J Mater Sci: Mater Electron (2008) 19:357362

DOI 10.1007/s10854-007-9343-0

PTCR characteristics of semiconducting barium titanate ceramics

produced by high-energy ball-milling
K. Park J.-G. Ha C.-W. Kim Jun-Gyu Kim

Received: 2 February 2007 / Accepted: 29 May 2007 / Published online: 22 August 2007

Springer Science+Business Media, LLC 2007

Abstract We studied the influence of potato-starch

content and ball-milling time on the positive temperature
coefficient of resistance (PTCR) characteristics of porous
and semiconducting barium titanate ceramics, which were
produced by high-energy ball-milling followed by solid
state reaction. The sintered samples at room temperature
crystallized in the tetragonal structure, irrespective of the
potato-starch content and ball-milling time. As the ballmilling time increased, the porosity and pore size of the
samples decreased, while and the grain size increased.
Higher potato-starch content yielded a smaller grain size
and higher porosity. The potato-starch additive and ballmilling time had little influence on the donor concentration of the grains. A larger PTCR jump was obtained with
the addition of potato-starch mainly as a consequence of
an increase in the porosity. A higher ball-milling time
yielded both lower electrical resistivity and a lower PTCR
jump.

K. Park
Department of Advanced Materials Engineering, Sejong
University, Seoul 143-747, South Korea
J.-G. Ha
Department of Electronic Materials Engineering, Kwangwoon
University, Seoul 139-701, South Korea
C.-W. Kim
Research Institute of Industrial Science & Technology (RIST),
Pohang 790-330, South Korea
J.-G. Kim (&)
Inorganic Chemistry Examination Team, Korean Intellectual
Property Office, Daejeon 302-701, Korea
e-mail: iamjgkim@hanmail.net

1 Introduction
Pure barium titanate (BaTiO3) is an electrical insulator, because
of its large energy gap [13]. However, the barium titanate
becomes a semiconducting material after the partial substitution
of Ba2+ by trivalent cations, or Ti4+ by pentavalent cations [4
7]. Semiconducting barium titanate ceramics show a positive
temperature coefficient of resistance (PTCR) characteristics [1
26]. In 1971, Heywang [8] explained the PTCR characteristics
in terms of the double Schottky barriers at the grain boundaries.
According to this model, the barriers result from electron
trapping by acceptor states at the grain boundaries [12, 13].
Since then, the model has been extended by Jonker, considering
the influence of polarization on the resistivity below the Curie
point [9]. To date, various fabrication techniques have been
attempted to improve the PTCR characteristics [2730].
It has been reported that porous BaTiO3 ceramics exhibit a
large PTCR effect [31]. The porous ceramics are more
favorable for forming surface acceptor states compared with
ordinary dense ones [31]. Also, the porous BaTiO3 ceramics
show better heat resistance than dense ones, and thus can be
used for PTC thermistors, which can protect against overcurrent in electric circuits [14, 15]. It is generally accepted that
the composition and the processing of the thermistors significantly affect the microstructure and thus change the electrical
properties. In the present study, in order to fabricate porous
ceramics and to further improve the PTCR characteristics, the
addition of potato-starch in (Ba,Sr)TiO3 was attempted. Also,
we controlled the microstructure and electrical properties by
changing the high-energy ball-milling time.
2 Experimental
The semiconducting barium titanate samples containing
015 wt.% potato-starch were prepared by high-energy

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J Mater Sci: Mater Electron (2008) 19:357362

