STRUCTURAL AND DIELECTRIC

CHARACTERIZATION OF BARIUM TITANATE

A Dissertation Report Submitted to

Department of Physics

In partial fulfillment of the requirement

For the degree of

INTEGRATED MASTER OF SCIENCE

IN
APPLIED PHYSICS

BY

AMIT BISWAL
Regd no- 1812106004

Under the guidance of

Mrs. Anita Kumari Panda

COLLEGE OF ENGINEERING AND TECHNOLIGY

(A Constituent college of BPUT,Rourkela,Odisha)
Techno campus,Ghatikia,Bhubaneswar-751029
 DEPARTMENT OF PHYSICS
COLLEGE OF ENGINEERING AND TECHNOLOGY
(A Constituent College of BPUT,Rourkela,Odisha)
Techno campus,Ghatikia,Bhubaneswar-751029

CERTIFICATE
This is to certify that the dissertation report entitled,
“STRUCTURAL AND DIELECTRIC CHARACTERIZATION
OF FERROELECTRIC CERAMICS” submitted by Amit
Biswal bearing “Regd no.- 1812106004” in partial fulfilments of
requirements of the award of Integrated M.Sc. in Applied
Physics, at College of Engineering and Technology,
Bhubaneswar is an authentic work carried out by him under our
supervision and guidance. To the best of our knowledge, the
matter embodied in the project report has not been submitted to
the other university/ institute for the award of any M.Sc./ In.
M.Sc. degree.

Dr. Babita Ojha Mrs. Anita Kumari Panda

HOD Guide
Dept. Of Physics
 DECLRATION

This is to certify that the review report entitled “Structural and

Dielectric Characterization of Ferroelectric Ceramics” being
submitted to the Department of Physics, College of Engineering
and Technology, Bhubaneswar, for In. M.Sc. degree in Physics
has not been submitted to any other University or Institute for
the award of any degree or diploma.

AMIT BISWAL
Regd No- 1812106004
 ACKNOWLEDGEMENT: -

I would like to express my sincere gratitude to my dissertation

guide Mrs. Anita Kumari Panda for her vital support, guidance
and encouragement for guiding immensely through the course of
this project on the topic “Structural and Dielectric
Characterization of Ferrolectric Ceramics ”. She always
evinced keen interest in my work. Her constructive advice and
constant motivation have been responsible for completion of my
dissertation.
Secondly, I would like to express my gratitude to our H O.D.
Ma’am & other faculty members of our Physics Department
for their support during my dissertation.

AMIT BISWAL
 Contents
Sl No Topic Page No
1 Abstract 1
2 Literature Review
2.1 Introduction 2
2.2 Ferroelectric Ceramics 2
2.3 Dielectric Materials 3
2.4 Piezoelectricity 5
2.5 Pyroelectricity 5
2.6 Ferroelectricity 6
2.7 Barium Titanate 8
2.8 Structure of Barium Titanate 9
3 Synthesis
3.1 Methods of preparation of BaTiO3 10
3.2 Solid state reaction 12
3.3 BaCO3/TiO2 powder mixture 13
4 Analysis
4.1 X-ray diffraction study of BaCO3/TiO2 milled 13
mixture
4.2 Pressing and Sintering 14
4.3 Dielectric properties 15
4.4 Effect of dopants or additive in BaTiO3 18
properties
5 Application
5.1 Application of ferroelectric ceramics 20
5.2 Ceramic capacitors 20
6 Conclusion 22
7 References 23
 LIST OF FIGURES
Fig 1: ceramic insulator
fig2: ceramic capacitor
Fig 3: Shift in the distribution of charge in a ceramic insulator
when it is placed in an electric field between two electrically
conductive electrodes
Fig 4: Hysteresis loops resulting from plots of polarization vs.
applied voltage
Fig 5: pervoskite structure of Barium Titanate
Fig 6: schematic representation of preparation of BaTiO3
Fig 7: XRD pattern of the powders at different calcination
temperatures
Figure (8): Dielectric properties as a function in temperature and
frequency for the BaTiO3 prepared from BaCO3/TiO2-c
powder mixture, milled for 7.5h, calcined at 800°C/3h, and
sintered at 1300°C/3h
Figure (9): Dielectric properties as a function in temperature and
frequency for the BaTiO3 prepared from BaCO3/TiO2-c
powder mixture, milled for 7.5h, calcined at 800°C/3h, and
sintered at 1350°C/3h
Fig 10: single layer ceramic capacitors
 ABSTRACT
BaTiO3 powder was prepared at low temperature using solid state
reaction, starting with BaCO3/TiO2 powder mixture. It was found that, a
single phase BaTiO3 was formed after calcination at 750°C for 10h and
at 600°C for 6h for the first and second mixtures, respectively. Thermal
and XRD analyses were used to study the formation kinetics of BaTiO3.
Characterization and the dielectric properties of the sintered BaTiO3 were
investigated. The relative permittivity and the dielectric loss measured at
room temperature and at 1kHz were 2028.5 and 0.043 for BaTiO3
prepared from BaCO3/Ti

