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Robust and wear resistant in-situ carbon nanotube/

Si3N4 nanocomposites with a high loading
of nanotubes

Jesus Gonzalez-Julian a, Amit Datye b, Kuang-Hsi Wu c, Johannes Schneider d,

Manuel Belmonte e,*
a
Institute of Materials Science and Technology (IMT), Friedrich Schiller University, 07743 Jena, Germany
b
Department of Materials Science and Engineering, The University of Tennessee, Knoxville, TN 37996, USA
c
Department of Mechanical and Materials Engineering, Florida International University, Miami, FL 33174, USA
d
Institute for Applied Materials, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
e
Institute of Ceramics and Glass (ICV-CSIC), Kelsen 5, 28049 Madrid, Spain

A R T I C L E I N F O A B S T R A C T

Article history:
Received 5 November 2013
Accepted 2 February 2014
Available online 8 February 2014
Highly homogenous carbon nanotube (CNT)/silicon nitride (Si3N4) nanocomposites with
high CNTs loadings, up to 22 vol.%, are developed through the in-situ synthesis of CNTs
on the ceramic powders, and further densification using the spark plasma sintering tech-
nique. The CNTs dispersion degree, the composite density, and their properties, especially
the tribological ones, are evaluated and compared with those obtained for nanocomposites
processed by the ex-situ method based on the mixing of nanotubes and ceramic powders in
a solvent media. Fully dense in-situ 12 vol.% CNTs nanocomposites are 87% and 65% more
wear resistant than monolithic Si3N4 materials and ex-situ nanocomposites, respectively,
in the latter case due to the higher nanotubes dispersion and better mechanical properties
attained by the in-situ process. These new in-situ CNTs nanocomposites present multi-
functionality and are promising for emerging applications, especially for gasoline direct
injection systems.
 2014 Elsevier Ltd. All rights reserved.

1. Introduction obtained at laboratory scale [3], especially for electrical [4]

Despite the promising career of the carbon nanotubes (CNTs)
into the scientific panorama has been partially eclipsed since
graphene burst in 2004 [1], the number of commercial appli-
cations of CNTs containing composites have continuously in-
creased in the transportation, energy and sports industry [2],
which confirms the good health of this carbon nanostructure.
However, most of those commercial products are polymer-
based composites, becoming hardly to find CNTs/ceramic
components in spite of some excellent properties have been
and tribological ones [5]. Interestingly, although CNTs/ceram-
ics composites are good candidates for emerging applications
linked to energy and environmental fields, their scarce spread
into commercial products can be due to the complexity for
manufacturing them. Issues such as CNTs dispersion within
the ceramic matrix, optimum nanotube-matrix interface
strength, lack of composite density, and nanotubes damage
during the densification process at high temperature are key
factors. To overcome these difficulties, many efforts have
been made. In this sense, the use of the spark plasma

* Corresponding author: Fax: +34 917355843.

