Materials Science and Engineering A 554 (2012) 15

Contents lists available at SciVerse ScienceDirect

Materials Science and Engineering A
j our nal homepage: www. el sevi er . com/ l ocat e/ msea
Preparation and mechanical properties of NiCrAl
2
O
3
ZrO
2
(8Y) ceramic
composites
Feng-Jiao Liu
a
, Ming-Hao Fang
a,b,
, Zhao-Hui Huang
a
, Yan-Gai Liu
a
, Sai-Fang Huang
a
,
Xin Min
a
, Mei-Ling Hu
a
, Hai-Peng Ji
a
a
School of Materials Science and Technology, China University of Geosciences (Beijing), Beijing 100083, PR China
b
Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109, USA
a r t i c l e i n f o
Article history:
Received 29 July 2011
Received in revised form6 March 2012
Accepted 3 May 2012
Available online 2 June 2012
Keywords:
Zirconia ceramic composite
NiCr alloy
Carbothermal protecting sintering, SOFC
anodic material
Strengthening and toughening
a b s t r a c t
The mechanical properties of the 8 mol% yttria stabilized zirconia (8YSZ), as a promising anodic material
for solid oxide fuel cell, should be improved to increase its reliability and service life. NiCrAl
2
O
3
ZrO
2
(8Y)
ceramic composites were successfully fabricated by pressureless sintering in the carbothermal protecting
atmosphere, and the mechanical properties and microstructure were investigated as well. The results
showed that 8YSZ matrix composites had good mechanical properties due to the NiCr alloy and -Al
2
O
3
secondary phases. The bending strength and fracture toughness could reach at a range of 224300 MPa,
3.84.6 MPa m
1/2
, respectively, when 012vol.% of NiCr alloy and 10 vol.% alumina particles were added
into 8YSZ ceramic. 10vol.% -Al
2
O
3
obviously enhanced the densication of the 8YSZ ceramic.
2012 Elsevier B.V. All rights reserved.
1. Introduction
In recent decades, the 8mol.% yttria stabilized cubic zirco-
nia ceramic (8YSZ) without phase transformation has attracted
increasing attention as a promising anodic material for solid oxide
fuel cells (SOFC) because of its excellent ionic conductivity [14].
Therefore, the functionality of 8YSZ ceramic has been extensively
studied and notably enhanced. The mechanical properties, how-
ever, should be improved to increase its reliability and service
life, considering that the pure 8YSZ ceramic has poor strength
and toughness of about 200MPa and 1.72MPa m
1/2
[5,6]. It is an
attractive method to fabricate zirconia matrix ceramic composite
reinforced by secondary phases of metal [7] and ceramic particles
[8,9] via various mechanisms. It has been reported that the tough-
ness of 8YSZ ceramic can be improved by nickel particle [10]. But,
it is known that the ceramic composite toughened by ductile metal
particles always has a decreased strength.
In the present work, we aimto develop 8YSZ ceramic compos-
ites with good mechanical properties reinforced by Ni80Cr20 alloy
and -Al
2
O
3
particles. This composite could be an alternative can-
didate material used as the anode of SOFC. This paper focuses on

Corresponding author at: School of Materials Science and Technology, China

Universityof Geosciences (Beijing), Beijing100083, PRChina. Tel.: +861082322186;
fax: +86 10 82322186.
E-mail address: fmh@cugb.edu.cn (M.-H. Fang).
the preparation, phase composition, and mechanical properties.
The effects of Ni80Cr20 alloy and -Al
2
O
3
particles addition on
the bending strength, fracture toughness and hardness of the 8YSZ
ceramic matrix composite were also studied.
2. Experimental details
The raw materials were as follows: 8YSZ (Fanmeiya (Jiujiang)
High-Tech Material Limited, China); -Al
2
O
3
(Tongtai Powder
TechnologyLimited, Chongqing, China) andNi80Cr20alloy(Mining
and Metallurgy Institute of General Research, Beijing, China). The
characteristics of the starting powders are described in Table 1.
The compositions of 8YSZ matrix composites are shown in
Table 2. Various volume fractions of 0, 6%, 12%, 18%, 24% and 30%
of NiCr alloy powder were added to the 8YSZ powders, with a xed
additionof 10vol.%Al
2
O
3
(notedas samples S0S5). Andthesample
8Ywithpure 8YSZ was also set as a comparison. After ball milling in
ethanol for 6h, the as-prepared slurries were dried in rotary evap-
orator at 60

