Materials Letters 59 (2005) 3881 3884

www.elsevier.com/locate/matlet

High temperature NTC BaTiO3-based ceramic resistors

Ying Luo a,b,c,*, Xinyu Liu a,b
a

College of Materials Science and Engineering, Central south University, Changsha 410083, PR China
Research Center for Materials Science and Engineering, Guilin University of Electronic Technology, Jinji Road No. 1, GuiLin,
Guangxi, Province, 541004, PR China
c
Guilin Academy of Air Force, Guilin 541004, PR China
Received 3 February 2005; accepted 30 June 2005
Available online 25 July 2005

Abstract
In our research it was firstly found that BaTiO3 materials doped BaBiO3 compounds only showed NTC effect in wide temperature scale.
The effect of the composition on the microstructure and electrical properties of BaTiO3-based NTC thermistors was studied. Major phases
present in the sintered bodies were the solid solutions of BaTiO3 compounds with a perovskite structure and BaBiO3 compounds with a
monoclinal structure. The average grain size of the samples increased with increasing BaBiO3 contents. It is apparent that the samples q 450
and B 450 / 600 constant decreased with an increase in BaBiO3 content.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Negative temperature coefficient; Solid solutions; BaBiO3; Microstructure; Electrical properties

1. Introduction
Negative temperature coefficient (NTC) thermistors are
thermally sensitive resistors whose resistance decreases with
increasing temperature [1]. They are mainly used in
electronics for the suppression of in-rush current, for
temperature measurement and control, and for compensation for other circuit elements [2 4]. There is a large choice
of NTC materials, but those most used in practice are based
on solid solutions of transition metal oxides, such as Mn3O4,
Co3O4, and NiO, with the spinel structure of the general
formula AB2O4 [5 8].
However, their application is commonly limited to
temperatures below 200 -C. Rare earth oxide (Sm, Tb, Y
. . .) can be used for measurements at high temperature. The
conduction of such oxide is dependent on the atmosphere
(PO2) and densification [9]. These effects can be limited by
* Corresponding author. Research Center for Materials Science and
Engineering, Guilin University of Electronic Technology, Jinji Road No. 1,
GuiLin, Guangxi, Province, 541004, PR China. Tel.: +86 773 5601 434;
fax: +86 773 5605 683.
E-mail address: luoying_li@21cn.com (Y. Luo).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.06.065

doping. Wang et al. have studied the doping of Y2O3 by

ZrO2 and CaZrO3 for NTC high temperature components
[10]. Their high resistivity (some MV at 800 -C) and B
value around 24 000 K are not applicable for ambient to
1000 -C applications. Feltz and Polzl have proposed a
system of compositions Fex Niy Mn3
x
y O4 based on the
spinel structure for high temperature applications. Resistivities at 25 -C are ranging from 4.7 to 950 kV cm and B
values from 3300 to 5000 K. Yet B values are not stable for
temperatures below 400 -C, which limits the temperature
range for applications [11]. Another system, Srx La1
x Tix+y
Co1
x
y O3 with perovskite structure, is proposed by one of
these authors. Resistivities at 25 -C are ranging from 1 to
50 MV cm and B values from 1900 to 6900 K [12]. These
components synthesized by solid-state reaction and sintered
at 1350 -C do not show aging phenomenon and could be
used to applications from ambient to 1000 -C.
It is well known that doped BaTiO3 ceramics show good
positive temperature coefficient (PTC) effect. As a kind of
perovskite materials, (Sr, Pb)TiO3 ceramics exhibit novel
NTC PTC composite effect. Recently, in our research it
was firstly found that BaTiO3 materials doped BaBiO3
compounds only showed NTC effect in wide temperature

Y. Luo, X. Liu / Materials Letters 59 (2005) 3881 3884

scale. In the present study, the influence of composition on

the electrical properties of BaTiO3-based NTC thermistors
was studied.

2. Experimental
Analytical grade BaTiO3, Y2O3, MnO2, Al2O3, SiO2,
TiO2 and BaBiO3 powders were weighed in appropriate
proportions, as shown in Table 1. The weighed powders
were agate milled in planetary for 24 h in alcohol. The ballmilled slurries were dried at 120 -C in an oven for 6 h. The
dried powders were ground carefully in mortar and passed
through a 250-mesh sieve. Subsequently, the mixture of
powders was pressed at 175 MPa into 18 mm diameter and
about 2.5 mm high cylindrical pellets. Pellets were sintered
at 1350 -C for 1 h in air, and then furnace cooled. The Ag
pastes with thickness of about 15 Am were spread on
opposite-side surface of the sintered samples using a screen
printer. After the pastes were dried at room temperature, the
samples were heated at 600 -C for 30 min.
The crystalline structure of the prepared samples was
analyzed with X-ray diffraction (XRD) using Cu Ka
radiation at 40 kV and 25 mA. The microstructure of the
samples was investigated by using a scanning electron
microscope (SEM). The average grain size of the samples
was estimated by using the line-intersecting method. The
samples of each composition were prepared for measuring
electrical resistance. The samples were held with a holder in
a tube furnace, and their temperatures were measured with a
digital thermometer. The electrical resistance of the samples
in the furnace was measured with a digital multimeter
(Fluke 45) from 450 to 800 -C in steps of 20 -C. The
accuracy of the furnace measurements is T0.5 -C.

BaTiO3
BaBiO3

Relative Intensity /a. u.

3882

20

BaTiO3:BaBiO3=100:10

BaTiO3:BaBiO3=100:7

BaTiO3:BaBiO3=100:5

30

40

50

60

70

2 (degree)
Fig. 1. XRD patterns of sample M3 (BaTiO3 : BaBiO3 = 100 : 5), M4
(BaTiO3 : BaBiO3 = 100 : 7), and M5 -(BaTiO3 : BaBiO3 = 100 : 10) sintered
at 1350 -C for 1 h.