E-mail address: mbelmonte@icv.csic.es (M. Belmonte).
http://dx.doi.org/10.1016/j.carbon.2014.02.014
0008-6223/ 2014 Elsevier Ltd. All rights reserved.
 CARBON 7 2 (2 0 1 4) 3 3 834 7
sintering (SPS) technique allows getting fully dense CNTs/
ceramic composites avoiding the nanotubes degradation [6],
while different processing routes have been investigated
(mechanical procedures, colloidal processing, solgel process-
ing, and in-situ growth of CNTs by catalytic chemical vapor
decomposition, CCVD [3]) to obtain an homogenous distribu-
tion of the nanotubes within the ceramic matrix. Finally, the
nanotube-matrix interface strength has been enhanced func-
tionalizing the nanotubes by means of oxidation or boron ni-
tride and silicon oxide coatings [7]. However, the success of all
these approaches is limited for large CNTs contents, typically
above 35 wt.%, restricting the potential benefits of using
CNTs in ceramic emerging applications.
Focusing on silicon nitride (Si3N4)-based composites, the
most promising high temperature structural ceramics, some
of the present authors have previously obtained homogenous
and fully dense nanocomposites containing up to 5 wt.% of
multi-walled CNTs (MWCNTs, 8.6 vol.%) using sonicating
and mechanical stirring procedures in ethanol media and fur-
ther densification by SPS [8]. The nanocomposites decreased
the friction coefficient and enhanced the wear resistance in
about 40% and 80%, respectively, as compared with the mono-
lithics, emerging as an excellent material for gasoline direct
injection systems (GDI) that are able to reduce the fuel con-
sumption and the particulate emissions [5]. These systems
require pressures above 30 MPa, that combined with the poor
lubricating conditions of gasoline, lead to extensive friction
and wear of the current metallic sliding components. There-
fore, the searching for new materials with enhanced tribolog-
ical properties becomes an urgent need. Besides, these
nanocomposites contained an electrical conductive nano-
tubes network within the ceramic, increasing the Si3N4 elec-
trical conductivity (re) in more than 15 orders of magnitude
with a maximum re value of 474 S m1 when 3 wt.%
(5.3 vol.%) of undoped nanotubes were added [9]. This new
functionality allowed electrically discharge machining (EDM)
a Si3N4 microgear [10], the first step to develop intricate cera-
mic parts for new engineering and biomedical applications.
Other authors have attempted to introduce larger CNTs con-
tents (10 wt.% [11] and 12 wt.% [12]), but Si3N4 composites
contained CNTs agglomerates [13] or the nanotubes simply
disappeared after reacting to form SiC [12], in both cases lead-
ing to a decrease on the final density and, consequently, to a
deleterious effect on the composite properties. Therefore, it
seems that 5 wt.% is the CNTs content threshold to assure
both the homogeneous dispersion of the nanotubes into the
ceramic and the full densification of the composite.
Considering the excellent CNTs/Si3N4 nanocomposite
properties attained until now, new questions arise such as:
can these properties be enhanced introducing larger CNTs
contents? And the most important, will it be possible to dis-
perse them? In this sense, Peigney et al. [14] obtained highly
homogeneous nanotubes dispersion within different ceramic
powders (Al2O3, MgAl2O4 and MgO) with CNTs contents up to
14.5 wt.%, which were in-situ synthesized on the ceramic
powders by CCVD using distinct catalysts (iron, cobalt, molyb-
denum). As an example, these authors reported a continuous
increment on the MgAl2O4 electrical conductivity with the
CNTs content, re ranging from 0.4 S m1, for monolithics, to
850 S m1, for 12.2 wt.% (24.5 vol.%) CNTs nanocomposites
339
[15]. However, despite the good CNTs dispersion achieved,
the density of the hot-pressed CNTs/MgAl2O4 compositions
decreased with the nanotubes content, reaching density val-
ues below 98% for contents higher than 2.5 wt.% (5.3 vol.%)
and a minimum value of 68% for the highest CNTs content
[15]. Some of the present authors used CCVD and a cobalt ni-
trate catalyst precursor to in-situ grow 4 wt.% of MWCNTs
on yttria stabilized zirconia (3YTZP) particles [16]. The SPSed
nanocomposites exhibited full densification with a uniform
distribution of CNTs, enhancing the flexural strength in
20% compared to the monolithic material. However, the
growth of larger CNTs contents was not attempted.
The aim of the present work is to develop CNTs/Si3N4
nanocomposites with a nanotubes content above 5 wt.%
using cobalt catalyst assisted CVD method and further densi-
fication by SPS. The CNTs dispersion degree, the composite
density, and their properties, especially the tribological ones
looking for future GDI applications, are evaluated and com-
pared with those obtained for nanocomposites processed by
the ex-situ method, i.e., the conventional route mixing the
nanotubes and the ceramic powders in a solvent media.
2. Experimental procedure
2.1. In-situ CNTs/Si3N4 nanocomposites
Si3N4 composition was constituted by 93 wt.% of a-Si3N4 (SN-
E10 grade, UBE Industries, average particle size = 200 nm),
2 wt.% of Al2O3 (SM8, Baikowski Chimie, average particle si-
ze = 300 nm) and 5 wt.% of Y2O3 (Grade C, H.C. Starck GmbH
& Co., average particle size = 900 nm) powders that were
mixed together by attrition milling in ethanol for 2 h using
Si3N4 grinding media. The solvent was evaporated from the
suspension in a rotary-evaporator at 90 C and the resulting
mixture was dried at 120 C before sieving through a 63 lm
mesh. The ceramic powder composition was then mixed in
methanol with cobalt (II) nitrate hexahydrate (Co(NO3)26H2O),
used as catalyst precursor, and sonicated for 15 min. Two dif-
ferent cobalt contents (Co/Si3N4 = 2.5 and 5.0 wt.%) were se-
lected in order to grow high CNTs contents. Afterwards, the
suspension was dried overnight at 125 C in an oven, and
the dried powder mixture was sieved using a 63 lm mesh.
For the CNTs synthesis, the powder mixture was placed in a
tube furnace modified with stirrers. CVD process was carried
out at 750 C for 15 min via thermal decomposition of the
acetylene precursor using H2 as the process gas. Finally, the
powder was heated at 300 C during 30 min in air to remove
the amorphous carbon followed by sieving through a 63 lm
mesh. Discs of 20 mm in diameter and 3 mm in thickness
were obtained by spark plasma sintering (SPS, Dr. Sinter,
