Materials Science and Engineering A356 (2003) 443
/446

www.elsevier.com/locate/msea

Spark-plasma-sintered BaTiO3/Al2O3 nanocomposites

Guo-Dong Zhan, Joshua Kuntz, Julin Wan, Javier Garay, Amiya K. Mukherjee *
Department of Chemical Engineering and Materials Science, University of California at Davis, One Shields Avenue, Davis, CA 95616-5294, USA

Received 18 March 2002; received in revised form 12 September 2002

Abstract

Using spark plasma sintering (SPS), BaTiO3/Al2O3 nanocomposites were successfully consolidated to more than 99% of
theoretical density at a sintering temperature as low as 1150 8C in only 3 min. The processing methods for these dense
nanocomposites where the retained grain size of alumina matrix was in the nanometer level were developed. The maximum volume
content of BaTiO3 in the nanocrystalline matrix for toughening was around 15 vol.%. A significant increase in fracture toughness up
to 5.36 MPa1/2 has been achieved in the 7.5 vol.% BaTiO3/Al2O3 nanocomposite. The toughening mechanism might be related to
ferroelastic domain switching of ferroelectric phase in these nanocomposites.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Alumina nanocomposite; Spark plasma sintering; Toughening

1. Introduction surfaces are cleaned and activated, and the material is

The sintering of nanocrystalline ceramics is an excit-
ing theme in materials research because such bulk
nanocrystalline ceramics exhibit novel properties and
functions. Much progress has been made in consolidat-
ing nanocrystalline powders by a number of consolida-
tion methods during the past several years. However,
these studies have highlighted the problem of consoli-
dating these nanopowders into full dense ceramics
without excessive grain growth [1
/6]. Therefore, search-
ing for a new processing technique that requires shorter
duration could be the ideal choice. Spark plasma
sintering (SPS), a fast consolidation technique that can
enhance sintering kinetics and reduce the time available
for grain growth, has been used in the present study. It is
a pressure-assisted sintering method based on the short-
lived generation of high-temperature spark plasma at
the interfaces between powder particles. The basic
configuration of an SPS system consists of a sintering
die with a uniaxial pressurization mechanism, specially
designed punch electrodes, vacuum chamber with va-
cuum atmosphere control, a DC-pulse generator, and
control units. During SPS processing, the powder
* Corresponding author. Fax: /1-530-752-9554.
E-mail address: akmukerjee@ucdavis.edu (A.K. Mukherjee).
0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0921-5093(02)00812-2
transferred at both the micro and macro levels. Thus, a
high quality sintered compact is obtained at a lower
temperature and in a shorter time than conventional
sintering [7].
On the other hand, nanocrystalline ceramics do not
appear to possess high fracture toughness, as was
anticipated [8]. Therefore, research on processing fully
dense bulk nanocomposites that retain nanocrystalline
grain size in matrix and possess moderate fracture
toughness as well, is still a challenging problem. Domain
switching as a toughening mechanism has been recog-
nized in ferroelectric materials where either an applied
compressive stress or electrical field led to domain
switching [9]. This behavior has been demonstrated by
the facts that anisotropic fracture toughness was ob-
served in these poled materials and the fracture tough-
ness depends on the volume fraction of domains that are
aligned favorably in front of the crack tip [10
/13]. R -
curve behavior due to stress-induced ferroelastic domain
switching was also found in BaTiO3 [14]. Moreover, the
contribution to toughening due to domain switching in
zirconia was almost three times that of the intrinsic
toughness [15]. Recently, a new approach for toughen-
ing of ceramics has been proposed and investigated
where piezoelectric and ferroelectric second phases were
incorporated into the ceramic matrix as toughening
444 G.-D. Zhan et al. / Materials Science and Engineering A356 (2003) 443
/446
phase and energy dissipation by the piezoelectric effect
was suggested as a new toughening mechanism [16,17].
In the present study, BaTiO3 was selected as a model
ferroelectric toughening second phase for the present
study because it has been extensively characterized with
regards to its ferroelectric and ferroelastic properties.
This paper will report the microstructure, mechanical
properties, and toughening mechanisms in BaTiO3/
Al2O3 nanocomposites consolidated by this novel pro-
cessing technique.
2. Experimental procedures
Cubic BaTiO3 nanopowders were provided by Cabot
Corporation, which were prepared by hydrothermal
reaction of barium hydroxide (Ba(OH)2) with titanium
hydroxide (Ti(OH)4). The average particle size is 60 nm.
The pure a-Al2O3 nanopowder used in the present study
had an average particle size of
/50 nm (obtained from
Baikowski International, Charlotte, NC) and surface
area of 30 m2 g1. The gas condensation synthesized g-
Al2O3 with an average particle size of 32 nm was
obtained from Nanophase Technologies Corporation
