SYNTHESIS AND ELECTRICAL

PROPERTIES OF BISMUTH
SUBSTITUTED BARIUM TITANATE
A PROJECT REPORT SUBMITTED IN PARTIAL
FULFILMENT
OF THE REQUIRMENTS FOR THE DEGREE OF
Integrated M.Sc. in Applied Physics
By
Biswajit Samal
REGISTRATION NO.: -1412106038
Under the Supervision of
Dr. Jyoshnarani Rout
Department of APPILED PHYSICS

COLLEGE OF ENGINEERIG AND TECHNOLOGY

Bhubaneswar-751003

1
 College of Engineering and Technology
(A Constituent College of BPUT, Odisha, Rourkela)

Certificate
This is to certify that the project report entitled, “SYNTHESIS AND
ELECTRICAL PROPERTIES OF BISMUTH SUBSTITUTED BARIUM
TITANATE” Submitted by Biswajit Samal in partial fulfilment of the
requirements of the award of Integrated Master of Science in Applied
Physics, at the College of Engineering and Technology, Bhubaneswar is an
authentic work carried out by him under our supervision.
To the best of our knowledge, the matter embodied in the project
has not been submitted to any other university / institute for the award
of any Integrated M.Sc degree.

Signature of the HOD Signature of the Guide

Date: ……………….. Date: ………………

2
 DECLARATION
I am Biswajit Samal (Regd. No: 1412106038), hereby submit my project
entitled “ Synthesis and Electrical properties of Bismuth substituted
Barium Titanate” for the consideration for the award of the degree of
Integrated M.Sc in Applied Physics, is a research work carried out by me at
College of Engineering And Technology, Bhubaneswar under the guidance
of Dr. Jyoshnarani Rout. All the work contained in the thesis is my original
work except where otherwise acknowledged and has not been submitted in
part or in full by me for any degree to this or any other university or to
an examining body in India or abroad. The complete project report is
prepared and written by me.

Biswajit Samal
Integrated M.Sc. in Applied Physics
Regd. no;1412106038

3
 ACKNOWLEDGEMENT

First of all, I would like to express my sincere gratitude to my guide Dr.

Jyoshnarani Rout for her support, her guidance and her acceptance of me as an

Int.M.Sc student working under her guidance.

I also express my regards to Dr. Babita Ojha (Head of the department) for her

valuable encouragement and continuous help not only for project work, throughout

the entire Int. M.Sc. course.

Further it gives me an immense pleasure to thank PhD Scholar Ms. Shwetapadma

Swain , Dr. Abhinna Mishra and my friends of my group for helping me in

completing my project. I want to thank all the lecturers and staff members of the

department of Physics for their cooperation extended to me during of this work.

It is my great pleasure to take this opportunity to thank all those who helped me

directly or indirectly in preparation and completion of this report.

Name:Biswajit Samal

Date: 21st Dec 2018

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 ABSTRACT
In this project work the main effort is for the enhancement of the characteristics of
BaTiO3 by doping with Bismuth (Bi) which is a dia-magnetic element.
Ba1-xTiBixO3ceramics are synthesized by solid state reaction method. X-ray
structural analysis shows that the compound taken exhibit tetragonal crystal
structure. The dielectric properties were studied by using LCR Meter. Analysis of
Dielectric properties shows that doping of Bismuth to Barium Titanate reduces the
dependence of dielectric loss and dielectric constant on frequency. Bismuth doping
reduces the dielectric loss of the material as compared to that of parent BaTiO 3.
Doping of Bismuth enhances the dielectric constant of the material.