SPS-510CE) using 1585 C of maximum temperature, holding
time of 5 min, and 4 Pa of vacuum atmosphere. 3 g of each
ceramic/CNTs powder composition were put into the SPS
graphite die and pressed at 20 MPa at room temperature.
Afterwards, a uniaxial pressure of 50 MPa was applied during
the first minute of the heating process (below 600 C) and
maintained during the heatingholding cycle, decreasing the
pressure to 20 MPa on the cooling step. Sintering tests were
carried out using a heating rate of 133 C min1 between 600
340 CARBON 7 2 ( 2 0 1 4 ) 3 3 8 3 4 7
and 1400 C, and 50 C min1 from this temperature up to
1585 C to avoid temperature overshooting. At the end of
the holding time, the current was shut off leading to cooling
rates of 300 C min1.
2.2. Ex-situ CNTs/Si3N4 nanocomposites
Si3N4 nanocomposites containing 12 vol.% of commercial
MWCNTs (Nanolab Inc.) were processed as described else-
where [8]. In brief, CNTs and the Si3N4 composition, the same
as detailed above, were separately dispersed in ethanol media
and, then, all together mixed at given proportions in an ultra-
sonic bath under continuous mechanical stirring. Later on,
the solvent was removed and the resulting powder mixture
was dried, sieved and sintered following the same procedure
than for the in-situ process. A Si3N4 monolithic specimen was
equally processed for comparison.
2.3. Characterization
Thermogravimetric analysis/thermodifferential analysis
(TGA/TDA, STA 409, Netzsch) were performed in air atmo-
sphere from room temperature up to 800 C and a heating rate
of 10 Cmin1. Micro-Raman (Renishaw inVia) spectra were
recorded using an excitation energy of 2.54 eV and a laser
wavelength of 514.5 nm. CNTs were observed by transmission
electron microscopy (TEM, JEOL 2010F) and field emission
scanning electron microscopy (FESEM, S-4700, Hitachi), while
the microstructure of the different materials was studied by
FESEM on both fracture specimens and polished and plasma
etched (CF4/5 vol.% O2 at 100 W for 40 s) surfaces. Apparent
density was measured by the water immersion method, and
the relative density was estimated assuming a theoretical
density (qth) of 3.23 and 1.80 g cm3 for Si3N4 and CNTs,
respectively. Crystalline phases were determined by X-ray dif-
fraction (XRD, Bruker D5000, Siemens) analysis, and the
a ! bSi3N4 transformation degree was quantified by the
expression of Gazzara and Messier [17]. Median grain size
(d50) and aspect ratio (AR50) of the matrix were quantified by
imaging analysis methods on FESEM micrographs considering
more than 1000 features.
2.4. Properties
2.4.1. Mechanical properties
Nanoindentation experiments were performed on mechani-
cally mirror polished samples using a MTS Nanoindenter XP
(MTS, Oak Ridge, TN, USA) with a berkovich tip of approxi-
mate tip radius of 150 nm. The CSM (Continuous Stiffness
Module) was used with a constant strain rate of 0.05 s1. A
fused silica specimen with a known modulus (72.1 GPa) was
used to calculate the area function and calibrate the stiffness
of the system. Indentations were done at a peak load of
500 mN separated by 20 times the maximum penetration
depth. The unloading curve was used to calculate the reduced
modulus, which took into account the modulus and Poissons
ratio of the diamond indenter, 1147 GPa and 0.07, respectively.
The elastic modulus of the sample was then calculated
assuming a Poissons ratio of 0.24 for silicon nitride. The data
reported was an average of at least 16 indents. The
OliverPharrs method [18,19] was used to evaluate the elastic
modulus (E) and the hardness (H) of the samples. Fracture
toughness (KIC) was measured by Vickers indentation
(Zwick/Roell, Zhu 2.5) at a load of 196 N, and using Miranzo
et al.s equation [20]. At least five indentations were per-
formed for each specimen.
2.4.2. Tribological properties
Isooctane lubricated reciprocating ball-on-plate tests (SRV
tester, Optimol) were conducted to simulate the GDI operating
conditions and the friction and the wear volume of the mate-
rials were analyzed. Commercial Si3N4 balls (10.3 mm diame-
ter, SN101C, Saint Gobain) were used as counterbodies. The
tests were run at the following conditions: stroke length of
2.5 mm, frequency of 20 Hz (0.1 m s1), sliding distance of
360 m, and normal applied load of 50200 N that corre-
sponded to Hertzian contact pressures of 2.03.4 GPa at the
very beginning of the tests. At least three tests were per-
formed for each load condition and data represent their aver-
age. The steady state friction coefficient (lss) was estimated
within the 250350 m interval. The wear volume (WV) was as-
sessed from the depth and the diameter of the wear scars [5],
and the wear rate (WR) was calculated by the equation WR =
WV/(FNs), where FN is the normal load and s the sliding dis-
tance. Worn surfaces were characterized by FESEM.
2.4.3. Electrical properties
DC electrical conductivity was measured using the four-probe
method and a DC voltage range of 0200 mV (Agilent E3646A
dc source and an Agilent 34401A voltmeter).
3. Results and discussion
The characterization of the in-situ CNTs grown on the cera-
mic powders is depicted in Figs. 1 and 2, and compared to that
for the commercial MWCNTs used for the ex-situ process.
The three characteristics Raman bands associated to CNTs
were clearly observed (Fig. 1a) at 1340 (D-band), 1593
(G-band), and 2700 cm1 (G 0 -band). Besides, the intensity ratio
between D and G bands (ID/IG), commonly used as a tool to
estimate the crystallinity of CNTs, gave a value of 0.97 and
1.13 (Table 1) for the nanotubes grown using 2.5 and
5.0 wt.% of cobalt, respectively. As it can be seen, the catalyst
content hardly modified the crystallinity of the nanotubes,
although they presented more defects than commercial
MWCNTs (ID/IG = 0.89). The in-plane crystallite size (La) of
the different nanotubes was assessed using Raman data
and Cancado et al.s equation [21]:
 1
ID
La nm 2:4  1010 kl 1
IG
where kl is the laser line wavelength, in this particular case
514.5 nm. La values for CNTs in-situ grown were 1617 nm
(Table 1), quite close to data obtained for commercial nano-
tubes (19 nm).
TGA analysis was used to determine the amount of nano-
tubes incorporated to the Si3N4 powder composition after the
CVD growth (Fig. 1b). In the same way to data reported by
other authors [22], the current nanotubes started to oxidize
at 400 C, followed by a rapid oxidation up to 520 C
 CARBON 7 2 (2 0 1 4) 3 3 834 7 341

