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Scripta Materialia 58 (2008) 520–523

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Zirconia/carbon nanofiber composite

Annamária Duszová,a Ján Dusza,b,* Karel Tomášek,a Jerzy Morgiel,c
Gurdial Blugand and Jakob Kueblerd
a
Technical University of Košice, Faculty of Metallurgy, Letná 9, 042 00 Košice, Slovak Republic
b
Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 04353 Košice, Slovak Republic
c
Institute of Metallurgy and Materials Science of Polish Academy of Sciences, Reymonta 25, 30 059 Krakow, Poland
d
Empa, Swiss Federal Laboratories for Materials Testing and Research, Laboratory for High Performance Ceramics,
8600 Duebendorf, Switzerland
Received 28 September 2007; revised 2 November 2007; accepted 4 November 2007
Available online 3 December 2007

The effect of the addition of carbon nanofibers (CNFs) on the microstructure, fracture/mechanical and electrical properties of the
CNF/zirconia composite has been investigated. The microstructure of both ZrO2 and ZrO2–CNF composites consists of a very low
grain sized matrix (approximately 160 nm) with relatively well dispersed carbon nanofibers in the composite. The mechanical prop-
erties slightly decreased after the addition of CNFs to the ZrO2 but the electrical resistivity decreased significantly, exhibiting
approximately 0.1 X cm.
Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: 3Y-TZP; Carbon nanofiber; Microstructure; Fracture; Electrical resistivity

During the last few years new ceramic/carbon nano-
tube composites have been developed with two aims: to
improve the mechanical properties of the ceramic mate-
rials by reinforcing with carbon nanotubes (CNTs) and
to develop functionalized ceramics with improved mag-
netic and electrical properties [1–3]. It seems that single-
wall CNTs (SWCNTs) or multi-wall CNTs (MWCNTs)
should be ideal reinforcing/functionalizing elements for
composites due to their small size, low density, high
aspect ratio, exceptional high tensile strength, and high
electrical and thermal conductivity. A number of
authors have reported improved mechanical and func-
tional properties in the case of ceramic/CNT composites
compared with the monolithic material [4–6]. According
to the results of Zhan et al. [3], CNT/ceramic nanocom-
posites exhibit thermoelastic properties which give them
the potential for use as promising thermoelastic materi-
als. The investigations to date have focused mainly on
alumina-based ceramic composites, with only limited
work having been done on other systems, e.g. those
based on silicon nitride or zirconia [7–10].
Zirconia (3Y-TZP) is a material extensively used for
many structural applications due to its good mechanical
* Corresponding author. E-mail: jan_dusza@yahoo.co.uk
properties. Zirconia and/or zirconia-based composites
are interesting multifunctional materials that have been
used for many applications, such as solid-oxide fuel
cells, oxygen sensors and ceramic membranes, due to
their good high-temperature stability, high breakdown
electrical field or large energy bandgap [11].
As well as CNTs, there are similar carbon-based fila-
mentous nanomaterials, e.g. hollow carbon fibers or car-
bon nanocoils, with similar mechanical and electrical
properties but with slightly different sizes and shapes,
which can also be utilized as reinforcing elements in
ceramic-based composites [12–14].
The aim of the present contribution is to investigate
the influence of carbon nanofiber additions on the
microstructure, mechanical, fracture and electrical prop-
erties of zirconia.
The starting materials were ZrO2 powder (TZ-3Y,
Tosoh, Japan) and carbon nanofiber (1.07 wt.%). Car-
bon nanofiber (HTF150FF, Electrovac, Austria) with
an average diameter of 80–150 nm, specific surface area
in the range of 20–100 m2 g 1, Young’s modulus
500 GPa, tensile strength 7 GPa and electrical
resistivity of 10 3–10 4 X cm was used. A water-based
mixture was prepared with dispersant (DODECYLE
MARANIL), carbon nanofibers (CNFs), ZrO2 and
a polyvinylbutryl binder (MOWITAL B30T). The