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 CONTENTS
No Page
CHAPTER-1

1. Introduction……………………………………………………….….10
1.1 Ferroelecrtic….……………………………………………….........12
1.2 Ferroelectric crystal………………………………..........................13
1.3 Relaxor Ferroelectrics……………………………………………..15

CHAPTER-2

2. Literature Review …………………………….……………………18

2.1 Barium Titanate (BaTiO3)………………………………………..18

2.2 Motivation………………………………………………………...20

2.3 Objectives………………………………………………………....20

CHAPTER-3

3. Sample Preparation……………………………………………………21

3.1 General methods of preparing ceramic samples…………………...21

3.2 Solid state reaction method / Mixed oxide method………………..21

3.3 Preparation of the ceramics ..……………………………………...21

3.4 Working Formula………………………………………………….23

3.5Procedure………………………………………………………..…25

3.5.1 Weighing of Sample…………………………………………….25

3.5.2 Grinding…………………………………………………………26

3.5.3 Calcination………………………………………………………26

3.5.4 PVA Preparation………………………………………………...27

3.5.5 Grinding with PVA and pellet preparation………………………27

3.5.6 Sintering………………………………………………………….27
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 CHAPTER – 4

4.Characterization Techique…………………..………………………28

4.1 X-ray Diffraction (XRD)…………………………………………28

4.2 Goldschmidt's tolerance factor…………………………………...31

4.3 Dielectric Material Properties Using LCR Meters…………………………31

4.3.1 Dielectric constant……………………………………………………………….31
4.3.2 Dielectric loss……………………………………………………………………….32

CHAPTER - 5

5. Results and Discussion……………………………………………34

5.1 Structural characteristics………………………………………..34

5.2 Analysis of Dielectric properties using LCR meter…………….36

CHAPTER-6

6. Summary and Conclusion…………………………………………38

References……………………………………………………………..38

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List of figure
Fig.1: Lattice structure of a symmetric perovskite crystal

Fig.2: Polarization of a tetragonal distorted crystal

Fig.3: Polarization Vs Electric field (P-E) loop for different materials

Fig.4: Polarization vs. Electric Field (P-E) hysteresis loop for a typical ferroelectric crystal

Fig.5: Different polarization directions in the relaxor perovskite structure

Fig.6: Schematic of the perovskite structure of BaTiO3

Fig.7: Reversal in the direction of spontaneous polarization in BaTiO3 by reversal of the

direction of the applied field

Fig.8 : Flowchart for the preparation of sample

Fig.9: Weight balance

Fig.10: Agate motor

Fig.11: Mixture of Powder

Fig.12: Muffle Furnace

Fig.13: Crucible

Fig.14 : Pellet maker

Fig.15: Apparatus used in Making pellets

Fig.16: Pellet

Fig.17: XRD image

Fig.18(a): X-ray diffraction pattern of BaTi03 sample

Fig.18(b): X-ray diffraction pattern of Ba0.9Bi0.1Ti03 sample

Fig.18(c) : X-ray diffraction pattern of Ba0.8Bi0.2Ti03 sample

Fig.19: Dielectric constant vs Frequency

Fig.20: Dielectric loss vs Frequency

8
 LIST OF ABBRIVIATIONS
PVA Polyvinyl Alcohol

XRD X-Ray diffraction

CCD Charge coupled device

DOS Density of state

EDS Energy dispersive Spectrum

SEM Scanning electron microscopy

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 CHAPTER-1
1.INTRODUCTION
Ferroelectricity was discovered in 1920 by J. Valasek. The first known ferroelectric material was
Rochelle salt (NaKC4H4O6.4H2O). Unfortunately, Rochelle salt loses its ferroelectric properties
if the composition is slightly changed, which made it rather unattractive for industrial applications.
After that Barium titanate (BaTiO3) was discovered to be ferroelectric behavior in 1945 by A Von
Hippel and is perhaps the most commonly through of material when one thinks of ferroelectricity.
BaTiO3 is stable perovskite type, which is one of the fundamental crystal lattice structures.
Perovskites form is the most important class of ferroelectric materials. The perfect perovskites
structure follows the formula ABO3, where A is a mono- or divalent and B is a tetra- or pentavalent
metal. In (Fig.1) the A atoms form the corners of the cubic cells, B atoms are in the center and the
oxygen atoms are situated in the faces centers of the cubic cell and the lattice is center of symmetry
so here no ferroelectricity can be observed.