(a) G Ex-situ
(b) 100
D In situ 2.5 wt.% Co
In situ 5.0 wt.% Co
95
Ex-situ

Weight loss (%)

Intensity (a.u.)
In situ 2.5 wt.% Co
G' In situ 5.0 wt.% Co
90

85

80
500 1000 1500 2000 2500 3000 0 100 200 300 400 500 600 700 800
Raman shift (cm-1) Temperature (oC)

Fig. 1 (a) Micro-Raman spectra for the commercial MWCNTs used for the ex-situ process and for in-situ grown by CCVD
method employing 2.5 and 5.0 wt.% of cobalt content, and (b) the corresponding TGA curves for the ex-situ and in-situ
ceramic/CNTs powder compositions as a function of the nanotube type (commercial or in-situ grown). (A color version of this
figure can be viewed online.)

Fig. 2 TEM micrographs of the commercial MWCNTs (a) and grown by the in-situ CCVD method using 2.5 wt.% (b) and
5.0 wt.% (c) of cobalt content, and FESEM micrographs of the ex-situ (d) and in-situ 12 vol.% (e) and 22 vol.% (f) CNTs/ceramic
powder mixtures. CNTs agglomerates in (d) are pointed by arrows.

Table 1 Microstructural features of the monolithic Si3N4 and the nanocomposites containing MWCNTs obtained by the
ex-situ and in-situ methods: relative densities (% qth), median grain size (d50), aspect ratio (AR50) and a-phase content of the
matrix, intensity (integrated area) ratios between D and G bands (ID/IG) before and after the sintering process by SPS, and
in-plane crystallite size (La) of the nanotubes.