ball-milling followed by solid-state reaction. The semiconducting barium titanate powders used were
commercially available high-purity (Ba,Sr)TiO3 powders
containing 25 mol% SrO and 0.2 mol% Y2O3 (Toho
Titanium Co. Ltd, Japan). The mean particle size and ferroelectric Curie temperature of the powders were 0.7 lm
and 61 C, respectively. The potato-starch powders (purity:
[99.9%, mean particle size: 25 lm, Shinyo Pure Chemicals Co. Ltd, Japan) were added into the (Ba,Sr)TiO3
powders. A mixture of the (Ba,Sr)TiO3 and potato-starch
powders and ethanol was milled with a planetary mill
(Fritsch, Germany) at 500 rpm for 120 h using ZrO2 balls
(/ 2 mm) as a grinding media. Subsequently, the mixed
powders were dried at 100 C for 4 h. The resulting dried
powders were compacted by die-pressing at 40 MPa to
prepare the green compacts (15 12 7 mm3). The green
compacts were sintered at 1,350 C for 1 h in air and then
cooled to room temperature. The samples obtained are
given in Table 1.
A thermal analysis of the mixed powders was carried out
using a differential thermal/thermogravimetric analysis
(DT/TGA: SDT Q600) in the temperature range of 0
1,000 C at a heating rate of 10 C min1 in air. A scanning electron microscopy (SEM: S-4200, Hitachi) was used
for the analysis of the microstructure of the sintered
ceramics. An X-ray diffractometer (XRD: PW-1710, Philips) was used in order to investigate the effects of the
potato-starch additive and ball-milling time on the crystal
structure. The grain size of the ceramics was estimated by
the line-intersecting method and the porosity and pore size
of the ceramics were measured with a mercury porosimeter. The electrical resistance was measured with a digital
multi-meter in air from 25 C up to 300 C. In order to
calculate the electrical potential barrier of grain boundaries
and the donor concentration of grains, the capacitance
voltage (CV) characteristics were measured with an
impedance analyzer at room temperature at a frequency of
10 kHz.

3 Results and discussion

We found that an increase in the ball-milling time leads to
a slight decrease in the powder size and in the narrow size
distribution. The SEM micrographs of the mixed powders
for samples P15(1H), P15(10H), and P15(20H) are shown
in Fig. 1ac, respectively. The mean sizes of the powders
for samples P15(1H), P15(10H), and P15(20H) are 0.80,
0.71, and 0.62 lm, respectively. Moreover, the added
potato-starch did not significantly affect the thermal
behavior. The typical result of DT/TGA measurements for

Table 1 Summary of the samples prepared in this study

Sample

Ball-milling time (h)

Potato-starch content (wt.%)

P0(1H)

P5(1H)

P10(1H)

10

P15(1H)

15

P15(5H)

15

P15(10H)

10

15

P15(15H)

15

15

P15(20H)

20

15

123

Fig. 1 SEM micrographs of the mixed powders for the potato-starch

added samples (a) P15(1H), (b) P15(10H), and (c) P15(20H)

J Mater Sci: Mater Electron (2008) 19:357362

359

Endo

Weight (%)

Exo

, respectively [32]. It was also found

are 1.16 and 1.35 A
that the diffraction patterns at room temperature for the
other samples ball-milled for 520 h were basically
equivalent to those of Fig. 3. These results indicate that
both the potato-starch content and the high-energy ballmilling time had no significant influence on the crystal
structure.
Figure 4 shows the dependence of the electrical resistivity on temperature for samples P0(1H)P15(1H) milled
for 1 h, showing PTCR characteristics. Higher potatostarch content yielded a larger PTCR jump. The PTCR
jumps of samples P0(1H), P5(1H), P10(1H), and P15(1H)
are 3.01 105, 3.03 105, 3.08 105, and 4.97 105,
respectively. The highest PTCR jump was obtained for
sample P15(1H). In addition, the electrical resistivity of the
potato-starch added samples P5(1H), P10(1H), and
P15(1H) was higher than that of the potato-starch-free
sample P0(1H) over the measured temperature range. In
order to reduce the resistivity of the potato-starch containing samples, we ball-milled for a longer time (520 h)
and controlled the microstructure.
Figure 5 shows the electrical resistivity as a function of
the temperature for samples P15(1H)P15(20H) ball-milled for 120 h. A higher ball-milling time yielded a lower
electrical resistivity. For example, the room-temperature
resistivities of samples P15(1H), P15(10H), and P15(20H)
are 1.40 102, 9.55 10, and 5.02 10 X cm, respectively. In addition, a lower PTCR jump was observed with
ball-milling time. The PTCR jump of samples P15(1H),
P15(10H), and P15(20H) are 4.97 105, 3.19 105, and
1.11 105, respectively. Room-temperature electrical
resistivity (q25 C), maximum electrical resistivity (qmax),
and PTCR jumps (qmax/q25 C) of all the samples are given
in Table 2. In order to understand the change in electrical

1000

Fig. 2 Result of DTA and TGA measurements for the mixed

powders of the potato-starch added sample P15(1H)

the mixed powders of sample P15(1H) is shown in Fig. 2.