3. Results and discussion

The crystalline structure of the samples was analyzed by XRD.
Major phases present in the sintered bodies were the solid solutions
of BaTiO3 compounds with a perovskite structure and BaBiO3 with
a monoclinic structure. As expected, increasing the amount of
added BaBiO3, increased the intensity of the BaBiO3 peaks. For

Table 1
Chemical composition of the samples designed in this study
Sample

Composition (molecular ratio)

M1

100BaTiO3 + 1BaBiO3 + 0.25Y2O3 + 0.06MnO2 + 1(4Al2O3 +

9SiO2 + 3TiO2)
100BaTiO3 + 3BaBiO3 + 0.25Y2O3 + 0.06MnO2 + 1(4Al2O3 +
9SiO2 + 3TiO2)
100BaTiO3 + 5BaBiO3 + 0.25Y2O3 + 0.06MnO2 +
1(4Al2O3 + 9SiO2 + 3TiO2)
100BaTiO3 + 7BaBiO3 + 0.25Y2O3 + 0.06MnO2 +
1(4Al2O3 + 9SiO2 + 3TiO2)
100BaTiO3 + 10BaBiO3 + 0.25Y2O3 + 0.06MnO2 +
1(4Al2O3 + 9SiO2 + 3TiO2)

M2
M3
M4
M5

Fig. 2. SEM images of as-sintered samples (a) BaTiO3 : BaBiO3 = 100 : 3, (b)
BaTiO3 : BaBiO3 = 100 : 5, and (c) BaTiO3 : BaBiO3 = 100 : 7.

10

10

BaTiO3:BaBiO3=100:1
BaTiO3:BaBiO3=100:3
BaTiO3:BaBiO3=100:5
BaTiO3:BaBiO3=100:7
BaTiO3:BaBiO3=100:10

10 5

108

24000

Resistivity
20000
B450/600

10

106
16000

105

10

10

10

10

10

101
0

104

12000

103

8000

10
400 450 500 550 600 650 700 750 800 850

4000
2

Fig. 3. Resistivity temperature curves of BaTiO3-based ceramics sintered

at 1350 -C for 1 h.

example, the XRD pattern of samples M3, M4 and M5 sintered at

1350 -C is shown in Fig. 1.
The SEM images of samples M2, M3, and M4 are shown in
Fig. 2(a c), respectively. The BaTiO3-based ceramics were
relatively dense, ranging from 92% to 96% of the theoretical
density. Most pores were located at the grain boundaries. It was
found that the grain size increased considerably with increasing
BaBiO3 contents due to the increase of liquid phase at grain
boundaries. The melting point of BaBiO3 is about 1100 -C.
However the sintering temperature was higher than the melting
point of BaBiO3. When temperature in the furnace was up to the
melting point, the BaBiO3 compounds became the liquid phase.
The grains which touched the liquid phase grew quickly. Because
the driving force of grain growth is caused by the elimination of
grain boundary area, the retardation of grain growth is associated
with the decrease of energy of the grain boundary [13].
The resistivity temperature curves of BaTiO3-based ceramics
sintered at 1350 -C for different compositions are shown in Fig. 3.
The samples exhibit typical NTC characteristic. As a kind of
perovskite materials, (Sr,Pb)TiO3 ceramics exhibit novel NTC
PTC composite effect. However in our research it was firstly found
that BaTiO3 materials doped BaBiO3 only showed typical NTC
effect in wide temperature scale. BaBiO3 compounds are semiconducting materials. At the same time they show good NTC
effect. Fig. 4 presents NTC curve of pure BaBiO3 compounds. The
10 5
BaBiO3

10 4

10

12

Composition (%)

Temperature (C)

Resistivity .cm

3883

B450/600 Constant (K)

10

Resistivity .cm

Resistivity .cm

Y. Luo, X. Liu / Materials Letters 59 (2005) 3881 3884

Fig. 5. Specific resistivity at 450 -C and B 450 / 600 value of BaTiO3-based

ceramics as a function of BaBiO3 content, x.

pellets of pure BaBiO3 compounds were sintered at 850 -C for 1 h

in air, and then furnace cooled. Fig. 5 shows q 450, the specific
resistivity at 450 -C, and calculated B 450 / 600 values as a function
of x, BaBiO3 content. It is apparent that the samples q 450
decreased with an increase in BaBiO3 content. This is attributed to
the fact that BaBiO3 is semiconductor. The B 450 / 600 constant can
be calculated by the following equation [14]:
B450=600

lnq450 =q600
1=T450
1=T600

where q 450 and q 600 are the resistivities measured at 450 and 600
-C, respectively. The B 450 / 600 constant decreased with an increase
in BaBiO3 content.

4. Conclusion
NTC effect in BaTiO3 materials which doped BaBiO3
compounds was found. The samples only exhibit NTC
characteristic in wide temperature scale. It was detected
that the sintered bodies of BaTiO3-based ceramics were
composed of the solid solutions of BaTiO3 compounds
with a perovskite structure and BaBiO3 compounds with a
monoclinal structure. The difference between large grains
and fine grains in size became bigger and bigger with
increasing BaBiO3 contents due to the increase of liquid
phase at grain boundaries. The samples q 450 decreased
and their B 450 / 600 constant increased with an increase in
BaBiO3 content.

10 3

References
10 2
10 1
10 0
0

50

100

150

200

250

300

Temperature (C)
Fig. 4. Resistivity temperature curves of pure BaBiO3 sintered at 850 -C
for 1 h.

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