10
While In (Fig.2) shows that B atom is displace from its center when the electric field is applied
and the lattice is polarized. The phase is transform from cubic to tetragonal and the lattice is non-
centre symmetry so here ferroelectricity should be observed[1-3].

While there are some 250+ materials that exhibit ferroelectric properties, some of the more
common/significant materials include: Lead titanate (PbTiO3), Lead zirconate titanate (PZT),
Lead lanthanum zirconate titanate (PLZT). Ferroelectricity has also been called Seignette
electricity, as Seignette or Rochelle Salt (RS) was the first material found to show ferroelectric
properties such as a spontaneous polarization on cooling below the Curie point, ferroelectric
domains and a ferroelectric hysteresis loop.

The discovery of new classes of ferroelectrics advances in first principles theoretical

techniques, and an expanded range of applications, mixed relaxor and ferroelectric ABO 3-type
single crystals. A major breakthrough in the field of ferroelectricity occurred around 1960 with the
publication of Cochran‟s seminal work. He advanced the concept that certain ferroelectric
transitions are driven by instability of the crystal lattice against a soft optical phonon mode. These
experimental techniques proved for the first time the microscopic nature of the static and dynamic
properties of ferroelectric transitions. In spite of the fact that the soft mode concept was very
successful in elucidating the microscopic mechanism not only for ferroelectric transitions but for
structural phase transitions in general, the atomic-level origin of ferroelectricity, particularly in the
ABO3 perovskite, remained unclear. Most perplexing was the vastly different behaviors of
seemingly very similar compounds such as KtaO3 and KNbO3, and BaTiO3 and SrTiO3. The
domain of first-principles theory and the remarkable progress in the application of this theory to
ferroelectrics in the past decade has paid significant dividends. Calculations for several ABO 3
compounds have identified hybridization between the oxygen 2p and transition-metal d states as
the origin of the ferroelectric instability. Relaxor behavior generally results from crystalline
disorder[4-5].

The occurrence of ferroelectricity is determined by a delicate balance between competing

long-range Coulomb forces, which favor the ferroelectric state, and short-range repulsive forces,
which favor the non-polar state. Hydrostatic pressure has been shown to be an excellent variable
for tuning this balance and thereby providing new insights into the underlying for tuning this
balance and thereby providing new insights into the underlying physics. Additionally, there is
intimate coupling between the polarization and lattice strain (or volume).

Ferroelectric materials may be divided into two classes: classical ferroelectrics and relaxors

i. Typically relaxors have at least one crystallographic site that is occupied

by two or more ions. In addition to usual application for classical
ferroelectrics, relaxors have great interest for dielectrics in capacitors and
actuators

11
 ii. Most relaxors lead based ceramics such as PbMg1/3Nb2/3O 3 (PMN) and
derived compounds. Or Pb (M`1/2M”1/2)O3 with long range polar order.
However, these compositions have the obvious disadvantages associated
with the volatility and toxicity of PbO. Therefore, much current research
is directed towards more environmentally friendly Pb-free relaxor
materials.

1.1 Ferroelecrtic:
Most materials are polarized linearly with external electric field; nonlinearities are
insignificant. This is called dielectric polarization (Fig.3). Some materials, known as
paraelectric materials, demonstrate a more pronounced nonlinear polarization. The
electric permittivity, corresponding to the slope of the polarization curve, is thereby a
function of the external electric field. In addition to being nonlinear, ferroelectric
materials demonstrate a spontaneous (zero field) polarization. Such materials are
generally called pyroelectrics. The distinguishing feature of ferroelectrics is that the
direction of the spontaneous polarization can be reversed by an applied electric field,
yielding a hysteresis loop. Typically, materials demonstrate ferroelectricity only below a
certain phase transition temperature, called the Curie temperature, T c, and are paraelectric
above this temperature.

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1.2Ferroelectric Crystal:
A ferroelectric crystals is crystals that possess reversible spontaneous polarization as exhibited by
a dielectric hysteresis loop (reversibility of the polarization).