Two exothermic peaks, accompanied with a great weight
loss, are seen in the temperature range of 260460 C. It
was found that the results of DT/TGA for the other samples
were basically the same as those of sample P15(1H).
The XRD patterns measured at room temperature for
samples P0(1H)P15(1H) milled for 1 h are shown in
Fig. 3. The diffraction patterns show reflections of a single (Ba,Sr)TiO3 phase with the tetragonal structure. No
secondary phase such as carbon was detected. Also,
because the lattice parameters of the tetragonal and cubic
phases in (Ba,Sr)TiO3 are quite similar, we analyzed the
diffraction patterns at high angles. In Fig. 3, the (103) and
(310) peaks of the tetragonal phase are detected at
2h = 75.21 and 75.75, respectively. The reflected peaks
are slightly shifted towards higher angles compared with
BaTiO3 because the added Sr is present at the Ba site of
the (Ba,Sr)TiO3 lattice. The ionic radii of Sr and Ba atoms

O (Ba ,Sr)TiO3
O

O O

20

73

76

77

78

74

75

76

77

78

77

78

Degree (2 )

30

75

Degree (2 )

74

P0 (1H)

P5 (1H)

(310)

P10(1H)

73

O O
Intensity

Intensity (a. u.)

P15(1H)

(103)

(310)

Fig. 3 XRD patterns measured

at room temperature for samples
P0(1H)P15(1H) milled for 1 h

(103)

800

(310)

600

(103)

400

Temperature ( C )

Intensity

200

Intensity

40

50

2 (degree)

60

70

80
73

74

75

76

Degree (2 )

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J Mater Sci: Mater Electron (2008) 19:357362

8

Table 2 Room-temperature electrical resistivity (q25 C), maximum

electrical resistivity (qmax), and PTCR jumps (qmax/q25 C) for the
samples

10

Electrical resistivity ( cm)

10

Sample
P0(1H)

10

P5(1H)
4

10

P0 (1H)
P5 (1H)
P10 (1H)
P15 (1H)

10

3.18 10

9.57 106

3.01 105

5.05 10

3.03 105

3.08 105

4.97 105

2.64 105

9.09 10

P15(1H)

P15(5H)

10

50

100

150

200

250

Fig. 4 Dependence of the electrical resistivity on temperature for

samples P0(1H)P15(1H) milled for 1 h

10

P15 (1H)
P15 (5H)
P15 (10H)
P15 (15H)
P15 (20H)

10

10

10

10

10

10

50

100

150

200

250

1.16 10

2.80 10
6.96 10
3.06 10

9.55 10

3.05 10

3.19 105

P15(15H)

7.80 10

1.50 107

1.92 105

5.02 10

1.11 105

5.57 10

300

Temperature ( C)

10

1.40 10

1.53 10

P15(10H)
P15(20H)

10

Electrical resistivity ( cm)

PTCR jump
(qmax/q25 C)

P10(1H)

300

Temperature ( C)

Fig. 5 Electrical resistivity as a function of temperature for samples

P15(1H)P15(20H) ball-milled for 120 h

resistivity depending on the potato-starch content and ballmilling time, as shown in Figs. 4 and 5, we investigated the
microstructure, the donor concentration of grains and the
electrical barrier height of grain boundaries.
The SEM images from the fractured surfaces for the assintered samples P15(1H), P15(10H), and P15(20H) are
shown in Fig. 6ac, respectively. The samples were highly
porous, which are favorable to oxidize the grain boundaries
[31]. With increasing ball-milling time, the porosity and
pore size of the samples decreased and the grain size
increased due to the pore pinning effect. These results are
responsible for the increase in the time between the

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qmax (X cm)

q25 C (X cm)