1359-6462/$ - see front matter Ó 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2007.11.002
 A. Duszová et al. / Scripta Materialia 58 (2008) 520–523
dispersion was primarily done using ultrasonics and a
magnetic stirrer. After the dispersion, the mixture was
subsequently spray dried. Specimens in the form of discs
with diameter of 10 and 20 mm were die pressed and
then hot-pressed at 1300 °C and 40 MPa in argon. For
comparison, monolithic ZrO2 was prepared under
similar conditions (but without any binder).
The CNFs have been characterized by scanning and
transmission electron microscopy (SEM, TEM; Jeol
Ltd). The density of the experimental materials has been
measured using the Archimedes method. X-ray diffrac-
tion (XRD) analysis (Phillips, X-pert) was used for the
determination of the phase composition of the experi-
mental materials. Specimens for microstructure exami-
nation were prepared by diamond cutting, grinding,
polishing and thermal etching. The microhardness (Leco
instruments) and hardness were studied by the Vickers
indentation method at loads from 0.25 to 150 N. Inden-
tation toughness testing was carried out for estimation
of the toughness of the materials at 150 N using a Vick-
ers indenter and the Shetty equation [15].
The microstructure and the fracture surface of the
materials were studied using SEM. The specimens were
thermally etched at a temperature of 1250 °C and micro-
fractography was used to analyse the fracture lines and
surfaces of the specimens.
The electrical resistivity was measured at room
temperature using a four-point method. Specimens of
dimensions of 1.5 mm  1.5 mm  10 mm were cut
from the center of the hot-pressed samples for these
measurements.
The SEM and TEM analysis revealed that the CNFs
used are in two forms: pipe-shaped hollow nanofibers,
with an outside diameter of approximately 150–200 nm
and an inside diameter of approximately 80 nm; and
nanofibers with a ‘‘bamboo-like” structure consisting
of several lateral units (Fig. 1a and b).
The hot-pressed monolithic zirconia exhibits full den-
sity but the density of the ZrO2–CNF composite was
lower due to the porosity in the composite attributable
mainly to the clusters of CNFs present in its microstruc-
ture. XRD analysis revealed that the experimental mate-
rials consist of mainly t-ZrO2; however, a small amount
of monoclinic zirconia and yttrium oxide carbide has
also been found.
In Figure 2 the microstructure of the bulk zirconia
and the composite is illustrated. The monolithic zirconia
consists of very small, submicron/nanometer-sized
grains with randomly occurring defects in the form of
Figure 1. Characteristic shapes of the carbon nanotubes used, as
determined by SEM and TEM.
521
Figure 2. Microstructure of monolithic zirconia (a) and the CNF/
zirconia (b) composite, as seen by thermal etching/SEM.
very small pores, approximately 100–200 nm in diameter
(Fig. 2a). The microstructure of the composite consists
of similar sized or an even smaller grained matrix with
relatively well dispersed CNFs (pores with their shape/
orientation indicating the locations of the burned out
CNFs during the thermal etching) in the matrix
(Fig. 2b). The smaller grain size of the zirconia in the
composite compared with the monolithic material is evi-
dence that the CNFs may hinder the grain growth in the
composite during the sintering.
A relatively high number of clusters of CNFs were
found on the polished surface and the fracture surface
of the samples, indicating that the mixing procedure needs
to be improved (Fig. 3). The size of the clusters varies from
a few microns up to approximately 20 lm, and porosity
was always connected with these clusters. The presence
of such clusters in the composite connected with porosity
is the main reason for the lower density compared with the
theoretical one (approximately 5.8 g cm 3).
In Table 1 the basic properties such as the hardness
and indentation toughness is presented together with
the values of the electrical resistivity for the monolithic
zirconia and for the composite. The hardness and inden-
tation toughness decreased after addition of CNFs to
the zirconia. On the other hand, the electrical resistivity
decreased significantly, from a very high value of
approximately 1012 (the exact value was not possible
to measure because the resistivity was so high it was be-
yond the limitations of our measuring equipment) to a
value of 0.105 X cm.
Figure 3. Cluster of CNFs accompanished with porosity on the
fracture surface, as seen by SEM.
Table 1. Properties of the investigated materials
Material/ Density HV1 KI-indentation Electrical
properties (g/cm3) (km/mm2) (MPa m0.5) resistance
(X cm)
ZrO2 6.05 1395 ± 26 6.24 ± 0.1 ca. 1.0  1012
ZrO2–CNF 5.22 830 ± 28 5.60 ± 0.15 0.105 ± 0.05
522 A. Duszová et al. / Scripta Materialia 58 (2008) 520–523
The fracture mechanisms in the bulk zirconia mate-
rial are mainly intergranular, with very little roughness
of the fracture lines/surface, only apparent at the nano-
meter scale. No toughening mechanisms were revealed
on the fracture lines/surfaces in this system. The com-
posite reinforced by CNFs exhibits a slightly different
behavior, with rougher fracture line/surfaces and crack
deflection at the larger singular CNFs (Fig. 4a). The
crack deflection is similar to that seen in whisker-rein-
forced ceramics, and represents one of the toughening
mechanisms in similar systems which can improve the
fracture toughness of composites. Besides the crack
deflection, crack bridging and CNF pull-outs were often
detected on the fracture surface of the failed composite;
however, the pull-out length was usually short (Fig. 4b).
Comparing the results of the present investigation
with the results of a similar study, there are two main
differences in the processing step. In our investigation
we used CNFs with different geometry, with a larger
diameter and a lower aspect ratio, compared with the
CNTs in the similar investigations of ZrO2–CNT sys-