1
INTRODUCTION
Ferroelectric ceramics or ferroelectrics refer to the group of dielectrics
having the property of spontaneous polarization (i.e., they retain a dipole
even after an applied voltage has been removed). The key characteristics
of a ferroelectric crystal are that the direction of the polarization can be
reversed by application of an electric field and that a hysteresis loop
results. Ferroelectrics mainly have two characteristics, asymmetry and
high dielectric constant or high permittivity

Barium titanate is one of the most widely used ferroelectric materials due
to its high dielectric constant and low loss characteristics. As advanced
miniaturization requires smaller circuit area, the multilayer ceramic
capacitors
(MLCCs) with higher efficiency were developed. The MLCCs films
(thick or thin) usually require a sub-micron grain size of the ceramic.
Conventionally, BaTiO3 powders are manufactured at high temperatures,
by solid-state reaction or from chemically derived precursors. These
methods produce large, nonuniform, and agglomerated particles that have
to be milled and heat treated again to obtain the required particle size
(0.5-1.5μm) to fabricate reliable MLCCs
Another possibility to obtain the required grain size could be by
mechanical activation of raw materials during powder preparation
process. The mechanical activation using high energy milling process is
one of the most effective methods for obtaining highly dispersed
powders. It results in a decrease of particle size that leads to the initiation
of solid state reaction between the starting components at lower
temperatures

FERROELECTRIC CERAMICS
Ceramic materials have a wide range of electrical properties. Some of
them do not allow passage of an electric current even in a very strong
electric field and thus are excellent insulators. Others allow passage of an
electric current and have application as electrical conductors. The third
type allows an electric current to pass only under certain conditions or
when an energy threshold has been reached and thus are useful
semiconductors. However, some ceramics do not conduct electricity but
undergo internal charge polarization that allows the material to be used
for storage of an electrical charge in capacitors
Examples of electro-ceramics include Zinc oxide for varistors, lead
zirconium titanate (PZT) for piezoelectrics, barium titanate for

2
capacitors, tin oxide as gas sensors, lead lanthanum zirconium titanate
(PLZT) and lithium niobate for electro-optic devices.

3
Fig 1: ceramic insulator fig2: ceramic capacitor

Dielectric materials
Ceramic materials that are good electrical insulators are referred to as
dielectric materials. Although these materials do not conduct electrical
current when an electric field is applied, they are not inert to the electric
field (E). The field causes a slight shift in the balance of charge within the
material as shown in Figure , so that the system acquires an electrical
dipole moment (P) . The dipole moment per unit volume is called
polarization. This moment is proportional to the electric field, E

Fig 3: Shift in the distribution of charge in a ceramic insulator when it is placed in an electric field
between two electrically conductive electrodes

4
The field that a molecule in the interior of a dielectric situated between
the plates of a charged condenser actually experiences is known to be
larger than the applied field. This is related to the polarization is always
proportional to the applied field; thus
P = εoχeE
Since the dielectric
susceptibility χe is equal to (εr-1), where εr is the relative permittivity, the
polarization will be :
P = εoE (εr-1)

The degree of polarizability or charge storage capability of a material is

identified by the term dielectric constant or as relative permittivity.
When an electric field is applied to two flat plates of a metal, one plate
becomes positive and the other negative. The electric field causes
polarization in the material in the space between the conductive plates.
The relative dielectric constant (k΄) compares the polarizability of the
material with that of the vacuum between the plates.
k΄ = kmaterial / kvacuum
In other references; the relative permittivity is quoted as εr , while ε0 is
defined as the permittivity of the free space (8.85 x 10-14 farads/cm), and
ε is the permittivity of the dielectric material. In this thesis the
permittivity terms (εr, ε0, ε) will be used according to Equation
εr= ε/ ε0

An ideal dielectric would allow no flow of electric charge, only a

displacement of charge via polarization. Hence the current leads the
voltage by 90°C; or out of phase by a quarter-cycle. Real materials
always have some loss. The phase angle between the current and voltage
is not exactly 90°C; the current leads the voltage by 90- δ, where δ is
defined as the angle of lag. The angle of lag, δ, is the measure of the
dielectric power loss.
Power loss = πƒVo2 εrtanδ

The product "εr tanδ" is called the loss factor and "tanδ" is referred to as
the loss tangent or the dissipation factor. The loss factor consequently
characterizes the usefulness of a material as a dielectric or as insulator; in
both cases a low loss tangent is desirable