C for 20min and in oven at 100

C for 3h, followed by

sifting with a sieve size of 150mand die-pressing with the max-
imum pressure of 40MPa to get the 4mm6mm40mm green
bars. Subsequently, they were further compacted by cold isostatic
pressingat 200MPa for 1min. Finally, thegreenbars werepressure-
less sintered at 1550

C for 3h in a weak carbothermal protecting

atmosphere, because excessive carbon in atmosphere would cause
the precipitation of yttria. So in this work, a spot of carbon powder
was introduced and placed at the top of the sagger and departed
0921-5093/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msea.2012.05.004
2 F.-J. Liu et al. / Materials Science and Engineering A 554 (2012) 15
Table 1
Starting powders characteristics.
Materials Purity (%) d
50
(m)
8YSZ 99.90% 0.7
containing Y
2
O
3
-Al
2
O
3
99.90% 0.5
Ni80Cr20 alloy Ni 79.60wt.%; 10
Cr 19.90wt.%
Table 2
Compositions of samples.
Specimen 8YSZ (vol.%) Al
2
O
3
(vol.%) NiCr (vol.%)
8Y 100 0 0
S0 90 10 0
S1 84 10 6
S2 78 10 12
S3 72 10 18
S4 66 10 24
S5 60 10 30
Fig. 1. The schematic diagramof carbothermal protecting sintering approach.
from the green compacts by alumina hollow spheres as shown in
Fig. 1. During sintering process, the oxygen in the sagger was con-
sumed by carbon, and the metal or alloy component was protected
from oxidation. This preparation method can serve as a relatively
low-cost route for fabricating the metal/alloy containing compos-
ites.
The bulk density of the prepared composites was measured by
Archimedes method, and the phase compositions of them were
determined by X-ray Diffractometer (XRD) with Cu K
1
radiation.
Microstructure of the composites was observed using scanning
electron microscopy (SEM, Hitachi JSM-6460LV) with energy dis-
persive analysis (EDS).
The bending strength was determined using three-point bend-
ing method. The fracture toughness was measured via single edge
notchbeam(SENB) three-point bendingmethodaccordingtoASTM
C1421-01b(R2007) using the bars with 5mm4mm30mm
dimensions, with a span of 20mm at a cross-head speed of
0.05mmmin
1
. The depthof the notches was about 2.5mmandthe
width was 0.2mm. The Rockwell hardness (HRA) of the composites
was measured under a load of 60kg holding for 10s.
3. Results and discussion
3.1. Phase composition and microstructure of samples
According to the NiCr binary phase diagram, liquid phase
appears when the temperature is over 1450

C. The sintering tem-

perature was 1550

C in the present work to get a fully sintered

Fig. 2. XRD patterns of NiCr alloy and 8YSZ matrix composites (8Y, S0S5) sintered
at 1550