tems. The second difference was in the way the mixture
was sintered: we used hot pressing, while similar investi-
gations used spark plasma sintering (SPS) or pressure-
less sintering + post-hot isostatic pressing (HIP)
treatment.
The thermoelectric properties of 10 vol.% SWCNT/
3Y-TZP composite produced by SPS have been studied
by Zhan et al. [3]. According to these results, the
electrical resistivity increased from approximately
0.02–0.5 X cm when the temperature increased from
temperature to 545 K. Further increasing the testing
temperature resulted in the slight decrease in electrical
resistivity. Shi and Liang studied the effect of the
MWCNT addition on the electrical and dielectric prop-
erties of MWCNT/3Y-TZP composite prepared by the
SPS method [16]. They found a low percolation thresh-
old of 1.7 wt.% of MWNTS for the composite and
found the system attractive for some electrical applica-
tions. MWCNT/3Y-TZP composite was prepared by
pressureless sintering + HIP by Ukai et al. [6]. For the
materials with CNTs from 0.25 to 1.0 wt.% the electrical
resistivity was found to be in the interval from 21 to
1.7 X cm, in very good agreement with our results. The
electrical resistivity in our case was even lower than
the results of Ukai et al., indicating the potential of
the whisker-like nanotubes for improving the function-
ality of the ceramics.
There are only a limited number of publications deal-
ing with the mechanical properties of CNT/ZrO2 com-
posites [5,6].
Figure 4. Fracture surface in the CNF/zirconia composite illustrating
the crack deflections at CNFs.
Sun et al. [5] studied the mechanical and fracture
behavior of MWCNT/3Y-TZP composites containing
0.1–1.0 wt.% MWCNTs and SWCNTs prepared by
SPS. They found that the addition of CNTs had a negative
influence on the hardness of the composites and no influ-
ence (at 0.5 wt.%) or a negative influence on the fracture
toughness. Comparing the influence of the addition of
SWCNTs and MWCNTs on the fracture toughness, they
found that the MWCNT are more effective in the tough-
ening. However, they used the indentation technique for
the toughness measurements, which is useful only for
comparison purposes, cannot be considered a true mate-
rial property and also tends to overestimate the KIc value
as described by Quinn et al. [17]. Similar results were
found by Sun et al. [6], who studied the failure properties
of MWCNT- and SWCNT-reinforced zirconia prepared
by the SPS process. According to them, the CNTs often
agglomerate at the ZrO2 boundaries, and the weak bond-
ing between the CNTs and zirconia are the reason why the
reinforcing effect of the CNTs is limited. The results of the
present investigation are in a very good agreement with
these results and with the results of Ukai et al. [6] as re-
gards the influence of the CNTs addition on the mechan-
ical properties of zirconia (Fig. 5).
As regards the mechanical properties, our results
show that even the use of relatively coarse whisker-like
CNFs is not effective in toughening the zirconia ceramic
matrix at the current amounts used. On the other hand,
we have to note that on the fracture surface/line we fre-
quently found different toughening mechanisms, mainly
in the form of crack deflection at the CNFs. The reason
for the relatively low indentation fracture toughness is
probably the poor dispersion and therefore the limited
toughening effect of the CNFs. A more reliable
technique (e.g. SEVNB ref.) has to be used for the mea-
surement of the fracture toughness on fully dense com-
posites to obtain information concerning the true effect
of the CNFs on the fracture toughness. However, the
indentation test can be used for characterization of dif-
ferent mechanical/damage properties of CNT- and
CNF-reinforced composites. Wang et al. [18] investi-
gated the contact-damage resistance of dense Al2O3/
SWNT composites prepared by the SPS method. Vick-
ers and Hertzian indentation tests revealed that these
composites are highly contact-damage resistant due to
the shear-deformable SWNTs heterogeneities in the
composites which help redistribute the stress field under
Figure 5. Influence of the CNT addition on the Vickers hardness and
indentation toughness of the CNT/3Y-TZP composites [5,6].
 A. Duszová et al. / Scripta Materialia 58 (2008) 520–523
indentation, imparting the composites with contact-
damage resistance.
The lesser hardness of the composite compared with
the monolithic material is dependent on the residual
porosity which remains in the material after sintering,
similar to that observed in other investigations [5]. To-
gether with the porosity, the clusters of the CNFs/CNTs
are characteristic processing defects present in our mate-
rial and presented in all contributions dealing with
similar composites. This indicates that there are still
difficulties in the preparation of defect-free CNT- or
CNF-reinforced ceramic composites, but that there is
potential for the improvement of their functional and
mechanical properties.
Dense ZrO2/carbon nanofiber composites have been
developed which exhibit slightly lower mechanical prop-
erties but significantly higher electrical conductivity
compared with monolithic zirconia. The results point
out the possibilities of improving the mechanical and
functional properties of the ZrO2/carbon nanofiber
composites by further optimizing the processing route
of the composite. A future goal is to produce fully dense
composites with improved dispersion of the CNFs.
A.D. acknowledges the financial support of Empa
during her stay there with the aim to prepare her diplo-
ma thesis. Further, the authors would like to thank Iza-
bel Silveira, Katarina Ďurišinová and Marián Mihalik
for their help with the dispersion of the CNT, XRD
measurements and electrical resistivity measurements,
respectively. The work was supported by NANO-
SMART, Centre of Excellence, SAS, by the Slovak
Grant Agency for Science, grant No. 2/7914/27 and by
the KMM-NoE EU 6FP Project.
523
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