Dielectric strength is the capability of the material to withstand an electric

field without breaking down and allowing electrical current to pass. It has

5
units of volts per unit of thickness of the dielectric material, volts per mil
(thousandth of an inch) or volts per centimeter are often used.
If the applied field exceeds certain critical value, the dielectric material
breaks down and conducts electricity and this limits the operating
conditions for dielectrics which are used in insulators or in capacitors

Piezoelectricity
Piezoelectricity is the ability of certain crystalline materials to develop an
electrical charge proportional to a mechanical stress.
Polarization occurs in single crystals of some materials when a stress is
applied, one side of the crystal derives a net positive charge and the
opposite side derives a net negative charge. Only crystals that are
anisotropic with no center of symmetry are piezoelectric (there are 32
crystal classes, 20 of them are piezoelectric). Even these are not
piezoelectric in all directions. The piezoelectric effect is reversible in that,
piezoelectric crystals when subjected to an externally applied voltage,
they change shape by a small amount .
The piezoelectric effect was discovered by Pierre and Jacques curie and
first reported in 1880. Piezoelectricity was identified by the Curies in a
number of naturally occurring and laboratory grown single crystals.
Examples included quartz, zinc blende (sphalerite), boracite, tourmaline,
topaz, sugar, and Rochelle salt (sodium-potassium tartrate tetrahydrate
(NaKC4H4O6.4H2O).
The piezoelectric phenomenon has led to the widespread use of
piezoelectric ceramics as transducers in ultrasonic devices, microphones,
phonograph pickups, accelerometers, and sonar devices

Pyroelectricity
Pyroelectric crystals are a special class of piezoelectric crystals. They
contain within their crystal structure a preexisting spontaneous
polarization along at least one crystallographic direction, heating of the
crystal results in mechanical deformation due to thermal expansion,
which causes a change in the extent of polarization. Of the piezoelectric
crystal classes, 10 are pyroelectric.
Examples of pyroelectric crystals include würtzite, tourmaline, Rochelle
salt, triglycine sulfate, BaTiO3.
Most pyroelectric materials lose their pyroelectric behavior as the
temperature is increased to a few hundred degrees except the
LiTaO3 material, which retains its pyroelectric behavior up to 609°C. As
a result, LiTaO3 has been developed into a scanning microcalorimeter

6
capable of sensitivity in the sub-microcalorie range. It has also been used
as a highsensitivity microenthalpimeter for monitoring catalytic processes

Ferroelectricity
Ferroelectricity is a phenomena discovered in 1921, it is analogous to the
ferromagnetic phenomena of iron. Ferroelectric materials do not show
any connection with iron at all. The term was devised to explain a
spontaneous polarization upon cooling below a curie temperature as well
as a display of ferroelectric domains and ferroelectric hysteresis loop.
Ferroelectrics (ferroelectric materials) are a subclass of pyroelectric
crystals, exhibiting spontaneous polarization; they retain a dipole even
after an applied voltage has been removed. Ferroelectric behavior is
dependent on the crystal structure.
The crystal must be noncentric and contain alternate atom positions or
molecular orientations to permit the reversal of dipole and the retention of
polarization after the voltage is removed. Ferroelectric ceramics do not
absorb moisture, nor do they dissolve in water, being able to perform over
a wide range of operating temperatures. However, every ferroelectric has
a temperature point above which the material becomes substantially non-
electric, i.e. dielectric, known as its Curie temperature
Ferroelectric crystals possess regions with uniform polarization called
ferroelectric domains. Within a domain, all the electric dipoles are
aligned in the same direction. There are many domains in a crystal
separated by interfaces called domain walls. A ferroelectric single crystal,
when grown, has multiple ferroelectric domains. A single domain can be
obtained by domain wall motion made possible by the application of an
electric field. A very strong field could lead to the reversal of the
polarization in the domain, known as domain switching
The key characteristic of a ferroelectric crystal is that the direction of the
polarization can be reversed by application of an electric field and that
hysteresis loops result. Figure describes what happens in a ferroelectric
crystal such as tetragonal BaTiO3 when an electric field is applied. The
ferroelectric domains are randomly oriented prior to application of the
electric field, that is at E = 0 and the net polarization is zero (Pnet= 0). As
an electric field is applied, and upon increasing this electric field the
domains begin to move in the BaTiO3 and align parallel to the applied
field. This results in increase in net polarization. The polarization reaches
a saturation value when all the domains are aligned in the direction of the
field. If the electric field is reduced to zero,
many of the domains will remain aligned such that a remanent
polarization (Pr) exists. Interpolation of the line BC until it intersects the

