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CERAMICS
INTERNATIONAL
Ceramics International 41 (2015) S63–S68
www.elsevier.com/locate/ceramint

Effects of Mg addition and sintering temperatures on chemical compositions,

microstructures, densities and dielectric properties of strontium titanate
Oratai Jongprateepa,n, Jednupong Palomasb
a
Materials Innovation Center, Faculty of Engineering, Kasetsart University, 50 Ngamwongwan Rd, Ladyao, Chatuchak, Bangkok 10900, Thailand
b
Department of Materials Engineering, Faculty of Engineering, Kasetsart University, 50 Ngamwongwan Rd, Ladyao, Chatuchak, Bangkok 10900, Thailand
Received 26 October 2014; accepted 4 March 2015
Available online 1 April 2015

Abstract

Increasing demands in dielectric capacitors for electronic applications require continuous improvement of dielectric materials in terms of
enhanced dielectric constant and minimal dielectric loss. This study aimed at synthesizing strontium titanate powders doped with 10, 20, and
30 at% of Mg, and examining relationships among additive concentrations, chemical compositions, sintering temperatures, microstructures, and
dielectric properties of strontium titanate. Experimental findings indicated that increasing doping concentrations resulted in increased secondary
phase content, MgO, which seemed to have consequently led to grain size reduction. However, MgO concentrations were found to be lower than
10 wt%, which possibly have not significantly changed the sample's dielectric properties. The results also revealed that a higher sintering
temperature has led to an increase in sample density as well as to an enhancement in dielectric constant. It was further observed that strontium
titanate samples doped with 30 at% Mg and sintered at 1330 1C gave the highest dielectric constant value, which was ten times higher than the
samples with 10 at% Mg sintered at 1250 1C, the sample with the lowest dielectric constant. All samples in the study though yielded dielectric
losses of less than 3%, which are within the acceptable range for practical applications.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: Ceramics processing; Combustion synthesis; Strontium titanate; Microstructure dielectric

1. Introduction
Strontium titanate has been utilized in a number of energy-
related applications; for example, owing to its moderately high
dielectric constant and low dielectric losses loss [1,2], it can be
used as a high temperature semiconductor, the main compo-
nent of a capacitor. It has been widely accepted that proper
quantities of dopants can lead to enhancement of dielectric
properties, while excessive quantities of dopants often promote
formation of secondary phases. Rhim et al. has reported that
high quantities of secondary phases could lead to reduction of
dielectric constant in BaTiO3 [3,4].
In addition to doping and chemical compositions, microstructure
and sample densities are also factors contributing to variation of
n
Corresponding author.
E-mail address: oratai.j@ku.ac.th (O. Jongprateep).
dielectric properties [5–17]. Grain size can play a significant role in
the enhancement or reduction of dielectric constant. It has been
reported that finer grains, in micrometer range, contribute to higher
dielectric constant. However, for grains sizes in nanometer range,
reduction in grain size results in a decrease in dielectric constant
[11–16]. In addition, sample densities also affect dielectric constant.
Dielectric materials with densities higher than 95% of their
respective theoretical densities are required to boost higher
dielectric constant 17,18].
To attain desirable characteristics, low secondary phase inclu-
sion, fine grain sizes, and high sintered densities, synthesis and
processing of dielectric materials need to be carefully monitored.
Powder synthesis is the key step in fabricating dielectric
capacitors. Common techniques employed in the synthesis
process of dielectric materials include solid-state reaction, co-
precipitation, hydrothermal, sol–gel and solution combustion
technique [19–25]. The solution combustion technique is a

http://dx.doi.org/10.1016/j.ceramint.2015.03.192
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S64 O. Jongprateep, J. Palomas / Ceramics International 41 (2015) S63–S68

