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Materials Science and Engineering A356 (2003) 443 /446

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


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

transferred at both the micro and macro levels. Thus, a
The sintering of nanocrystalline ceramics is an excit- high quality sintered compact is obtained at a lower
ing theme in materials research because such bulk temperature and in a shorter time than conventional
nanocrystalline ceramics exhibit novel properties and sintering [7].
functions. Much progress has been made in consolidat- On the other hand, nanocrystalline ceramics do not
ing nanocrystalline powders by a number of consolida- appear to possess high fracture toughness, as was
tion methods during the past several years. However, anticipated [8]. Therefore, research on processing fully
these studies have highlighted the problem of consoli- dense bulk nanocomposites that retain nanocrystalline
dating these nanopowders into full dense ceramics grain size in matrix and possess moderate fracture
without excessive grain growth [1 /6]. Therefore, search- toughness as well, is still a challenging problem. Domain
ing for a new processing technique that requires shorter switching as a toughening mechanism has been recog-
duration could be the ideal choice. Spark plasma nized in ferroelectric materials where either an applied
sintering (SPS), a fast consolidation technique that can compressive stress or electrical field led to domain
enhance sintering kinetics and reduce the time available switching [9]. This behavior has been demonstrated by
for grain growth, has been used in the present study. It is the facts that anisotropic fracture toughness was ob-
a pressure-assisted sintering method based on the short- served in these poled materials and the fracture tough-
lived generation of high-temperature spark plasma at ness depends on the volume fraction of domains that are
the interfaces between powder particles. The basic aligned favorably in front of the crack tip [10 /13]. R -
configuration of an SPS system consists of a sintering curve behavior due to stress-induced ferroelastic domain
die with a uniaxial pressurization mechanism, specially switching was also found in BaTiO3 [14]. Moreover, the
designed punch electrodes, vacuum chamber with va-
contribution to toughening due to domain switching in
cuum atmosphere control, a DC-pulse generator, and
zirconia was almost three times that of the intrinsic
control units. During SPS processing, the powder
toughness [15]. Recently, a new approach for toughen-
ing of ceramics has been proposed and investigated
* Corresponding author. Fax: /1-530-752-9554. where piezoelectric and ferroelectric second phases were
E-mail address: (A.K. Mukherjee). incorporated into the ceramic matrix as toughening
0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
444 G.-D. Zhan et al. / Materials Science and Engineering A356 (2003) 443 /446

phase and energy dissipation by the piezoelectric effect magnification over 600 k /. Grain sizes were estimated
was suggested as a new toughening mechanism [16,17]. from high-resolution SEM of fractured surfaces. Frac-
In the present study, BaTiO3 was selected as a model ture toughness (KIC) was measured by indentation
ferroelectric toughening second phase for the present techniques. Indentation tests were performed on a
study because it has been extensively characterized with Wilson Tukon hardness tester with a diamond Vickers
regards to its ferroelectric and ferroelastic properties. indenter. The indentation parameters for fracture
This paper will report the microstructure, mechanical toughness (KIC) were a 1.5 kg load with a dwell of 15
properties, and toughening mechanisms in BaTiO3/ s. The following equation, proposed by Antis et al., [18]
Al2O3 nanocomposites consolidated by this novel pro- was used for the calculation:
cessing technique.  1=2  
KIC 0:016 (1)
Hv c3=2
2. Experimental procedures where E , Hv, P and c represent Young’s modulus,
Vickers hardness, the applied indentation load, and the
Cubic BaTiO3 nanopowders were provided by Cabot half-length of the radial crack, respectively.
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 3. Results and discussion
had an average particle size of /50 nm (obtained from
Baikowski International, Charlotte, NC) and surface The relative densities for all the SPS materials are
area of 30 m2 g1. The gas condensation synthesized g- given in Table 1. It can be noted that all the materials
Al2O3 with an average particle size of 32 nm was could be consolidated by SPS at 1150 8C only for 3 min
obtained from Nanophase Technologies Corporation to get almost full density. This is quite different from the
(Darien, IL 60651). The BaTiO3 powders at different pressureless-sintered BaTiO3/Al2O3 composites where
volume contents were mixed with the a-Al2O3 nano- the sintering temperatures were higher than 1450 8C
powder for 24 h in ethanol using zirconia ball media. A but the maximum bulk density obtained was just 92% of
high-energy ball-milling method was used to prepare the the theoretical density of alumina [16]. The microstruc-
starting g-Al2O3 nanopowders. This is that the g-Al2O3 tures of the fractured surface in the pure alumina and
and BaTiO3 powders are high-energy ball-milled with a BaTiO3/a-Al2O3 nanocomposites in the present study
WC ball and vial set for 24 h. In order to prevent severe are shown in Fig. 1. It is very interesting to note that the
powder agglomeration one weight percent polyvinyl pure a-Al2O3 consolidated by SPS exhibited a mixture
alcohol (PVA), a dry milling agent, was added. The of fracture modes (Fig. 1(a)). This is different from the
PVA is removed after ball-milling through a 350 8C conventionally sintered monolithic alumina exhibiting
heat treatment in vacuum. SPS was carried out under intergranular fracture. However, the fracture modes are
vacuum in a Dr. Sinter 1050 SPS apparatus (Sumitomo mainly intergranular in these BaTiO3/Al2O3 nanocom-
Coal Mining Co., Japan). The powder mixtures were posites, as shown in Fig. 1(b) to (e) for 5, 7.5, 10, and 15
placed into a graphite die (20 mm in inner diameter) and vol.% BaTiO3/Al2O3 nanocomposites, respectively. It is
cold-pressed at 200 MPa to green-body with /57% of obvious that the microstructures consisted of nanoscale
theoretical density. The SPS processing parameters used grain sizes in these sintered nanocomposites. It can also
in the present study were as follows: (1) an applied be noted that a dramatic grain growth occurred for the
pressure of 63 MPa, (2) the heating rate of 200 8C pure BaTiO3 with grain size up to 15 mm (Fig. 1(f)).
min 1 from 600 8C to the desired temperatures, (3) the These results demonstrate the effectiveness of SPS over
pulse duration time of 12 ms and the interval between conventional method in obtaining nanocrystalline alu-
pulse of 2 ms, and (4) the pulse current of /2000 A and mina matrix nanocomposites at quite lower tempera-
a voltage of 10 V. The temperature was monitored with tures and shorter sintering duration resulting in high
an optical pyrometer that was focused on the ‘non- density and nanosized grain size. Moreover, it is very
through’ hole (0.5 mm in diameter and 2 mm in depth) interesting to note that the grain size for the 7.5
of the graphite die. The final densities of the sintered vol.%BaTiO3/g-Al2O3 nanocomposite through high-en-
compacts were determined by the Archimedes’ method ergy ball-milling was as small as 190 nm. It is much finer
with deionized water as the immersion medium. The than 7.5 vol.%BaTiO3/a-Al2O3 nanocomposite without
theoretical densities of the specimens were calculated high-energy ball-milling, suggesting that high-energy
according to the rule of mixtures. The microstructural ball-milling procedure can lead to more refined struc-
observation and microanalysis were carried out using an ture.
FEI XL30-SFEG high-resolution scanning electron Table 1 also summarizes the fracture toughness for
microscopy with a resolution better than 2 nm and 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

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.


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.

Fig. 2. Relationship between fracture toughness and BaTiO3 contents

in spark-plasma-sintered BaTiO3/Al2O3 nanocomposites. References

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