See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/330113226

Effect of Calcination and Sintering Temperatures on Physical Properties of

Barium Titanate Ceramic

Article · January 2019

CITATIONS READS

3 2,970

5 authors, including:

Muhammad Ali Siddiqui Fayaz Hussain

NED University of Engineering and Technology, Karachi NED University of Engineering and Technology, Karachi
42 PUBLICATIONS 345 CITATIONS 66 PUBLICATIONS 873 CITATIONS

SEE PROFILE SEE PROFILE

Ahmad Azmin Mohamad Muhammad Tufail

Universiti Sains Malaysia NED University of Engineering and Technology, Karachi
192 PUBLICATIONS 4,654 CITATIONS 62 PUBLICATIONS 275 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Muhammad Ali Siddiqui on 09 June 2020.

The user has requested enhancement of the downloaded file.

 Int. J. Electroactive Mater. 6 (2018) 42-47
www.electroactmater.com

RECEIVED Effect of Calcination and Sintering Temperatures on Physical

22 October 2018
Properties of Barium Titanate Ceramic
REVISED Muhammad Ali Siddiqui1, Fayaz Hussain2*, M Sohail Hanif2, Ahmad Azmin Mohamad3, Muhammad
11 November 2018
Tufail2
ACCEPTED FOR
1
Department of Metallurgical Engineering, NED University of Engineering and Technology, Pakistan.
PUBLICATION 2
Department of Materials Engineering, NED University of Engineering and Technology, Pakistan.
12 December 2018 3
School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300, NibongTebal,
PUBLISHED Penang, Malaysia.
18 December 2018 E-mail: fhussain@neduet.edu.pk*

ABSTRACT: Barium titanate based perovskite structured ceramics are well known dielectrics in the
category of functional materials. This study was conducted to investigate the effect on the perovskite
structure purity and density due to change in calcination and sintering temperatures of barium titanate
(BaTiO3) ceramics; synthesized by conventional solid-state reaction technique. These characteristics are
directly affecting the dielectric property of BaTiO3. Calcination of the powders accomplished at five
different temperatures i.e., 930, 960, 1000, 1030 and 1060 °C for 4 h and sintering was done of pellet at
four different temperatures i.e., 1250, 1300 and 1350 °C for 4 h. XRD patterns of calcined-samples
revealed the presence of BaTiO3 as a single phase with low intensity peaks of intermediate phases i.e.
BaCO3 and TiO2. The patterns also confirm tetragonal phase in all the sintered samples. The highest
amount 95.15 % of perovskite phase achieved which was calcined at 960 °C temperature. The best
sintering temperature was recorded as 1350 °C in terms of bulk density of about 5.8 g/cm3and a true
porosity of about 3.6 %.
Key Words: Barium Titanate, Calcination, Sintering, Bulk density, True porosity

1. Introduction
Barium titanate (BaTiO3) is commercially available ferroelectric ceramic with ABO3 type of perovskite
structure having a high dielectric constant [1-3], huge range of piezoelectric values [4] would attract more as
electronic devices for a diversity of electro optic devices such as piezo sensors, multilayer capacitor
(MLCCs), piezo transducer and printed circuit board [1-6].
The crystal structure of barium titanate (BaTiO3) has a major role that provides a high dielectric constant.
The crystallographic dimension of this material varies as temperature varies. It has been known that
calcination temperatures have a strong effect on the crystal structure and polarization characteristic of BaTiO3
[1-6]. On the other hand, composition homogeneity, particle shape, particle size distribution density,
microstructures and single phase are equally important to get good piezoelectric properties of BaTiO3 [6-8].
It has been addressed that the finer size powder would rapidly sintered more, comparatively at lower
temperature than coarser powder. Conventionally, BaTiO3 has been prepared through a solid-state method by
utilizing BaCO3 and TiO2 as starting raw powders [1-6].
The rational of this paper is actually to develop the basic understanding for new researchers to understand
the calcination and sintering behavior (how to optimize these temperatures), and how to calculate the
perovskite phase from the X-ray diffraction (XRD) data of BT. In addition to this, the effect of these
temperatures on physical properties of BT was added. Overall processing and purity of Barium titanate
materials was essential.
Nonetheless, bulk density of ABO3 ceramics is very important for ferroelectric properties; porosities are
not needed for miniaturizations of devices in the case of thin multilayers. So, this research explored to
optimize the calcination and sintering temperatures where single phase was equally important to get the
homogenous behavior throughout the sample. The crystal structure, morphology and density with porosity
were characterized by XRD, scanning electron microscope (SEM) and Archimedes method, respectively.