Material % qth d50 (nm) AR50 a-Phase (%) ID/IG La (nm)

Before SPS After SPS

Si3N4 99.9 297 1.79 42 na na na

Ex-situ 12 vol.% 98.6 218 1.52 48 0.89 0.86 19
In-situ 12 vol.% 99.7 198 1.50 47 0.97 1.10 17
In-situ 22 vol.% 94.1 250 1.71 49 1.03 0.94 16

(2.5 wt.% Co) and 580 C (5.0 wt.% Co), and then completing synthesized using 2.5 and 5.0 wt.% Co, respectively, which
the oxidation process at 630 C and 670 C, respectively. corresponded to 12.0 and 22.0 vol.% of MWCNTs, referred to
Based on these data, the estimated weight loss associated to the Si3N4 powder. In comparison, commercial MWCNTs used
MWCNTs was 7.4 and 13.6 wt.% for the nanotubes for the ex-situ powder composition were more oxidation
342 CARBON 7 2 ( 2 0 1 4 ) 3 3 8 3 4 7
resistant, starting the oxidation process at higher tempera-
tures (500 C), although it ended at values close to the in-situ
CNTs (680 C), with an estimated weight loss of 7.8 wt.%.
The slight differences in the maximum weight loss between
the ex-situ and in-situ compositions containing 12 vol.%
CNTs (0.4 wt.%) could be associated to the difficulty to deter-
mine the weight loss of minor components, such as CNTs,
within the ceramic powder composition. From now, the nano-
composite specimens will be labeled according to their CNTs
volume content, i.e., 12 and 22 vol.%.
The TEM study (Fig. 2ac) showed that both commercial
and in-situ synthesized MWCNTs had an average diameter
of 15 nm, which is in good agreement with La values. FESEM
images revealed (Fig. 2d and e) that their average length were
in the range of 15 lm, with a high concentration of nano-
tubes grown into the ceramic powders, especially for a cata-
lyst content of 5.0 wt.% (Fig. 2e). Besides, in-situ synthesized
MWCNTs appeared homogenously distributed within the ma-
trix, whereas some nanotubes agglomerates were detected in
the ex-situ powder composition (Fig. 2d).
Table 1 summarizes some of the main microstructural
characteristics of the different SPSed specimens, including
the reference ex-situ 12 vol.% CNTs nanocomposite and the
monolithic material. Almost full densification was attained
for Si3N4 (99.9% qth) and nanocomposites containing
12 vol.% MWCNTs obtained by both methods, ex-situ (98.6%
qth) and in-situ (99.7% qth), although in the latter case the den-
sity was slightly higher probably due to a better distribution of
the nanotubes within the material. However, the in-situ
nanocomposite with the highest MWCNTs content (22 vol.%)
underwent a substantial decrease on the density (94.7% qth),
which is mainly due to the formation of a CNTs network that
hinders the densification of the composites [23,24].
The a-phase content for all the materials (Table 1) after the
sintering process was very similar (4249%), which allows
comparing their properties considering that, for instance, a-
phase materials are harder than b-phase ones. In addition,
Fig. 3 FESEM micrographs of the fracture surfaces corresponding to ex-situ 12 vol.% (a and d), in-situ 12 vol.% (b and e), and
in-situ 22 vol.% (c and f) MWCNTs nanocomposites. CNTs anchored to (e) or protruding from (f) the matrix are pointed by
arrows.
the use of the SPS technique avoided the nanotubes degrada-
tion during the sintering process at high temperature, as con-
firmed the almost negligible changes on the Raman ID/IG
values (Table 1).
At first glance, a good dispersion of the nanotubes within
the matrix was observed by FESEM on the fracture surfaces
of all MWCNTs nanocomposites (Fig. 3), including for the in-
situ 22 vol.% material (Fig. 3c). However, when the optical
images of the polished surfaces for the ex-situ and in-situ
specimens containing the same amount of CNTs (12 vol.%)
were compared (Fig. 4), a larger number of black spots, which
are linked to the presence of CNTs agglomerates, were ob-
served in the ex-situ composite (Fig. 4a). Therefore, this con-
firms that 5 wt.% can be considered the nanotubes content
threshold to fully disperse them into the material when col-
loidal processing is used. Interestingly, in-situ grown
MWCNTs also seem to be better anchored to Si3N4 grains
(Fig. 3e and f) than ex-situ commercial ones (Fig. 3d), which
can be evidenced by numerous examples of nanotubes bridg-
ing and pull-out (protruding) mechanisms in the in-situ mate-
rials pointed by arrows in Fig. 3e and f. These phenomena can
play an important role on the mechanical properties [7], as it
will be detailed below.
It is well known that the addition of CNTs refines the ma-
trix grain size when similar relative densities are compared
[23] and, in this sense, d50 and AR50 decreased from 297 nm
and 1.8, respectively, for monolithic Si3N4, to 200220 nm
and 1.5 for both 12 vol.% MWCNTs nanocomposites (Table 1).
Surprisingly, this trend does not continue for the in-situ
22 vol.% material, as its morphological parameters aug-
mented (d50 = 250 nm, AR50 = 1.7) compared to composites
having less amount of CNTs. This behavior could be ex-
plained considering Sudre et al.s model [25] for the densifica-
tion of ceramic powders containing non-sintering inclusions
and reinforcements, in the present case the nanotubes.
According to this model [25], compressive hydrostatic stress
field develops during sintering in areas between closely
 CARBON 7 2 (2 0 1 4) 3 3 834 7 343