simple and rapid production technique of ceramic powders. It is A scanning electron microscope (FEI Quanta 450) was
also capable of synthesizing fine powders with good chemical employed in the examination of morphology of particles and
homogeneity [20]. grains. Sizes of the particles and the grains were determined using
As mentioned previously, numerous researches have been Image J Software. Pressed and sintered pellets were tested for
reported on individual effects of additives, grain size, or density. An impedance analyzer (HewlettPackard, 16451B) was
density on dielectric properties of strontium titanate. Relation- employed in the measurements of dielectric constants and
ships among doping concentrations, sintering temperatures, dielectric losses of the pellets at the frequency of 1 MHz.
chemical compositions, microstructures, and dielectric proper-
ties of strontium titanate have not been extensively investi- 3. Results and discussions
gated as yet. This study therefore, was aimed at synthesizing
strontium titanate powders with addition of 10, 20, and 30 at% 3.1. Effects of additive concentrations on chemical
of Mg using the solution combustion technique, and at compositions
systematically examining the relationships among doping
concentrations, sintering temperatures, chemical compositions, Synthesized strontium titanate powders were characterized by
microstructures, and dielectric properties of strontium titanate. an x-ray diffractometer to examine chemical compositions.
Diffraction patterns of all synthesized powders exhibited promi-
nent peaks corresponding to SrMgxTi1–xO3 (JCPDS 73-0661). A
2. Materials and methods secondary phase, identified as MgO (JCPDS 65-0476) was also
observed in the powders, as shown in Fig. 1. A greater quantity
SrTiO3 powders with Mg addition were synthesized using of MgO was observed in the powders with higher additive
the solution combustion technique. The technique involved contents. Weight fractions of the MgO secondary phase were
preparation of aqueous solutions containing metal nitrate, Sr calculated from integrated intensities of (110) and mass attenua-
(NO3)2 (Emsures), and Mg(NO3)2
6H2O (Alpha Chemica), tion factors, using Klugg's equation. The quantitative analysis
with stoichiometric ratios of Mg:Sr ¼ 0.1, 0.2, and 0.3. TiO2 indicated that all powders contained less than 10 wt% of the
(Aldrich) was dispersed in nitric acid and added to the nitrate MgO, as shown in Table 1.
solutions. Glycine, acting as combusting fuel in the powder
synthesis process, was added to the prepared solution mixtures.
3.2. Effects of additive concentrations on grain sizes
To obtain homogeneous mixtures, the prepared solutions were
stirred by a magnetic stirrer at a speed of 100 rounds per
In the previous section, compositional analysis was con-
minute and subsequently placed in an ultrasonic bath for
ducted on synthesized powders. In this section, the pressed and
10 min. A low heating temperature of less than 400 1C was
sintered pellets were examined for microstructures. Scanning
applied to the solutions to initiate combustion. Upon comple-
electron micrographs of the sintered pellet samples revealed
tion of the combustion reaction, the powder product was
equiaxed grains of average size range of 0.62–1.13 μm.
collected and calcined at 900 1C for 6 h. Subsequently, the
Grain size analysis revealed that higher concentrations of the
powders were uniaxially pressed under the pressure of 30 MPa
dopant resulted in grain refinement, as shown in Fig. 2a–f. For
into pellets with a diameter of 20 mm. The pellets were
samples sintered at 1250 1C, average grain sizes of 1.03, 0.79
sintered at 1250 1C and 1330 1C for 3 h at a heating rate of
and 0.62 μm were observed in the powders with 10, 20, and
5 1C/min.
30 at% Mg, respectively. At a higher sintering temperature of
Compositions of the calcined powders were investigated
1330 1C, the samples exhibited a slight coarsening effect on
using an x-ray diffractometer (Bruker, D8 Advance), at angles
ranging from 51 to 801 in 2θ, with a 0.021 step size interval and
a scanning rate of 1.31/min. A quantitative analysis was
performed to determine weight fractions of the main phases
(SrMgxTi1–xO3) to the total powder weight. The weight
fractions were calculated from integrated intensities of the
prominent diffracted peaks and mass attenuation factors, using
the following equation:
ðI pure =I mix ÞAimpurity
f¼ ð1Þ
Apurity  ðI pure =I mix ÞðApurity  Aimpurity Þ
where f is the weight faction of the primary phase (SrMgxTi1–
mix
xO3–x) to the total powder, I is the integrated intensity of
pure phase and secondary phase, Ipure is the integrated intensity
of pure phase, Aimpurity is the mass attenuation factor of TiO2
and MgO, which are at 125.905 and 29.106, respectively and
Apurity is the mass attenuation factor of SrTiO3 or SrMgxTi1– Fig. 1. X-ray diffraction patterns of the powder indicating SrTiO3 and SrTiO3
xO3, which is at 110.773. with 10–30 at% Mg.
 O. Jongprateep, J. Palomas / Ceramics International 41 (2015) S63–S68 S65

grains as shown in Fig. 3. Average grain sizes of 1.13, 1.02,
and 0.68 μm were observed in the powders with 10, 20, and
30 at% Mg, respectively.
As mentioned in the previous section, higher doping
concentrations promoted formation of MgO phase. The results
were in agreement with the study of Park et al. which reported
that by adding MgO at concentrations higher than 5 mol% into
BaTiO3, grain size was reduced, which has been attributed to
the diffusion of MgO into the grain boundaries.
Accordingly, the MgO phase acted as a pinning agent that
prevented movement of grain boundaries, causing the inhibi-
tion of grain growth [26].
contained slightly larger grains than those sintered at lower
temperature, which seemed to be related to lower porosity.
However, the effects of doping concentrations on porosity
were not apparent. Results of sample density measurement
though were in agreement with the microstructural examina-
tion. Average sample densities sintered at 1250 1C ranged
from 62.7 to 66.9% of its theoretical density, while densities of
samples sintered at 1330 1C ranged from 82.1 to 83.2% of its
theoretical density (Fig. 4). Samples in this study exhibited
relatively low densities, which may considerably exert adverse

3.3. Effects of additive concentrations on densities

In addition to the grain size analysis, a microstructural

examination also provided information related to densities of
the samples. The samples sintered at a higher temperature
Table 1
Weight fractions of the primary phase (SrMgxTi1–xO3–x) and secondary phase
(MgO) to total powders.