7
polarization axis gives a value Ps , which refers to the spontaneous
polarization
If the electric field is reversed, the domain will switch direction. When
enough domains switch, the domains in one direction balance the
domains in the opposite direction and result in zero net polarization. This
occurs for an electric field called the coercive field (–Ec). Continued
increase in the negative electric field causes net polarization in the
opposite direction, reaching the point where all the available domains are
aligned.
Maximum alignment of domains can be achieved by cooling the BaTiO3
crystal through the 120°C (cubic-to-tetragonal transition or
Curie temperature) while an electric field is applied (this is referred to as
poling). Poling forces a maximum number of domains to form in one
direction and results in maximum polarization

The shape of the hysteresis loop varies for different temperatures below
the Curie temperature. It gets thinner as the temperature increases and
becomes single line above the Curie temperature when the material is no
longer ferroelectric. Ferroelectric behavior is dependent on the crystal
structure. The crystal must be noncentric and must contain alternate atom
positions or molecular orientations to permit the reversal of the dipole
and the retention of polarization after the voltage is removed.

Fig 4: Hysteresis loops resulting from plots of polarization vs. applied voltage

8
BARIUM TITANATE (BaTiO3)
Barium titanate (BaTiO3 or BTO) was synthesized to become the first and
the most widely studied ceramic material, due to its excellent dielectric,
ferroelectric and piezoelectric properties. The high dielectric constant of
BaTiO3 ceramics results from its crystal structure.

Barium titanate has three crystalline forms: cubic, tetragonal, and

hexagonal. The tetragonal polymorph is the most widely used because of
its excellent ferroelectric, piezoelectric, and thermoelectric properties.
Temperature has a strong effect on the crystal structure and polarization
characteristics of BaTiO3. Above 120°C (and up to 1400°C), BaTiO3 is
cubic and the BaTiO3 have a spontaneous random polarization as
described above.
In this temperature range the Ti4+ ion lies in the center of an octahedron
of oxygen ions . The thermal vibration is high enough to result in the
random orientation of the titanium ions in its octahedral interstitial
position in BaTiO3. The Ti4+ ion does shift position, resulting polarization
when electric field is applied, but it returns to its stable central position as
soon as the field is removed. Thus, there is no retained polarization, no
hysteresis loop, and no ferroelectric behavior.
As the temperature of BaTiO3 is lowered slightly below 120°C (Curie
temperature), a displacive transformation occurs in which the structure of
the BaTiO3 changes from cubic to tetragonal. One crystallographic axis
increases in length (unit cell goes from 4.010 to 4.022 Å) and the other
two decrease in length (from 4.010 to 4.004 Å). The Ti4+ ion moves off-
center toward one of the two oxygen ions of the long axis, resulting in a
spontaneous increase in positive charge in this direction.

Application of an electric field opposite to the polarity of this original

dipole will cause the Ti4+ ion to move through the center of the octahedral
site and to an equivalent off-center position.This results in a reversal
polarization, hysteresis in the E versus P curve, and ferroelectricity

The dielectric properties of BaTiO3 were found to be dependent on the

grain size and temperature. At the Curie point, large grained BaTiO3
(≥10 μm) has a high dielectric constant because of the formation of
multiple domains in a single grain, the motion of whose walls increases
the dielectric constant at Curie point.
For a BaTiO3 with fine-grains (~1μm), a single domain forms inside each
grain. The movement of domain walls is restricted by the grain
boundaries, thus leading to a low dielectric constant at the Curie point
compared to coarse-grained BaTiO3. At room temperature, the dielectric

9
constant of coarse-grained BaTiO3 ceramics was found to be in the range
of 1500-2000.
On the other hand, fine-grained BaTiO3 exhibits a room temperature
dielectric constant between 3500-6000. This is because the internal
stresses in fine grained BaTiO3 are greater than in the coarse grained
material, which leads to a higher permittivity at room temperature.

STRUCTURE OF BARIUM TITANATE

Fig 5: pervoskite structure of Barium Titanate

In Figure (5), each barium ion is surrounded by 12 oxygen ions. The

oxygen ions plus the barium ions form a face-centered cubic lattice. The
titanium atoms reside in octahedral interstitial positions surrounded by six
oxygen ions.
Because of the large size of the Ba ions, the octahedral interstitial
position in BaTiO3 is quite large compared to the size of the Ti ions. The
Ti ions are too small to be stable in this octahedral position. There are
minimum-energy positions off-center in the direction of each of the six
oxygen ions surrounding the Ti ion. Since each Ti ion has a +4 charge,
the degree of polarization is very high. When an electric field is applied,
the Ti ions can shift from random to aligned positions and result in high
bulk polarization and high dielectric constant

10
METHODS OF PREARATION OF BaTiO3
 Solid State Reaction
 Chemistry Based method
 Sol-gel processing
 Spray pyrolysis
 Hydrothermal method
 Other methods

But in this review work I’m going to explain only about the solid state
reaction method

Solid state reaction method

During the last decade a wide number of synthetic methods have been
developed for the preparation of barium titanate powders, but large scale
production is frequently based on solid-state reactions of mixed powders
BaCO3 and TiO2 at high temperatures (1100-1400°C).