2. Experimental
Solid-state reaction technique was used for the synthesis of barium titanate ceramic powder. For this,
barium carbonate (BaCO3) (RDH, 99.99 %) and titanium oxide TiO2 (BDH, 99.99 %) were used as a starting
material. These two ingredients were mixed in polyethylene jar for 1 h in a mixer by using ZrO2 ball. Both
ingredients were chosen with equal molar ratio according to the stoichiometric formula given in Equations 1
and 2.
Int. J. Electroactive Mater., Vol. 6, 2018 Siddiqui et al.

(mol % of BaCO3) (MW* of BaCO3)

Wt% BaCO3 = (mol % of BaCO3) (MW BaCO3) + (mol % of TiO2) (MW TiO2) ..... 1

Wt% TiO2 = (mol % of TiO2) (MW of TiO2) ..... 2

(mol % of BaCO3) (MW BaCO3) + (mol % of TiO2) (MW TiO2)
* Molecular weight.

The mixed powder was then grounded in alumina jar with ZrO2 ball for 2 h using 80 ml ethanol as a liquid
medium. It was later dried in an oven at 90˚C for 12 h. Dried powder was calcined at five different
temperatures i.e. 930, 960, 1000, 1030 and 1060 °C for 4 h for evaluation the effect of calcinations
temperature on the formation of pervoskite phase. The calcined powder was milled again in the presence of
10 wt% polyvinyl alcohol (PVA) binder to strengthen the green pellets. The powders were pressed into green
pellets having dimensions 25 mm diameter and 2 mm thick at 25 MPa pressure. The samples were heated in
a furnace for 4 h at 600 °C for binder burn off at a heating rate of 10 °C/min. The green pellets were then
sintered at four different sintering temperatures increment of 50 °C, start from 1200 °C to 1350 °C for study
the effect on morphology and density.
The calcined powder samples were phase characterized by using x-ray diffraction (PANalytical X’PERT
PRO, HOLLAND) with Cu (Kα) radiations λ = 1.54060 Å, operating at 30 mA and 40 KV, step size of
0.02°{2θ} and step time 0.3{s} from 10° to 80°. The percent amount or content of the BaTiO3 (Perovskite)
phase was examined by utilizing the XRD pattern data. The percentage of perovskite phase was calculated
by the given formula [9]. The relative amount of the phases was determined by measuring the high intensities
peak of X-ray for all the phases present.

I (Perovskite Phase)
Content of Perovskite Phase (%) =
I (Perovskite Phase) + I (Impurity Phase)

The morphology of the sintered ceramic was investigated by SEM on FEI Quanta 200S at an accelerating
voltage of 10 KV. The apparent porosity, true porosity and density (bulk density) of the sintered specimens
were determined by using Archimedes method as per standard ASTM-C373-88. The following formulas were
used for calculations [10].
Ww - Wd
Apparent Porosity, P = x 100 ..... 3
Ww - Ws

Wd
Bulk Density, B = x 100 ..... 4
Ww - Ws

ρ-B
True Porosity = x 100 ..... 5
Ρ
Where, Wd is dry weight (gm), Ws is suspended weight (weight in water) (gm) Ww is weight after
soaking 2h in water (gm), ρ is the true density of a BaTiO3 which is 6.02 g/cm3.

3. Results and discussion

XRD results of all calcined samples shown in Figure 1 (a-d). Where 930 °C sample indicates two
secondary phase peaks, like no 2, 3 and 5; whereas 2 and 5 matched with ICDD card no 00-005-0378 which
was of barium carbonate (BaCO3); it means BaCO3 was not completely reacted at this temperature. In
addition to this, peak around 27° (2θ) was of titanium dioxide (TiO2), as per ICDD card no. 01-087-0710.
The remaining peaks are the characteristic peaks of tetragonal structure of BaTiO3 (ICDD card no. 01-089-
1428), where the relative amount of BT phase was 84.86 % as per peak intensities calculations. This phase
percentage was determined from the raw data of XRD (Table 1) according to the formula given in
experimental section.
BaCO3 reaction was almost complete at 1000, 1030, and 1060 °C, respectively as shown in the Figure
1(c-e). The percentages of perovskite and secondary phases of all calcined samples shown in Figure 1(f). At
10030 °C and 1060 °C, the second phase that is unknown at 29° (2θ) (Figure1 d-e). The presence of
intermediate phases could be the result of various synthesis parameters such as variation in particle size, trace
impurities in raw materials, calculation error, not homogenous mixing and or human error.