(Darien, IL 60651). The BaTiO3 powders at different
volume contents were mixed with the a-Al2O3 nano-
powder for 24 h in ethanol using zirconia ball media. A
high-energy ball-milling method was used to prepare the
starting g-Al2O3 nanopowders. This is that the g-Al2O3
and BaTiO3 powders are high-energy ball-milled with a
WC ball and vial set for 24 h. In order to prevent severe
powder agglomeration one weight percent polyvinyl
alcohol (PVA), a dry milling agent, was added. The
PVA is removed after ball-milling through a 350 8C
heat treatment in vacuum. SPS was carried out under
vacuum in a Dr. Sinter 1050 SPS apparatus (Sumitomo
Coal Mining Co., Japan). The powder mixtures were
placed into a graphite die (20 mm in inner diameter) and
cold-pressed at 200 MPa to green-body with
/57% of
theoretical density. The SPS processing parameters used
in the present study were as follows: (1) an applied
pressure of 63 MPa, (2) the heating rate of 200 8C
min 1 from 600 8C to the desired temperatures, (3) the
pulse duration time of 12 ms and the interval between
pulse of 2 ms, and (4) the pulse current of
/2000 A and
a voltage of 10 V. The temperature was monitored with
an optical pyrometer that was focused on the ‘non-
through’ hole (0.5 mm in diameter and 2 mm in depth)
of the graphite die. The final densities of the sintered
compacts were determined by the Archimedes’ method
with deionized water as the immersion medium. The
theoretical densities of the specimens were calculated
according to the rule of mixtures. The microstructural
observation and microanalysis were carried out using an
FEI XL30-SFEG high-resolution scanning electron
microscopy with a resolution better than 2 nm and
magnification over 600 k /. Grain sizes were estimated
from high-resolution SEM of fractured surfaces. Frac-
ture toughness (KIC) was measured by indentation
techniques. Indentation tests were performed on a
Wilson Tukon hardness tester with a diamond Vickers
indenter. The indentation parameters for fracture
toughness (KIC) were a 1.5 kg load with a dwell of 15
s. The following equation, proposed by Antis et al., [18]
was used for the calculation:
 1=2  
E P
KIC 0:016 (1)
Hv c3=2
where E , Hv, P and c represent Young’s modulus,
Vickers hardness, the applied indentation load, and the
half-length of the radial crack, respectively.
3. Results and discussion
The relative densities for all the SPS materials are
given in Table 1. It can be noted that all the materials
could be consolidated by SPS at 1150 8C only for 3 min
to get almost full density. This is quite different from the
pressureless-sintered BaTiO3/Al2O3 composites where
the sintering temperatures were higher than 1450 8C
but the maximum bulk density obtained was just 92% of
the theoretical density of alumina [16]. The microstruc-
tures of the fractured surface in the pure alumina and
BaTiO3/a-Al2O3 nanocomposites in the present study
are shown in Fig. 1. It is very interesting to note that the
pure a-Al2O3 consolidated by SPS exhibited a mixture
of fracture modes (Fig. 1(a)). This is different from the
conventionally sintered monolithic alumina exhibiting
intergranular fracture. However, the fracture modes are
mainly intergranular in these BaTiO3/Al2O3 nanocom-
posites, as shown in Fig. 1(b) to (e) for 5, 7.5, 10, and 15
vol.% BaTiO3/Al2O3 nanocomposites, respectively. It is
obvious that the microstructures consisted of nanoscale
grain sizes in these sintered nanocomposites. It can also
be noted that a dramatic grain growth occurred for the
pure BaTiO3 with grain size up to 15 mm (Fig. 1(f)).
These results demonstrate the effectiveness of SPS over
conventional method in obtaining nanocrystalline alu-
mina matrix nanocomposites at quite lower tempera-
tures and shorter sintering duration resulting in high
density and nanosized grain size. Moreover, it is very
interesting to note that the grain size for the 7.5
vol.%BaTiO3/g-Al2O3 nanocomposite through high-en-
ergy ball-milling was as small as 190 nm. It is much finer
than 7.5 vol.%BaTiO3/a-Al2O3 nanocomposite without
high-energy ball-milling, suggesting that high-energy
ball-milling procedure can lead to more refined struc-
ture.
Table 1 also summarizes the fracture toughness for
the present materials. In comparison to other alumina
 G.-D. Zhan et al. / Materials Science and Engineering A356 (2003) 443
/446 445

Table 1
Physical and fracture toughness of BaTiO3/Al2O3 nanocomposites consolidated by SPS at 1150 8C per 3 min

Material Relative density (%) Mean grain size (nm) Fracture toughness (MPa m1/2)

Pure a-Al2O3 99.8 3499/10 3.309/0.14

5 vol.%BaTiO3/a-Al2O3 99.5 3689/19 4.749/0.31
7.5 vol.%BaTiO3/a-Al2O3 99.6 2569/13 5.369/0.38
7.5 vol.%BaTiO3/g-Al2O3 99.2 1909/15 5.269/0.34
10 vol.%BaTiO3/a-Al2O3 99.8 2819/13 4.989/0.13
15 vol.%BaTiO3/a-Al2O3 99.9 3269/18 4.349/0.39
Pure BaTiO3 99.9 15 6359/1969

nanocomposites [8] and pure alumina in the present Fig. 2 shows the relationship between toughness and
work, a significant improvement in fracture toughness BaTiO3 volume contents. It can be seen that the fracture
was observed in the present nanocomposite materials. toughness increases with increasing BaTiO3 content and