Fig. 4 Optical images of the polished surfaces corresponding to 12 vol.% MWCNTs specimens obtained by the ex-situ (a) and
in-situ (b) methods. (A color version of this figure can be viewed online.)

spaced inclusions, and depends on the volume fraction and
aspect ratio of the inclusions. Those regions densify faster
and then become susceptible to grain growth, forming a rigid
network that constraints the adjacent porous area, which will
be subjected to tensile stresses that promote the desintering
phenomena in that region. As result, the material will be
formed by both fine grain porous areas and dense zones
showing large grain growth that would be the responsible
for the lower density and higher d50 and AR50 values of the
in-situ 22 vol.% MWCNTs. In fact, FESEM observations of the
polished and plasma etched surfaces for both in-situ compos-
ites (Fig. 5) clearly show their different microstructure. While
the composite containing 12 vol.% of nanotubes presents an
homogenous distribution of small equiaxed Si3N4 grains
without signs of porosity (Fig. 5a), the material with the larg-
est MWCNTs content exhibits dense areas with a bimodal
microstructure of matrix grains surrounded by local porous
regions (Fig. 5b), in good agreement with Sudre et al.s model
[25] described above.
Loaddisplacement curves as well as the elastic modulus
(E) and hardness (H) evolution with the peak load for the dif-
ferent materials are plotted in Fig. 6, while the estimated E
and H values are summarized in Table 2. The loaddisplace-
ment curves (Fig. 6a) showed a trend of increasing energy
absorption as CNTs content augmented. It can also be seen
that the in-situ 12 vol.% MWCNTs nanocomposites have a
much better reproducibility than the ex-situ ones due to the
best CNTs distribution within the matrix in the former mate-
rial. Regarding E (Fig. 6b) and H (Fig. 6c), the presence of nano-
tubes within the ceramic material considerably decreased
both parameters, which is a direct consequence of the high
deformability of CNTs [26], the insufficient load transfer be-
tween the matrix and the nanotubes, and the nanocomposite
microstructure, where the nanotubes appear bent and
twisted at Si3N4 grain boundaries enhancing the grain
boundary sliding [6]. Interestingly, despite this decrease, the
in-situ nanocomposite exhibited a better mechanical perfor-
mance than the ex-situ one comparing the same CNTs con-
tent, i.e., 12 vol.%, with an increment on E and H of 39% and
55%, respectively (Table 2) over the ex-situ composite. This
fact would confirm that the in-situ method promotes a stron-
ger mechanical interlock between the nanotubes and the
Si3N4 grains, similarly to the effect observed when CNTs are
functionalized [7]. However, the mechanical values in the
present case are still far from the monolithic material due
to the high CNTs loading. In addition, for the 22 vol.%
MWCNTs nanocomposite, the decrease on E and H is more
pronounced, which is also linked to the porosity of the nano-
composite (qth = 94.1%, Table 1).
The benefits of the in-situ process versus the ex-situ one
are also reflected on the fracture toughness (Table 2). In this
way, considering that the morphological parameters are sim-
ilar for both 12 vol.% MWCNTs nanocomposites (Table 1), the
in-situ one was 23% tougher (KIC = 4.4 MPa m1/2) than the
ex-situ nanocomposite (KIC = 3.6 MPa m1/2), which confirms
that toughening mechanisms like crack bridging or CNTs
pull-out have a major contribution in this material (Fig. 7)
due to both a stronger nanotube/matrix interface and better
nanotubes dispersion. Once more the monolithic material
exhibited better properties, but in this particular case mainly
associated to their matrix grain growth, with d50 and AR50
50% and 20%, respectively, higher than for the nanocompos-
ite (Table 1) that would considerably enhance KIC. On the
contrary, 22 vol.% nanocomposite present a low KIC value,
where the porosity (>5%) has a decisive role.
In a previous work, some of the authors found that the tri-
bological performance of the Si3N4 materials under simulated
GDI conditions continuously enhanced with the CNTs content
and the load [5]. The goal now is to evaluate if that enhance-
ment can be improved introducing a larger amount of CNTs

Fig. 5 FESEM micrographs of the polished and plasma etched surfaces corresponding to the in-situ composites containing
12 vol.% (a) and 22 vol.% (b) of MWCNTs. CNTs network in (b) is pointed by arrows.
344 CARBON 7 2 ( 2 0 1 4 ) 3 3 8 3 4 7

Fig. 6 (a) Loaddisplacement curves, and (b) elastic modulus (E), and (c) hardness (H) evolution versus the peak load (Pmax)
determined by the nanoindentation technique for the different materials. (A color version of this figure can be viewed online.)