Despite the multiple advantages of the solid-state method for preparing

BaTiO3, being a single process and a low cost technique, there are some
problems with it to be solved.

In fact, the high calcination temperature required by the solid-state

reaction process leads to many disadvantages of the BaTiO3 powder such
as; large particle size, wide size distribution and high degree of particle
agglomeration, which generally limits the ability to fabricate reliable
electronic components out of it.

One approach used to influence initial powder microstructure and

sintering properties of the material is to mechanically activate the powder
using a high energy ball milling process (also known as
mechanochemical process)
This method is superior to both the conventional solid-state reaction and
the wet-chemistry-based processing routes for ceramic powder
preparation, since it allows the use of low-cost and widely available
oxides as starting materials and skips the calcination step at intermediate
temperatures, leading to a simplified process.
Furthermore, the mechanically activated powders possess a much higher
sinterability than those powders synthesized by conventional solid-state
reaction and the wet-chemistry-based processing routes

11
Applying high-energy ball milling process to a mixture of BaCO3 and
TiO2 powders, and obtained BaTiO3 at 800°C. This temperature is lower
than that required in the conventional solid-state reactionprocess and
comparable with those required by most of the chemical-based processing
routes.

BaCO3 TiO2 Ethyl Alcohol

Planetary ball mill

Drying at 900C

Crushing
Sieving, 112μm

Calcination

Characterization

Fig 6: schematic representation of preparation of BaTiO 3

12
The sintering mechanisms of mechanically activated BaTiO3 powder (for
60 and 120 min.) and compared it with the non-activated BaTiO3 powder.
They found that, the sintering of the mechanically activated BaTiO3 took
place in three stages with one sintering mechanism (grain boundary
diffusion) compared to the non-activated BaTiO3 where there was only
one stage with a volume diffusion mechanism. Also they found that, the
apparent activation energies were lower for the activated powder
compared to the non-activated one and are similar for the two
activation times.

The effects of mechanical activation of BaTiO3 on the evolution of the

microstructure during non-isothermal sintering and the influence of
mechanical activation on the electrical properties of activated BaTiO3.
They showed that, mechanical activation and sintering regime had a
significant influence on the dielectric properties of the specimens.
The relative permittivity of the activated samples was larger than that of
the non-activated samples. They suggested that, the small values of
dielectric permittivity for non-activated samples could be attributed to the
low densification and the high porosity of these samples.

The dielectric properties of BaTiO3 ceramics fabricated by solid-state

reaction from nano-size fine activated powders, and compared the results
with those obtained for the material fabricated from micro-size coarse
powders (prepared by ball milling). They found that, the crystal structure
and the dielectric properties of BaTiO3 ceramic depend on the grain size
of the raw material. They found that, when the particle size of the raw
material becomes finer, the crystal structure changes from tetragonal to
pseudo-cubic. The dielectric constant increases with decreasing grain size
(for pure nano-powders the room temperature dielectric constant is about
5000, and that of coarse powders is about 2200). The ferroelectric phase
transition temperature decreases with decreasing the grain size. The
sintering temperature of the ceramic using nano-powders as a raw
material is 150°C lower than that using pure coarse powder.

BaCO3/TiO2 Powder Mixture

The BaCO3 powder together with TiO2 were used as the starting materials
with a nominal composition of BaTiO3. The milling operation was carried
out using planetary ball mill. Two 250 ml plastic polyamide bowls and 32
agate balls (for each bowl), each ball has a diameter of

13
15mm and weight of 5.6 gm. The milling speed was set at 200rpm. The
milling was stopped for 5 min for every 30 min to cool down the system.

The powders were mixed with Ethyl Alcohol to form slurry, and then
milled in the planetary mill for different milling times: 2.5, 5, 7.5, 10, and
12.5 hours.
The slurry was dried at 900C in the drying furnace and then crushed in
agate mortar to eliminate agglomerates. After that, the powder was passed
through a sieve of size 112 µm. The sieved powder was calcined at
different temperatures (600-900°C) and for different calcination times,
using a heating rate of 10°C/min and then furnace cooled.