43
Int. J. Electroactive Mater., Vol. 6, 2018 Siddiqui et al.

Based upon the crystallographic information of the samples, the crystal structure of the sample was found
to be tetragonal, which is good agreement with Ogihara et al. [11]. It has been studied by Jose that the barium
titanate has four different forms of isomorphs, at very low temperature (below zero-°C) it is rhombohedral
and orthorhombic, whereas at above Troom it would be tetragonal and cubic depending on processing
parameters respectively [7]. Among four crystalline phases, two have been considered the most important
crystalline phases of BaTiO3 which are technologically useful in microelectronic industries. These two are
cubic and tetragonal structures, while cubic is most suitable for commercial capacitors due centro-
symmetrical paraelectric and tetragonal is non-centro-symmetrical best for the application of piezoelectricity
[5]. Maison et al. [3] reported that the formation of BaTiO3 starting first at the grain boundaries (i.e.,
BaTiO3/TiO2), it was further reacted with barium carbonate and converted into complex Ba2TiO4.
Finally, this complex compound plus TiO2 appeared into BaTiO3 [3], that could be the reason, getting
pure BT is not easier. Maison et al. [3] researched that the cubic phase was dominated at lower calcination
temperatures and as temperature raises the phase changes took place from cubic to tetragonal, as well as the
morphology of grains converted from spherical to acicular in shape. Jamal et al. [5] reported that, the phase
formation at 900 °C was not complete as discussed, the presence of BaTiO4 and BaCO3 constitutes when
synthesized by conventional solid-state method. Based upon the highest purity at 960 °C in terms of 2nd
phases, this calcination temperature was selected for sintering at different temperatures (Figure 4).

Figure 1: XRD Data of Barium titanate powder calcined at (a) 930 °C, (b) 960 °C, (c) 1000 °C, (d) 1030
°C (e) 1060 °C (f) Percentage of Perovskite phase and secondary phases

Table 1: Peak List of samples calcined at 930 °C

Position Height d-spacing Rel. Int.

Peak No
[°2Th.] [cts] [Å] [%]
1 22.131130 22.546060 4.01672 14.00
2 24.094690 23.873790 3.69364 14.82
3 26.852150 13.417960 3.32028 8.33
4 31.654060 161.064900 2.82670 100.00
5 34.256310 4.863602 2.61769 3.02
6 39.002330 40.097650 2.30940 24.90
7 45.355670 58.776370 1.99958 36.49
8 51.042900 14.010190 1.78934 8.70
9 56.315610 60.379030 1.63368 37.49
10 66.058320 29.830100 1.41439 18.52
11 70.562170 6.179924 1.33475 3.84
12 75.160310 17.188770 1.26410 10.67

44
Int. J. Electroactive Mater., Vol. 6, 2018 Siddiqui et al.

Figure 2 showing the stereo micrograph of BaTiO3 pellets sintered at 1200, 1250, 1300 and 1350 °C
respectively. It was observed that as the sintering temperature increased, the color of sample changed to dark
-brown at 1350 °C. This might be the result of cationic or anionic losses in the material, as reported by Li et
al. in the case of co-doping of Nb and In in rutile TiO2 [12].
The SEM images of BaTiO3 ceramic samples fired at 1250 °C and 1350 °C temperatures are shown in
Figure 3(a-b). It was noted that the samples sintered at 1250 °C were containing less bulk-density (58.13 %)
with definitely higher porosities. Despite to this, the samples sintered at 1350 °C, shown less porosity with
density improved to 96.34 %, as in Figures 4(a-b). This change could be inferred mainly due to the mobility
of grain boundaries; because grain boundaries are influenced by some processing parameters such as sintering
temperatures, mixing/milling, diffusion coefficient of compositions [13]. It was also reported that the average
grain size would be increased at higher sintering temperatures as was in the case of BZT ceramics [14].
Figures 4(a-b) indicates the variation in bulk density, true porosity and apparent porosity with sintering
temperature. The higher sintering temperature than calcination is always set to reduce porosity and enhance
density, which consequently enhances the relative permittivity [16]. In addition; doping, microstructure,
mainly grain size and density, are also major contributing factors to modify the dielectric constant. Moreover,
higher sintering temperature generally lead to higher diffusion rate that in result to affect the grain growth
[15].