C for 3h.
NiCr-alloy containing 8YSZ matrix composite. Only a little bit of
alloyphaseexudedtothecompositesurfacewhenthenominal con-
tent of alloy was more than 24vol.%, because zirconia ceramic was
the continuous phase and NiCr alloy was discrete phase. Therefore,
the calculated actual content of NiCr alloy in S4 and S5 was 23vol.%
and 27vol.%, respectively.
The phase compositions of the samples are shown in Fig. 2. As
can be seen, the main phases of sintered samples were c-ZrO
2
,
Ni, and -Al
2
O
3
. It should be mentioned that only nickel can be
detected by XRD because chromiumentered into the lattices of Ni
to form a Ni based solid solution. According to the SEM image of
the polished surface of sample S2 which is shown in Fig. 3, the
-Al
2
O
3
crystals (dark grey areas) were evenly distributed in the
zirconia matrix. An interface appeared around the NiCr alloy parti-
cles as shown in Fig. 4(a). This interface is possibly a solid solution
producedbyCr atoms comingintothelatticeof thealumina accord-
ing to the EDS patterns and the atomic percentage of O, Al, Cr as
shown in Fig. 4((c) and (d)). Some micro-pores were also found in
the composite.
The relative density of NiCrAl
2
O
3
ZrO
2
(8Y) ceramic compos-
ites as a function of the volume addition of NiCr alloy is shown in
Fig. 5. As it can be seen that, the sample S0 exclusively adding with
-Al
2
O
3
hadthe highest relative densityof 99.9%amongthese sam-
ples. And the relative density of samples S1S5 initially raised with
the increasing volume addition of NiCr alloy, and then gradually
decreased. The samples S1 and S2, adding with 6vol.% and 12vol.%
of NiCr alloy as well as 10vol.% -Al
2
O
3
, showed higher relative
density (96.7% and 97.4%, respectively) than pure 8YSZ ceramics
(96.6%). Theexudationof theNiCr alloymight betheprimaryreason
contributed to the decrease of density of samples S4 and S5.
It is believed that a proper amount of NiCr alloy and -Al
2
O
3
can
promote the densication of 8YSZ matrix composite, which makes
contribution to the improved mechanical properties as discussed
below.
3.2. Mechanical properties of samples
The mechanical properties of NiCrAl
2
O
3
ZrO
2
(8Y) compos-
ites are shown in Fig. 6. As is shown in Fig. 6(a), the fracture
toughness initially increased and reached a maximum value of
4.6MPa m
1/2
when the addition of NiCr alloy is 12vol.% (sample
S2), and then declined with the increase of NiCr alloy addition. The
fracture toughness of all samples S0S5 with additives, at a range
F.-J. Liu et al. / Materials Science and Engineering A 554 (2012) 15 3
Fig. 3. (a) Morphology and (b) EDS pattern of -Al
2
O
3
particles in NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composites (sample S2).
of 3.44.6MPa m
1/2
, were much higher than that of the pure 8YSZ
ceramic (2.0MPa m
1/2
) whichwas fabricatedinthe same condition.
The pure 8YSZ ceramic prepared in this work was about 54% higher
than the pure 8YSZ ceramic (1.3MPa m
1/2
) prepared at 1400

C
for 2h by Nam-Hee Kwon et al. [11]. For a comparison, the fracture
toughness of 8YSZ ceramic hot pressed at 1300