10

scattering events of charge carriers, thus decreasing the

resistivity. Furthermore, we found that a higher potatostarch content yielded smaller grain size and higher porosity
(not shown here). The higher porosity is caused by the pores
formed due to the burn-out of potato-starch during sintering.
The porosity, mean pore size, and mean grain size for all the
samples prepared are summarized in Table 3.
The plots of the capacitance versus the applied voltage
at room temperature for samples P0(1H) and P15(1H) are
shown in Fig. 7, showing a nearly linear dependence
between the two parameters. The donor concentrations of
the grains and the electrical potential barriers of the grain
boundaries for all the samples are calculated using the
equation proposed by Mukae et al. [33] and summarized in
Table 4. According to Table 4, the potato-starch content
and ball-milling time did not cause a noticeable change in
the donor concentration of grains. However, at a fixed ballmilling time of 1 h, the added potato-starch leads to an
increase in the electrical barrier height of grain boundaries
mainly because of the oxidation of the grain boundaries.
The oxygen in the porous ceramics is adsorbed at the grain
boundaries during sintering in air, thus increasing the
electrical potential barrier height, which results from an
increase of surface states density [8, 12, 13, 31]. Also, at a
given potato-starch content of 15 wt.%, the electrical barrier height of grain boundaries decreased as the ball-milling
time increased.
From the above electrical and microstructural properties, an increased resistivity with potato-starch content is
attributed to an increase in the electrical barrier height of
grain boundaries, porosity and the grain boundary area. In
addition, a decreased resistivity with ball-milling time is
largely due to a decrease in the electrical barrier height,
porosity, and grain boundary area. Furthermore, the PTCR
jump slightly increased with the potato-starch content as a
consequence of an increased porosity, which can be
explained by the barrier model proposed by Heywang [8,
12, 13]. We propose that the addition of potato-starch is

J Mater Sci: Mater Electron (2008) 19:357362

361

{1/C-1/(2C0)} (10 cm /F )

P15(1H)
P0 (1H)

3
2
1
0.0

0.5

1.0

1.5

2.0
-3

Applied voltage per grain boundary (10 V)

Fig. 7 Plots of the capacitance versus the applied voltage at room
temperature for samples P0(1H) and P15(1H)

Table 4 Donor concentrations of grains and electrical potential

barriers of grain boundaries at 25 C for the samples
Sample

Donor concentration
of grains (#/cm3)

Electrical potential barrier

of grain boundaries (eV)

P0(1H)

5.12 1018

0.005

P5(1H)

4.67 1018

0.008

P10(1H)

4.52 10

18

0.014

P15(1H)

4.38 1018

0.022

P15(5H)

4.45 1018

0.018

P15(10H)
P15(15H)

4.51 1018
4.59 1018

0.015
0.012

P15(20H)

4.78 1018

0.008

desirable for an increase in the PTCR jump and an increase

in milling time leads to a decrease in the resistivity over the
measured temperature range.
Fig. 6 SEM images from the fractured surfaces for the as-sintered
samples (a) P15(1H), (b) P15(10H), and (c) P15(20H)

Mean
pore
size (lm)

Mean
grain
size (lm)

The crystal structure, microstructure, and electrical properties of the porous and semiconducting barium titanate
ceramics, which were produced by high-energy ball-milling followed by solid state reaction, were studied. The
results obtained are as follows:

0.28

6.71

(1)

Table 3 Porosity, mean pore size and mean grain size of the samples
Sample

Porosity
(%)

P0(1H)

7.18

4 Conclusions

P5(1H)

15.86

0.92

5.76

P10(1H)
P15(1H)

20.95
25.87

1.45
2.47

5.01
4.68

P15(5H)

24.71

1.93

5.52

P15(10H)

22.83

1.55

6.45

P15(15H)

17.75

0.98

7.43

P15(20H)

15.53

0.42

7.91

(2)

The XRD patterns show reflections of a single

(Ba,Sr)TiO3 phase with the tetragonal structure. Both
the potato-starch content and high-energy ball-milling
had no significant influence on the crystal structure.
With increasing ball-milling time, the porosity and
pore size of the samples decreased and the grain size
increased due to the pore pinning effect. Higher
potato-starch content yielded a smaller grain size and
higher porosity.

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(3)

(4)

(5)

J Mater Sci: Mater Electron (2008) 19:357362

The potato-starch additive and ball-milling time did

not cause a noticeable change in the donor concentration of grains.
As the potato-starch content increased, the resistivity
also increased due to an increase in the electrical
barrier height of grain boundaries, porosity and grain
boundary area and the PTCR jump increased as a
consequence of an increased porosity.
A higher ball-milling time yielded a lower electrical
resistivity and a lower PTCR jump. The lower
electrical resistivity was attributed to an increase in
the electrical barrier height of the grain boundaries,
the porosity and the grain boundary area.

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