Compositions Quantity (wt%)

Primary phase Secondary phase

SrTiO3 with no additive 100 0.00

SrMgxTi1  xO3  x with 10 at% Mg 97.40 3.60
SrMgxTi1  xO3  x with 20 at% Mg 93.46 6.54
SrMgxTi1  xO3  x with 30 at% Mg 90.16 9.84 Fig. 3. Average grain sizes of the samples with 10, 20 and 30 at% Mg,
sintered at 1250 1C and 1330 1C

Fig. 2. Scanning electron micrograph showing grain morphology of the samples with 10 at% Mg (a), 20 at% Mg (b), 30 at% Mg (c) sintered at 1250 1C, and 10
at% Mg (d), 20 at% Mg (e), 30 at% Mg (f) sintered at 1330.
S66 O. Jongprateep, J. Palomas / Ceramics International 41 (2015) S63–S68
Fig. 4. Average densities of the samples with 10, 20 and 30 at% Mg, sintered
at 1250 1C and 1330 1C
impact on dielectric properties. The results suggested that a
higher sintering temperature or cold isostatic pressing might be
required to enhance density of the sintered samples.
3.4. Effects of grain sizes on dielectric constants
In this section, a relationship between grain sizes and
dielectric constants of the sintered samples was examined.
Average grain sizes ranging from 0.62 to 1.13 μm and average
dielectric constants (measured at 1 MHz) ranging from 20.1 to
212.0 were observed in this study. A plot presenting dielectric
constants vs. grain sizes, shown in Fig. 5., revealed that the
samples with finer grains were inclined to have higher
dielectric constants.
The results were in agreement with the study of Kim et al.
and Ying et al., who reported that dielectric materials in
micrometer grain size range enhance dielectric constant
[12,15].
3.5. Effects of densities on dielectric constants
The relationship between average densities and samples'
dielectric constants is presented in Fig. 6. It has been widely
found and accepted that higher densities result in the enhance-
ment of dielectric constants [17,18]. Knowing that air has a
very low dielectric permittivity of 1, it therefore follows that
samples containing high level of pores or air would be inclined
to have lower dielectric constants.
3.6. Relationships among additive concentration, sintering
temperature, grain sizes and density on dielectric constant
Additive concentrations of 10–30 at% Mg resulted in the
formation of small quantities of MgO phase. This amount of
MgO did not produce a pronounced effect on dielectric
constant deterioration. Formation of MgO, on the contrary,
resulted in the refinement of grain size that consequently led to
the enhancement of the dielectric constant.
Fig. 5. The relationship between dielectric constants and grain sizes of SrTiO3
samples doped with Mg 10–30 at% sintered at 1250 1C and 1330 1C
Fig. 6. The relationship between dielectric constants and theoretical densities
of the samples with Mg 10–30 at% Mg, sintered at 1250 1C and 1330 1C
As additive concentrations increased, two competing factors
contributing to the change of dielectric constant were evident.
Grain size enlargement, which generally results in a deleterious
effect on dielectric constants, and an increased density, resulting in
an enhancement of the dielectric constants, were observed. A slight
effect on grain coarsening and a significant effect on density
enhancement were observed in the samples sintered at 1250 1C and
1330 1C. Experimentation results also revealed that the samples
subjected to sintering at a higher temperature exhibited higher
dielectric constants, as shown in Fig. 7.
From the aforementioned results, it could be inferred that
enhancement of dielectric constant could be attained in the
samples with high additive concentrations and sintered at high
temperature. The strontium titanate sample with 30 at% of Mg
that was sintered at 1330 1C yielded the highest dielectric
constant, which was ten times higher than the samples with
10 at% of Mg and sintered at 1250 1C. Dielectric losses ranged
from 0.003 to 0.024, which were within the acceptable range
for practical applications (Table 2).
 O. Jongprateep, J. Palomas / Ceramics International 41 (2015) S63–S68 S67

Acknowledgment

The authors gratefully acknowledge financial support from

the National Science and Technology Development Agency of
Thailand(Grant No: SCH-NR2014-115). Equipment supports
from the Department of Materials Engineering, Faculty of
Engineering, Kasetsart University, and the Department of
Science Service, Ministry of Science and Technology, Thai-
land are gratefully acknowledged.

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