Raman spectroscopy is used to evaluate the degree of orderliness or randomness within the carbon materials, because
quantitative analysis can be achieved by the intensity ratio of the
D peak and G peak in Raman spectra. All the spectra taken from the
three composites at different positions (red points marked in Fig. 4)
exhibit two prominent peaks, which are the disorder-induced D
mode (1360 cm1 ) and the tangential G mode (1580 cm1 ), as
shown in Fig. 6. It is widely accepted that the lower intensity ratio
of the D peak and G peak, R (ID /IG ), corresponds to the higher quality of graphitization within carbon materials [22,23]. Furthermore,
it has been found empirically that the value of R is related to the
Fig. 5. SEM images of the cross-section of composites: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C (insets are enlarged views of the square areas marked in (b) and (c)). (For
interpretation of the references to color in the text, the reader is referred to the web version of this article.)
1024
Fig. 6. Raman spectra of composites at different positions: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C.
Table 2
R and La values of corresponding PyC obtained from Raman spectra.
Composite
C/C
Position
R
La
1.04
4.23
1.02
4.31
1.05
4.19
1.47
2.99
1.11
3.96
1.02
4.31
1.54
2.86
1.25
3.52
0.97
4.54
CNT 15C/C
1
ID /IG
(5)
CNT 45C/C
1025
Fig. 7. Schematics of C/C composites with CNTs of different extending lengths: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C.
Fig. 8. ILSS and ICS of C/C composites with CNTs of different extending lengths.
the typical failure of CNT 15C/C composite, the cracks are initiated from the top of specimen, which then link up and propagate
as a stable interply delamination. The cracks will traverse 5060% of
the specimen length before they are eventually arrested (Fig. 10(b)).
However, CNT 45C/C composite has much fewer cracks than those
in C/C and CNT 15C/C composites when subjected to the in-plane
compressive stress, and the cracks mainly develop roughly along
the diagonal of test specimen (Fig. 10(c)). Crack deection act as
energy absorbing mechanisms can endow high fracture strength
of composites [29,30]. The signicant change of crack propagation
Fig. 9. SEM images of the shearing fracture surface of composites: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C.
1026
Fig. 10. SEM images of failure composites after in-plane compression test: (a) C/C; (b) CNT 15C/C; (c) CNT 45C/C (dotted lines represent extending path of cracks). (For
interpretation of the references to color in the text, the reader is referred to the web version of this article.)
process results from the fully modied PyC matrix that is due
to the greatly-developed CNT extending length, which efciently
impedes the crack extending thus resulting in the more remarkable
increases in ILSS and ICS.
Fig. 11 shows the bending test results of three C/C composites. It
can be seen that the exural strength of C/C composites decreases
with the increase of CNT growth time. The exural strengths of
CNT 15C/C and CNT 45C/C composites have nearly 9.1% and
23.8% reduction compared with that of C/C composite, respectively.
Excessive loss of ber strength described before offsets the positive
effect created by CNTs and leads to the decrease of exural strength
of CNTC/C composites [31]. The results of this study show that
grafting carbon bers with CNTs of long extending length can well
modify the matrix PyC and create great higher matrix-dominated
performance of C/C composite, but at the expense of sacricing
more in-plane property.
4. Conclusions
High-purity CNTs with different extending lengths have been
uniformly grown on the surface of carbon cloths using ICVD
method by varying the reaction time. It demonstrates that the PyC
microstructure and the mechanical behavior of C/C composites are
Acknowledgements
This work has been supported by the Key Grant Project of the
Chinese Ministry of Education (Grant No. 313047), the Research
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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