Table 2 Mechanical properties of the monolithic Si3N4 and the nanocomposites containing MWCNTs obtained by the ex-situ
and in-situ methods: Elastic modulus (E), hardness (H), and fracture toughness (KIC).

Material E (GPa) H (GPa) KIC (MPa m1/2)

Si3N4 366 9 29.7 0.8 6.3 0.1

Ex-situ 12 vol.% 161 17 9.5 1.4 3.6 0.1
In-situ 12 vol.% 224 13 14.7 1.5 4.4 0.1
In-situ 22 vol.% 116 12 6.0 1.1 2.7 0.1

and, at the same time, if the processing route has any influ-
ence on the tribological parameters. For that reason only
12 vol.% MWCNTs compositions were selected and compared
with the monolithic material, 22 vol.% MWCNTs nanocom-
posite being not considered because of its lack of porosity
and mechanical properties.
The steady state friction coefficient and the wear volume
as a function of the applied load are plotted in Fig. 8. At low
load, 50 N, the lubricating effect of the nanotubes is clearly
visible for the ex-situ nanocomposite (Fig. 8a), decreasing
lss from 0.191, for Si3N4, to 0.128, for the nanocomposite;
whereas the in-situ material led to a moderate reduction on
lss (0.178). This different behavior between the nanocompos-
ites can be explained by their distinct MWCNTs/Si3N4
mechanical interlock that allows removing the nanotubes
from the ex-situ nanocomposite sliding surface more easily
than from the in-situ one and, hence, nanotubes started to
act as solid lubricant very soon. At 100 N, the in-situ nano-
composite exhibited a strong decrease on lss (0.120), the same
value than the ex-situ material and 32% lower than for the
monolithic. At the maximum load (200 N), the in-situ nano-
composite reached the lowest lss value (0.091) of all set of
materials, being 48% and 11% lower than the monolithic
and the ex-situ nanocomposite, respectively. Comparing with
the results previously reported for ex-situ materials contain-
ing 8.6 vol.% of MWCNTs using the same testing conditions
[5], where lss values of 0.180 and 0.102 were obtained at 50
and 200 N, respectively, the following conclusions can be
drawn: (i) larger nanotubes contents in ex-situ materials
accelerate the lubricating effect at low loads although no sig-
nificant differences can be found at high loads, (ii) when
nanotubes were in-situ grown their activation as solid
lubricants at low loads is retarded due to their higher
mechanical interlock, but after exceeding a load threshold
 CARBON 7 2 (2 0 1 4) 3 3 834 7 345

of 50 N the in-situ nanocomposite exhibits a significant

reduction on friction. This fact is a consequence of the high
nanotubes loadings and the homogeneous CNTs distribution,
which leads to an enhanced mechanical performance as well,
compared to the ex-situ nanocomposites.
Regarding the wear behavior, in-situ MWCNTs nanocom-
posites were the most wear resistant materials in the whole
range of loads (Fig. 8b), showing a remarkable decrease on
WV of 7287% and 5765% compared to the monolithic and
the ex-situ nanocomposite, respectively. Previous results at-
tained with ex-situ nanocomposites tested under the same
conditions [5] pointed out that nanotubes improved the wear
resistance of Si3N4 materials due to both their high shear
deformability and their location at the grain boundaries,
which promoted the redistribution of the stress field and,
hence, limited the growth of long cracks. Besides, a progres-
sive decrease of Wv with the nanotubes content was ob-
served, reaching a minimum WV value at 200 N of
1.84 103 mm3 for 8.6 vol.% MWCNTs nanocomposites [5].
However, if these results are plotted in the same graph than
the new ones obtained in the present work (Fig. 8c), it can
Fig. 7 FESEM micrographs showing toughening
be seen that the WV trend changes and increases for
mechanisms, such as MWCNTs bridges and pull-out, on the
nanotubes contents higher that 8.6 vol.%, the ex-situ
in-situ 12 vol.% nanocomposite at low (a) and high (b)
12 vol.% MWCNTs nanocomposite becoming less wear resis-
magnification.
tant, especially at high loads (WV = 2.83 103 mm3). This