Phase analysis and the crystallite size

X-ray diffractometer (XRD) was used to determine the different phases
present in the starting and the calcined powders, as well as the sintered
specimens. The diffraction patterns were recorded over the angular range
2θ from 20 to 80°.
The crystallite sizes (tc) of different samples were estimated from the
(110) peaks of XRD patterns, using Scherrer’s formula:
tc= Ķ λ/ßcosθ

Where, Ķ is the shape coefficient (value between 0.9 and 1.0), λ the wave
length, ß is the full-width at half-maximum, and θ the diffraction angle.
The full-width at half-maximum (ß) that is used for the calculation of
crystallite size must be corrected. For this purpose, we chose the single
peak at 2θ of 31.5° within the XRD pattern and a standard sample
(sintered at high temperature) with narrow peak width, bo, of 0.17°,
assuming coefficient Ķ=0.9. The ß parameter was corrected using the
following equation
B2 = β2 +b02

Where: B is the measured full-width at half-maximum (FWHM) of each

phase

X-RAY DIFFRACTION STUDY OF BACO3-TIO2 MILLED

MIXTURE

the XRD pattern for the as milled BaCO3 and TiO2 powder mixture milled
for 12.5h. It can be seen that, all the diffraction peaks correspond to either

14
BaCO3 or TiO2 phases. This implies that no reaction took place between
the BaCO3 and TiO2 powder mixtures during the mechanical milling.
Figure shows the XRD patterns for two equimolar mixtures of BaCO3
and titanium dioxide. In the first mixture the TiO2 powder was used,
while in the second the TiO2 obtained from the titanium tetra chloride
was used. The two mixtures were milled for 7.5h and calcined at 900/1h.
It can be seen from the figure that, the XRD pattern of the BaCO3/TiO2
powder mixture contained peaks corresponding to unreacted BaCO3 and
TiO2.
As for the BaCO3/TiO2 powder mixture, the XRD pattern showed only
BaTiO3 phase. This might be due to the relatively higher reactivity of the
fine TiO2 powder. Accordingly, it was decided to use the TiO2 powder in
the present review work for the BaTiO3 preparation.

Fig 7: XRD pattern of the powders at different calcination temperatures

Pressing and Sintering

The as prepared powders were die-pressed into discs of 12 mm diameter

and approximately 2mm thickness. The samples were pressed at different
pressures (381, 609, 762, and 1066 MPa) to optimize the highest green
density. Finally, the compact samples were sintered at 13000C for 3h.
The sintering process was done as follows; first, the compacted discs
were preheated at 600 for 3h in order to eliminate the binder and other
organic materials, then the temperature was raised to 13000C at a heating
rate of 2°C/min where the samples were soaked for 3h followed by
cooling at a rate of 2°C/min.

15
Dielectric Properties
The dielectric behaviors were investigated with RCL meter. For electrical
properties characterization, the sintered samples were surface ground
using silicon carbide grit 2400 to obtain parallel and flat faces. Thickness
and diameter of the samples were measured by a micrometer. Silver
electrodes were painted onto both main sides of the samples and then
these samples were heat-treated at 550°C for 30 min to ensure the contact
between the electrodes and the ceramic surface. After that, the samples
were placed between two platinum thin plates in a tube furnace and
connected to RCL meter by platinum wire.

The capacitance of the sintered samples was measured as functions in

both temperature and frequency. The dielectric properties were
determined over the temperature range from room temperature to 200°C
in the frequency range from 500Hz to 100 kHz. Before each heating run,
the samples were first heated up to the selected temperature and held
there for 30 min.
The dielectric constant or the relative permittivity (εr) was calculated
from the measured capacitance (C) according to the following equation:
Cd
ε r=
εo A
Where: d is the thickness of the dielectric, A is the total area of electrodes
and εo is the dielectric permittivity of vacuum (8.854x10-12 Farad/meter)

Figure (4.46) shows a plot of the relative permittivity, εr and dielectric

loss tanδ as functions of temperature and frequency for the sample made
from the as prepared BaTiO3 powder and sintered at 1300°C for three
hours, this sample has a sintered density of 87% of the theoretical density

From the figure it can be seen that, the dielectric properties

changed significantly with temperature. The maximum values of the
relative permittivity were obtained as expected at the Curie temperature at
120°C. Upon increasing the temperature above the Curie temperature εr
decreased to its values at the room temperature. While the dielectric
losses tanδ showed minimum values at the Curie temperature and then
increased to its values at the room temperature upon increasing the
temperature. The dielectric constant and dielectric losses slightly decrease
upon increasing the frequency. The sample sintered at higher temperature
of 1350°C/3h which is characterized by coarse grained microstructure
and high sintered density of 98 % T.D., showed higher relative
permittivity approaching 10000

16
 Figure (8): Dielectric properties as a function in temperature and frequency
for the BaTiO3 prepared from BaCO3/TiO2-c powder mixture, milled for 7.5h,
calcined at 800°C/3h, and sintered at 1300°C/3h

Figure (9): Dielectric properties as a function in temperature and frequency

for the BaTiO3 prepared from BaCO3/TiO2-c powder mixture, milled for 7.5h,
calcined at 800°C/3h, and sintered at 1350°C/3h