Ferroelectric crystals possess regions with uniform polarization called ferroelectric

domains. Within a domain, all the electric dipoles are aligned in the same direction. There may be
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 appropriate electric field. A very strong
field could lead to the reversal of the polarization in the domain, known as domain switching. All
ferroelectric materials are pyroelectric, however, not all pyroelectric materials are ferroelectric.
Below a transition temperature called the Curie temperature ferroelectric and pyroelectric
materials are polar and possess a spontaneous polarization or electric dipole moment. The non-
polar phase encountered above the Curie temperature is known as the paraelectric phase. The
direction of the spontaneous polarization conforms to the crystal symmetry of the material, while
the reorientation of the spontaneous polarization is a result of atomic displacements. The
magnitude of the spontaneous polarization is greatest at temperatures well below the Curie
temperature and approaches zero as the Curie temperature is neared[6].

The most characteristics property of a ferroelectric is the hysteresis loop is shown in (fig. 4).
As the electric field strength is increased, the domains start to align in the positive direction giving
rise to a rapid increase in the polarization. At very high field levels, the polarization reaches a
saturation value (Ps). The polarization does not fall to zero when the external field is removed. At
zero external field, some of the domains remain aligned in the positive direction, hence the crystal
will show a remnant polarization Pr. The crystal cannot be completely depolarized until a field of
magnitude is applied in the negative direction. The external field needed to reduce the polarization
to zero is called the coercive field strength Ec. If the field is increased to a more negative value,
the direction of polarization flips and hence a hysteresis loop is obtained. The value of the
spontaneous polarization Ps is obtained by extrapolating the curve onto the polarization axes.

13
 The relationship between D (or P) and E is linear up to relatively large fields. However, in
the case of ferroelectrics and must be defined more precisely owing to the more complicated
relationship between D (or P) and E. For most purposes of this review, and c are defined as the
slopes of the D vs. E and P vs. E curves, respectively, at the origin, i.e., the initial values.

= ( d/ E)E=0 and = ( P/ E)E=0 ---------- (1.1)

They are determined from measurements made at very low ac fields so as not to reverse any
domains. Although ferroelectric crystals are a widely varied group, they posses a number a general
characteristics properties, among these are the following:

1. The hysteresis loop disappears at a certain temperature, the Curie point Tc, above which
the crystal behaves as a normal dielectric. It should be noted, however, that in some
crystals melting or chemical decomposition may occur before the Curie point is
reached.
2. At Tc a ferroelectric crystal transforms to a phase of higher symmetry. This higher
temperature phase is usually nonpolar, or paraelectric (PE).

14
 3. The polar crystal structure of a ferroelectric can be derived from the high-temperature
PE structure by a slight distortion of the crystal lattice. This is the main reason behind
the success of the phenomenological theory of ferroelectricity which assumes that the
same free energy function is applicable for both the FE and PE phases.
4. Ferroelectrics generally have a large (or X), which rises to a peak value at Tc.
5. Above Tc, of a ferroelectric (measured along the polar axis) usually obeys the Curie-
Weiss law = C/(T-T0), where C and T0 are the Curie-Weiss constant and Curie-Weiss
temperature, respectively.

Finally, we should mention that there are substances which, on cooling, undergo a
transition from a nonpolar to an antipolar state. In this state the crystal has a superlattice
consisting arrays of antiparallel dipoles. If, in a given crystal, the coupling energy
between these arrays is comparable to that of the polar case, then the crystal is said to
be antiferroelectric (AFE). An antiferroelectric crystal can usually be made ferroelectric
by the application of a sufficiently large electric field [7].

1.3 Relaxor Ferroelectrics:

High and broad maxima in temperature dependence of both components of complex
permittivity ε* = ε′ – iε′′ and their shift to higher temperatures with raising measuring frequency
is a typical feature of relaxor ferroelectrics (RFEs). Relaxor ferroelectric exhibit many properties
similar to those of spin and dipolar glasses. Relaxor behavior is normally FE materials results from
compositionally induced disorder or frustration. This behavior has been observed and studied mist
extensively in disordered ABO3 perovskite ferroelectrics and is also seen in mixed crystals of
hydrogen-bonded FEs and AFEs, the so-called phonic glasses. In this section we restrict our
comments largely to the ABO3 oxides. Most of the RFEs with potential piezoelectric applications
are lead-based compounds with the perovskite structure; however there is currently an increased
need for more environmental friendly lead-free compounds.