Fig. 8 Average steady-state friction coefficient, lss, (a) and wear volume, WV, (b) data versus the applied load for Si3N4 and the
nanocomposites containing 12 vol.% of MWCNTs (ex-situ and in-situ). (c) Average WV versus the MWCNTs content for the
different loads, where previous data reported for ex-situ nanocomposites [5] are plotted with the new results obtained in the
present work. Full and empty symbols in (c) correspond to ex-situ and in-situ nanocomposites, respectively. Ex-situ results
are fitted using dashed lines, whereas straight lines connect in-situ values with previous reported data. (A color version of
this figure can be viewed online.)
346 CARBON 7 2 ( 2 0 1 4 ) 3 3 8 3 4 7
Fig. 9 FESEM micrographs of the worn surfaces tested over a sliding distance of 360 m at 200 N corresponding to monolithic
Si3N4 (a and d), ex-situ (b and e), and in-situ (c and f) 12 vol.% MWCNTs nanocomposites.
can be explained mainly by the formation of nanotubes
agglomerates during the ex-situ process of this nanocompos-
ite and their worse mechanical properties [5]. Interestingly,
the in-situ 12 vol.% MWCNTs nanocomposite (empty symbols
in Fig. 8c) fits quite well to the expected tendency of WV with
MWCNTs content if they were well dispersed into the mate-
rial. Furthermore, their mechanical properties are compara-
tively better, as it has been previously explained (Table 2).
The worn surfaces for the different materials tested at
200 N are shown in Fig. 9, illustrating the wear evolution
through the different specimens. In general, wear debris were
formed by the action of the microabrasion mechanism, being
compacted during the motion of the sliding pairs. In the case
of the most wear resistant material, the in-situ composite,
numerous compacted debris areas appeared well adhered to
the surface (Fig. 9c and f), which protected it against wear.
In the case of the ex-situ composite, the high contact pres-
sures attained during the sliding test cracked the debris layer
(Fig. 9b and e), starting to spall-off it and producing an incre-
ment on WV. This situation became more dramatic in the
monolithic specimen, the less wear resistant, as it can be
seen through the numerous wear craters exhibited on the
worn surface (Fig. 9a and d). In spite of this, all the materials
showed low WR values, in the order of 108 mm3 N1 m1, that
correspond with a mild wear process.
Last but not least, some of the future applications of Si3N4
materials will depend on the availability to manufacture 3D
micro-components for transportation/energy (micro-rotor or
micro-turbines), communications (MEMS/NEMS) or biomedi-
cal (implants) sectors. In this sense, EDM emerges as a suc-
cessful technique to get this goal if Si3N4 becomes an
electrical conductor [10], an issue that can be achieved intro-
ducing CNTs. Considering the excellent tribological proper-
ties attained with the in-situ CNTs/Si3N4 nanocomposites,
and the improvement on the mechanical properties com-
pared to those of ex-situ nanocomposites, DC electrical con-
ductivity was determined in dense and well dispersed
12 vol.% MWCNTs nanocomposites. A value of 313 S m1
was measured, about 15 orders of magnitude higher than
for the monolithic material (re 1013 S m1), although it is
slightly lower than that obtained for more crystalline com-
mercial MWCNTs (474 S m1 for 5.6 vol.% nanocomposite)
[9]. However, that electrical conductivity would be high en-
ough to assure a good EDM performance, where a minimum
re value of 1 S m1 is required.
4. Conclusions
Highly homogenous MWCNTs/Si3N4 nanocomposites con-
taining up to 22 vol.% of nanofillers are developed in-situ
growing the nanotubes into the ceramic powder composition
by means of cobalt catalyst assisted CVD method. Full densi-
fication of the nanocomposites with MWCNTs contents up to
12 vol.% is attained, avoiding at the same time the nanotubes
degradation during the SPS process. Compared to ex-situ
nanocomposites, in-situ ones exhibit much higher MWCNTs
dispersion and a stronger nanotube/matrix interface than
leads to an improved mechanical performance. In addition,
these nanocomposites exhibit an excellent tribological
behavior, being 87% and 65% more wear resistant than Si3N4
materials and ex-situ nanocomposites, respectively, also
leading to the lowest friction at high contact pressures, allow-
ing their use as components in GDI systems. The results con-
firm the benefits of high nanotubes loadings and the success
of the in-situ CNTs growing process to disperse high nanofil-
lers contents within the matrix, allowing the use of these
nanocomposites in emerging applications where multifunc-
tionality (electrical, mechanical, tribological) is required.
Acknowledgements
This work was supported by the Spanish Government under
the projects MAT2009-09600 and MAT2012-32944.
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