Figures (8 and 9) show the changes in the reciprocal permittivity with

17
temperature above the Curie temperature for samples sintered at 1300 and
1350°C for 3h respectively, where the dielectric behavior can be
characterized
by Curie-Weiss law.
C
ε =ε o+
T −Tc
Where, C is the Curie constant, Tc is the Curie temperature, εo is the
permittivity of the free space. The figures showed a straight line
relationship from the slope of which Curie constants of 1x 10 5 C and
1.67 x 105 C for samples sintered at 1300 and 1350°C for 3h,
respectively, were calculated

Materials with low dielectric constant are used for electrical insulator
applications. Materials with high dielectric constant are used in
capacitors for charge storage and other functions. The dielectric
constant is affected by temperature. The nature of the effect depends
on the source of polarization. Electronic polarization is relatively
insensitive to temperature, so temperature has little effect on the
dielectric constant. Molecular orientation polarization is opposed by
thermal agitation, so the dielectric constant goes down as the
temperature increases. Atomic/ionic polarization tends to increase with
temperature due to an increase in charge carriers and ion mobility. The
dielectric constant is also affected by the frequency of the applied
electric field or the frequency of other electromagnetic fields impinging
on the material.
The polarization requires time to respond to an applied field. Electronic
polarization occurs very rapidly and is present even at high frequencies.
For example, visible light is of relatively high frequency (1015 cycles per
second) and has an electric interaction with the electronic polarization
of a dielectric.
Molecular orientation polarization is only affected by low frequencies. In
high frequency field, the molecules do not have time to realign with each
cycle.

The dielectric loss results from several mechanisms: (1) ion migration;
(2) ion vibration and deformation; (3) electronic polarization. The most
important mechanism to most ceramics is ion migration. Ion migration is
strongly affected by temperature and frequency. The losses due to ion
migration increase at low frequencies and as the temperature increases.
Another undesirable energy loss in dielectrics arises from overheating or

18
cyclic heating, which leads to the degradation of the dielectric and
breakdown . Most dielectrics are, therefore, rated by three factors:
(1) Relative permittivity, (2) tangent of lag angle, and (3) dielectric
strength.

Dielectric breakdown begins with the appearance of a number of

electrons in the conduction band; these electrons are accelerated rapidly
by the high field in the dielectric, and attain high kinetic energies. Some
of the kinetic energy is transferred (by collisions) to valance electrons,
which are thereby elevated to the conduction band. If a large enough
number of electrons is initiated in this process, it multiplies itself, and an
avalanche of electrons is loosed in the conduction band. The current
through the dielectric increases rapidly; and the dielectric is apt to locally
melt, burn, or vaporize.

Conduction of electrons is required to initiate the process. These may

originate in a number of ways. A common origin is the arcing between a
high potential lead and the contaminated surface of an insulator. Impurity
atoms can also donate electrons to the conduction band. Interconnecting
pores in dielectrics sometimes provide direct breakdown channels as a
result of electrical gas discharge. Where a dielectric is subject to high
field over a long period, breakdown is generally preceded by local
melting. In old capacitors breakdown can occur at relatively low field
strengths if the dielectric has suffered chemical and mechanical abuse

EFFECTS OF DOPANTS OR ADDITIVES IN

BaTiO3 PROPERTIES

Pure barium titanate, exhibits a great change in dielectric constant near

the transition temperature. Generally, BaTiO3 is doped with small
amounts of impurities to modify its properties and to widen the number of
potential applications.

The polarization characteristics of BaTiO3 can be modified by crystal

chemical alterations of the crystal structure. Barium (Ba) ion is very large
and results in a large octahedral site in which the titanium ions can
readily move.
Substitution of smaller ions for Ba reduces the size of octahedral site and
restricts the motion of the Ti ion. Addition of CaZrO3 or MgZrO3 to
BaTiO3 results in a decrease in sensitivity to temperature by broadening

19
the temperature versus dielectric constant curve. Addition of PbTiO3 to
BaTiO3 increases the temperature at which the transformation occurs
(Curie temperature) where the dielectric constant is a maximum, while
the additions of SrTiO3, SrSnO3, CaSnO3, or BaSnO3 reduces the Curie
temperature

Y. Park , 1997 reported that adding CeO2: 1.5 TiO2 to BaTiO3 decreased
the ferroelectric transition temperature for cubic/tetragonal transformation
and increased the transition temperature of tetragonal/orthorhombic and
orthorhombic/rhomobohedral. They reported that, excess titanium dioxide
increased the solubility limit of cerium dioxide in barium titanate.
However, addition of CeO2 in a certain amount (0.4wt %) improves the
piezoelectric and dielectric of the BNBT [(Bi0.5Na0.5)0.94Ba0.06TiO3]
material. They found that CeO2 addition below 0.2wt% enhances the
grain growth, while CeO2 addition over 0.2wt% decreases the grain size.
the niobium had a prominent influence on the dielectric properties. They
found that barium titanate doped with a concentration of 0.6mole% of Nb
as donor dopant and 0.1mole% Mn, as acceptor dopant showed higher
dielectric constant than undoped BaTiO3.