C was 2.2MPa m
1/2
[8].
Obviously, thepreparedNiCrAl
2
O
3
ZrO
2
(8Y) ceramic compos-
itehadmuchbetter toughness thanpure8YSZceramic. Thepossible
toughening mechanisms are as follows. The plastic transformation
of ductile NiCr alloy could absorb and consume the crack propaga-
tion energy. The addition of Al
2
O
3
particles can also enhance the
fracture toughness of the ceramic composites by blocking the prop-
agationof thecrackandextendingthecrackpropagationpathwhen
primarycracks comeacross as showninFig. 7. Bothof theabovetwo
ways can improve the fracture toughness of NiCrAl
2
O
3
ZrO
2
(8Y)
ceramic composite. However, due to the lower density, the
fracture toughness of NiCrAl
2
O
3
ZrO
2
(8Y) composites declined
gradually when the addition of NiCr alloy was more than
12vol.%.
The bending strength of NiCrAl
2
O
3
ZrO
2
(8Y) composites as a
function of the volume addition of NiCr alloy is shown in Fig. 6(b).
The results indicated that the bending strength had a similar
tendency with the density of the composites, and reached the max-
imumvalue of 303MPa (sample S0 containing 10vol.% -Al
2
O
3
). It
is consideredthat the density was one of the major factors inuenc-
ing the bending strength of materials. Excessive NiCr alloy (more
than 12vol.%) can decrease the strength of the composite. Among
those samples with various addition of NiCr alloy, the sample S2
(12vol.% NiCr alloy and 10vol.% -Al
2
O
3
) had the highest bending
strength of 224MPa, which was 50% higher than that of pure 8YSZ
ceramic sample.
Rockwell hardness of the samples, as shown in Fig. 8, decreased
gradually with the increasing addition of NiCr alloy. The same
Fig. 4. (a) Morphology and (b) EDS pattern of NiCr alloy particle, (c) weight and atomic percentage and (d) EDS pattern of the interface around NiCr alloy particle in
NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composites.(sample S3).
4 F.-J. Liu et al. / Materials Science and Engineering A 554 (2012) 15
Fig. 5. The relative density of NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composite as a function
of the volume addition of NiCr alloy.
tendency was also found by Zhu et al. [12] and Jin et al. [13]. It is
a general knowledge that the added ductile metal and alloy can
decrease the hardness of ceramic composites.
Based on the mechanical properties of samples discussed
above, the addition of NiCr alloy can be optimized to be
012vol.% when 10vol.% -Al
2
O
3
was co-added into 8YSZ
ceramic. With the above suggested compositions, the bending
strength, fracture toughness and Rockwell hardness (HRA) could
reach at a range of 224300MPa, 3.84.6MPa m
1/2
and 8089,
respectively.
Fig. 6. (a) Fracture toughness and (b) bending strength of NiCrAl
2
O
3
ZrO
2
(8Y)
ceramic composite as a function of the volume addition of NiCr alloy.
Fig. 7. The function of Al
2
O
3
particles in blocking crack propagation in the
NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composites.
Fig. 8. Rockwell hardness of NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composite as a function
of the volume addition of NiCr alloy.
4. Conclusions
The NiCrAl
2
O
3
ZrO
2
(8Y) ceramic composites were success-
fully fabricated by the low cost carbothermal-protecting sintering
process. NiCrAl
2
O
3
ZrO
2
(8Y) composites showed higher fracture
toughness and bending strength than pure 8YSZ ceramic when
012vol. % of NiCr alloy and 10vol. % alumina particles were added
into 8YSZ ceramic. 10vol. % -Al
2
O
3
can enhance the densication
of the 8YSZ ceramic. The bending strength, fracture toughness and
Rockwell hardness (HRA) could reach at a range of 224300MPa,
3.84.6MPa m
1/2
and 8089, respectively, although the hardness
showed a slight decrease. The good mechanical properties mainly
attribute to the NiCr alloy particles and -Al
2
O
3
particles blocking
the propagation of the crack and extending the crack propagation
path.
Acknowledgements
This work was nancially supportedby the National Natural Sci-
ence Foundation of China (NSFC Grant Nos. 50802091, 50972134
and 51032007) and Fundamental Research Funds for the Central
Universities (Grant No. 2011PY0170 and 2010ZY31).
References
[1] H.S. Hong, U.S. Chae, S.T. Choo, K.S. Lee, J. Power Sources 149 (2005) 8489.
[2] E. Chinarro, F.M. Figueiredo, G.C. Mather, J.R. Jurado, J.R. Frade, J. Eur. Ceram.
Soc. 27 (2007) 42334236.
[3] Z.G. Lv, P. Yao, R.S. Guo, F.Y. Dai, Mater. Sci. Eng. A 458 (2007) 355360.
F.-J. Liu et al. / Materials Science and Engineering A 554 (2012) 15 5
[4] A.N. Kumar, B.F. Srensen, Mater. Sci. Eng. A 333 (2002) 380389.
[5] N. Bamba, Y.H. Choa, T. Sekino, K. Niihara, J. Eur. Ceram. Soc. 18 (1998) 693699.
[6] M. Ghatee, M.H. Shariat, J.T.S. Irvine, Solid State Ionics 180 (2009) 5762.
[7] A.M. Rodrguez, A.B. Len, G. Richter, M. Rhle, A.D. Rodrguez, M.J. Melendo,
Scripta Mater. 54 (2006) 20872090.
[8] L. Donzel, S.G. Roberts, J. Eur. Ceram. Soc. 20 (2000) 24572462.
[9] A.J. Feighery, J.T.S. Irvine, Solid State Ionics 121 (1999) 209216.
[10] X. Jin, L.Z. Wu, L.C. Guo, H.J. Yu, Y.G. Sun, Eng. Fract. Mech. 76(2009) 18001810.
[11] N.H. Kwon, G.H. Kim, H.S. Song, H.L. Lee, Mater. Sci. Eng. A. 299 (2001)
185194.
[12] J.C. Zhu, Z.H. Lai, Z.D. Yin, Mater. Chem. Phys. 68 (2001) 130135.
[13] X. Jin, L.Z. Wu, Y.G. Sun, Mater. Sci. Eng. A 509 (2009) 6368.