Figure 2: Stereo Micrograph at 7x, Ts= Sintering Temperature

(a) (b)

Figure 3: SEM Micrograph of Sintered BaTiO3 Pellet (a) at 1250 °C and (b) 1350 °C

45
Int. J. Electroactive Mater., Vol. 6, 2018 Siddiqui et al.

(a) (b)

Figure 4: Variation in (a) True and Apprent porosity (b) Bulk density

4. Conclusions
The effect of calcinations temperature on the crystallographic properties and sintering temperature effect
on the physical properties has been investigated in this work. The BaTiO3 (perovskite phase) was successfully
obtained by a well-known conventional method of solid-state reaction. The X-ray diffraction pattern showed
the BaTiO3 phase was obtained at all studied calcinations temperature with intermediate phases. The amount
of perovskite phase approximately similar when calcined at 960, 1000 and 1030 °C whereas, it was less
observed when calcined at 930 and 1060 °C due to the presence of secondary phases. The best reaction
temperature was observed 960 °C which has 95.15 % relative amount of BaTiO3 phase. Based upon the
crystallographic data, the crystal structure was recorded as a tetragonal at Troom. The effect on the bulk density
and on porosity was determined by ASTM-C373-88 and it has been observed that, due to increase in sintering
temperature the bulk density also increased whereas the apparent and true porosity have been decreased. The
colour changes to black which indicate the oxygen vacancies increases as increase sintering temperature. The
1350 °C temperature was observed as optimized sintering temperature which has a bulk density of about 5.8
g/cm3 and 3.6 % true porosity. The higher sintering temperature led to grain coarsening and reduced porosity
had probably accounted for the density enhancement noted in the samples.

Acknowledgement
Authors would like to thank to NED University of Engineering and Technology, Pakistan for financial
support and lab facilities.

References
1. L. Simon-Seveyrat, A. Hajjaji, Y. Emziane, B. Guiffard, D. Guyomar, Ceram. Int. 33 (2007) 35-40.
2. S.B. Majumder, V.N. Kulkarni, Y.N. Mohapatraand D.C. Agrawal, Bul. Mat. Sc. 17 (1994) 19-23.
3. W. Maison, R. Kleeberg, R.B. Heimann, S. Phanichphant, J. Euro. Ceram. Soc. 23 (2003) 127-132.
4. A. Sreenivasulu, T.N.V.K.V. Prasad, S. Buddhudu, In. J. Pure & Appl. Phys. 45 (2007) 741-744
5. Asad Jamal, Muhammad Naeem, Yaseen Iqbal, J. Pak. Mater. Soc. 2(2008) 91-95.
6. M. Gromada, M. Biglar, T. Trzepiecinski, F. Stachowicz, Bull. Mater. Sci., 40 (2017) 759-771.
7. H.-L. Wang, Structure and Dielectric Properties of Perovskite-Barium Titanate (BaTiO3), MatE 115,
Fall 2002.
8. D.W. Richerson, Modern Ceramics Engineering: Properties, Processing and Use in Design, CRC
Press, New York (2005), pp 330-334.
9. G. Feng, D. Zhenqi, Y. Le, C. Lihong, T. Changsheng, Ceram. Int. 35 (2009) 2885-2890.
10. H. Ohuchi, S. Tsukamoto, M. Ishii, H. Hayakawa, J Euro. Ceram. Soc. 19 (1999) 1191-1195.
11. H. Ogihara, C.A. Randall, S.T. McKinstry, J Am. Ceram. Soc. 92 (2009), 110-118.
12. J. Li, F. Li, Y. Zhuang, L. Jin, L. Wang, X. Wei, Z. Xu, S. Zhang, J. Appl. Phys. 116 (2014) 074105-1
074105-9.
13. W. Chaisan, R. Yimnirun, S. Ananta, Ferroelec. 346 (2007) 84-92.
14. W. Cai, F. Chunlin, J. Gao, H. Chen, J. Alloy. Compd. 480 (2009) 870-873.

46
 Int. J. Electroactive Mater., Vol. 6, 2018 Siddiqui et al.

15. O. Jongprateep, N. Sato, in: Proceedings of Materials Today Conference on the 10th Thailand
International Metallurgy (The 10th TIMETC), 30-31 March, 2017, Thailand, 9298-9305.
16. Y.C. Liou, S.L. Yang, Materials Science and Engineering B 142 (2007) 116-120.

© 2018 by the authors. Published by EMS (www.electroactmater.com). This article is an open access article
distributed under the terms and conditions of the Creative Commons Attribution license
(http://creativecommons.org/licenses/by/4.0/).

47

View publication stats