The addition of NaNbO3 to BaTiO3 causes a considerable change in the

microstructure of the sample (i.e. grain growth inhibition) and increase in
density, dielectric constant, and dielectric strength. In addition, they
found that, this kind of additives makes the dielectric constant flat in a
wide temperature range and of good stability with frequency

J. Fisher , 2005 studied the effect of Al2O3 dopant on the abnormal grain
growth (AGG) in BaTiO3 at various temperatures. They found that, for
samples sintered at temperature ≤1250°C, the addition of up to 0.1mole%
Al2O3 promotes the AGG, while further additions of Al2O3 inhibits it.
They attributed the promotion of AGG to the dissolution of Al2O3 in the
BaTiO3 lattice and the release of TiO2. While the inhibition occurs by
Al2O3 reacting with excess TiO2 and BaTiO3 to form Ba4Al2Ti10O27. When
sintering at temperature ≥1250°C, a thick liquid film is formed at the
grain boundaries. As the Al2O3 content increases, the volume of the liquid
film increases, retarding grain growth.

20
APPLICATION OF FERROELECTRIC
CERAMICS
Piezoelectric and ferroelectric ceramics are extremely important and
widely used in many technologies. Applications include phonograph
pickups, bandpass filters, and control of oscillator frequencies in
communication equipment, sonic delay lines, sonar, high-voltage step-up
transformers, ultrasonic cleaning, medical ultrasound uses, industrial
nondestructive inspection, watches, and accelerometers. With the
development of ceramic processing and thin film technology, many new
applications have emerged. These include; multilayer ceramic capacitors
(MLCCs), piezoelectric actuators, and positive temperature coefficient
resistors (PTCR), ferroelectric thin films for non volatile memories,
electro-optic devices , and for humidity sensors based on composite
material of nano-BaTiO3 and polymer RMX . synthetic nano-BTO and
nano-STO can be used for removing Cu2+ from aqueous solutions and
hence can be exploited in environment remedies.

However, the biggest use of ferroelectric ceramics has been in the area of
dielectric ceramics for ceramic capacitors. As the energy topic has
become of increasing importance, the preparation of dielectric materials
with high dielectric constant is highly demanded for the energy storage in
the form of ceramic capacitors.

CERAMIC CAPACITORS
A capacitor is a dielectric material placed between two electrically
conductive electrodes as shown in Figure

Fig 10: single layer ceramic capacitors

21
When the capacitor is placed in electric circuit, it is able to store electrical
charge. The higher the degree of polarizability of the dielectric material,
the higher the relative dielectric constant and consequently the more the
charge that can be stored. The amount of charge (Q) (in coulombs) that
can be stored is equal to the applied voltage (V) (in volt) times the
capacitance (C) (in farads).

Q=VC

When a dielectric of relative permittivity (εr) is inserted into a parallel-

plate capacitor the capacity which is:

Co = εo A/d

Will increase to:

C = Co εr = εo εr A/d

Where: A is the total area of the electrodes, εo is the permittivity of

vacuum (8.85 x 10-12 farads/m), d is the spacing between the two
electrodes or plates (i.e. thickness of the dielectric material). That is, the
dielectric has increased the capacity by a factor of εr. Then the
capacitance is dependent on the relative dielectric constant (εr) and the
geometry of the capacitor. The capacitance increases as the area and
relative dielectric constant increase and as the thickness of the dielectric
material decreases. Most capacitors have capacitance of much lower level
in the range of microfarads (10-6 F), or nanofarad (10-9 F), or picofarad
(10-12)

From the definition of capacity and current, we can write

V = Q/C = ∫ I dt/C
And differentiating this relation, we get:
I = C dV/dt
for the current through the capacitor. If the voltage used is sinusoidal, that
is, it varies as:
V = Vo sinωt
Vo is the maximum value of the voltage and ω = 2πf, where f is the
frequency, and t is the time. Then:
I = C Vo ω cosωt

22
 Conclusion
In this study, the BaTiO3 was synthesized by using the solid-state
reaction method, starting with BaCO3/TiO2

1- Milling for 7.5h of BaCO3/TiO2-c powder mixture followed by

calcination for 10h at 750°C was found enough to form a single phase
BaTiO3.
2- The use of a very reactive TiO2 in an equimolar BaCO3/TiO2-c
mixture, followed by mechanical activation, using planetary mill, led to
lowering the formation temperature of BaTiO3 (from ~1200 to 750°C).
3- Irrespective of the milling time, the rate of formation of BaTiO3 phase
increases with calcination time and calcination temperature.
4-The tetragonality of BaTiO3 ceramics increases with the sintering
temperature
5- The relative permittivity and the dielectric loss, measured at room
temperature and 1 kHz, were 2028.5 and 0.043, respectively.

23
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