Fig. 1. High-resolution scanning electron micrographs of fractured surfaces for; (a) pure a-Al2O3, (b) 5 vol.%BaTiO3/Al2O3, (c) 7.5 vol.%BaTiO3/
Al2O3 (d) 10 vol.%BaTiO3/Al2O3, (e) 15 vol.%BaTiO3/Al2O3, and (f) pure BaTiO3 nanocomposites consolidated by spark-plasma-sintering at
1150 8C for 3 min.
446 G.-D. Zhan et al. / Materials Science and Engineering A356 (2003) 443
/446
Fig. 2. Relationship between fracture toughness and BaTiO3 contents
in spark-plasma-sintered BaTiO3/Al2O3 nanocomposites.
reachs a maximum at 7.5 vol.%. More than 1.6 times
increase in fracture toughness over the pure nanocrystal-
line alumina has been achieved in the 7.5 vol.%BaTiO3/
Al2O3 nanocomposite, suggesting that adding ferro-
electric phase into nanocrystalline alumina is effective
for toughening. In regard to the particle toughening, it
could be ruled out due to the fact that grain size for the
second phase is in the nano-region for the present study.
Thus, the contributions to toughening by crack bridging
and crack deflection due to the second phase is likely to
be very small. Therefore, there may be a toughening
effect related to stress-induced domain switching tough-
ening of the ferroelectric second phase [19,20].
4. Conclusions
SPS to almost theoretical density at a quite low
temperature of 1150 8C for only 3 min could success-
fully consolidate BaTiO3/Al2O3 nanocomposites. The
7.5 vol.%BaTiO3/g-Al2O3 nanocomposite with a mean
gain size of alumina matrix as small as 190 nm could be
obtained through high-energy ball-milling process.
Fracture toughness depends on the contents of BaTiO3
in the nanocrystalline alumina matrix. The optimum
contents of BaTiO3 are less than 10 vol.%. A significant
increase in fracture toughness up to 5.36 MPa m1/2 was
achieved in the 7.5 vol.%BaTiO3/Al2O3 nanocomposite.
Acknowledgements
This work was supported by a grant (#G-DAAD 19-
00-1-0185) from US Army Research Office with Dr
William Mullins as the Program Manager.
References
[1] H. Gleiter, Prog. Mater. Sci. 33 (1989) 223.
[2] R.S. Mishra, J.A. Schneider, J.F. Shackelford, A.K. Mukherjee,
NanoStruct. Mater. 5 (1995) 525.
[3] E.J. Gonzalez, B. Hockey, G.J. Piermarini, Mater. Manufacturing
Processes 11 (1996) 951.
[4] M.J. Mayo, NanoStruct. Mater. 9 (1997) 717.
[5] S. Bhaduri, S.B. Bhaduri, NanoStruct. Mater. 8 (1997) 755.
[6] S.-C. Liao, Y.-J. Chen, B.H. Kear, W.E. Mayo, NanoStruct.
Mater. 10 (1998) 1063.
[7] M. Tokita, J. Soc. Powder Technol. Jpn. 30 (1993) 790
/804.
[8] R.S. Mishra, C.E. Lesher, A.K. Mukherjee, in: D.L. Bourell
(Ed.), Synthesis and Processing of Nanocrystalline Powder, TMS,
1996, p. 173.
[9] K. Mehta, A.V. Virkar, J. Am. Ceram. Soc. 73 (1990) 567.
[10] Z. Zhang, R. Raj, J. Am. Ceram. Soc. 78 (1995) 3363.
[11] C.S. Lynch, Acta Mater. 46 (1998) 599.
[12] R.A. Pferner, G. Thurn, F. Aldinger, Mater. Chem. Phys. 61
(1999) 24.
[13] M.J. Busche, K.J. Hsia, Scripta Mater. 44 (2001) 207.
[14] F. Meschke, A. Kolleck, G.A. Schneider, J. Eur. Ceram. Soc. 17
(1997) 1143.
[15] A.V. Virkar, R.L.K. Matsumoto, J. Am. Ceram. Soc. 69 (1986) c-
224.
[16] B. Yang, X.M. Chen, Mater. Lett. 33 (1997) 237.
[17] G.-D. Zhan, J. Kuntz, J. Wan, J. Garay, A.K. Mukherjee, Scripta
Mater. (revised, 2001).
[18] G.R. Antis, P. Chantikul, B.R. Lawn, D.B. Marshall, J. Am.
Ceram. Soc. 64 (1981) 533.
[19] G. Winfield, F. Azough, R. Freer, Ferroelectrics 133 (1992) 181.
[20] G.H. Haertling, J. Am. Ceram. Soc. 82 (1999) 797.