In the ABO3 oxides (Fig.5), shows the different polarization directions (marked by arrows) in
the relaxor perovskite structure. (A) Polarizations along T and R direction (B) The MA phase, for
which the polarization lies in the (110) plane, can be obtained by combining T and O direction (C).
The MC phase, for which the polarization lies in the (100) plane, can also be obtained by
combining T and O direction. Due to polarizabilities at both the A and B lattice sites produces
dipolar defects and can introduce a sufficiently high degree of disorder so as to break translational
symmetry and prevent the formation of a long-range ordered state. Instead, the dipolar motion in
such systems freezes into a glass-like state on cooling below the transition temperature, Tm.

15
(fig-5 Different polarization directions {marked by arrows} in the relaxor perovskite structure)

In these highly polarizable host lattices, the presence of a dipolar impurity on a given site can
induce dipoles in a number of adjacent unit cells within a correlation length of that site. We accept
the dipolar motion within this correlation length to be correlated, leading to the formation of polar
nanodomains. Indeed, such nanodomains have been observed in many ABO 3 relaxors at
temperatures far above the peak in (T), and their occurrence is now considered to be crucial to the
understanding of the properties of relaxors. We picture a distribution of sizes of such nanodomains
in which the orientational degrees of freedom are correlated within each domain, but uncorrelated
across the various domains. At sufficiently low temperatures, the dipolar motion within each
domain freezes, resulting in the formation of an orientational glass (relaxor) state. Such a state is
characterized by a distribution of relaxation times related to the sizes of the nanodomains. Two
important characteristics of this relaxor state that distinguish it from simple dipolar glasses or spin
glasses are the predominant existence of the dipolar nanodomains (vs. largely individual dipoles
or spins) and the presence of some degree of cooperative freezing of the orientational degrees of
freedom. Evidence of this cooperative effect comes from the observation of some remnant
polarization in electric field hysteresis loops. It should be noted, however, that such evidence is
also seen in systems of random dipoles in low polarizability hosts for doped alkali halides with
sufficiently high concentration of dipoles.
16
 In order to be a good piezoelectric material, the lattice shape must be able to change
significantly in response to an external electric field. Theoretical work has suggested that phase
instability may be responsible for this effect. The directional dependence of sound wave
propagation in the current study provides strong evidence that such phase instability does exist and
is indeed induced by the polar nano regions [8].

Table 1: Difference between normal and relaxor ferroelectric

Property Normal Ferroelectric Relaxor Ferroelectric

Dielectric temperature Sharp 1st or 2nd order Broad diffused phase

dependence
Dielectric frequency
dependence
Dielectric Behavior in
paraelectric range ( T > Tc)
Remnant polarization (Pr)
Scattering of light
Diffraction of X-Rays
transition at Curie point T
Weak Frequency dependence
Follows Curie - Weiss law
Strong Pr
Strong anisotropy
Line splitting due to
deformation from paraelectric
to ferroelectric phase
transition at Curie maxima
Strong frequency dependence
Follows Curie - Weiss square
law
Weak Pr
Very weak anisotropy to light
No X-Ray line splitting

This intrinsic instability apparently helps to facilitate the field-induced structural change and
contributes to the large piezoelectric response. In table-1 shows the properties of relaxors are
contrast to some of their properties with those of normal ferroelectrics[9-11].

17
 CHAPTER-2
2. LITERATURE RIVIEW:
2.1 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 [N.
Nikulin, 1988]. The high dielectric constant of BaTiO3 ceramics results from its crystal structure.
BaTiO3 has the perovskite structure as shown in Figure (6).

Fig .6: Schematic of the perovskite structure of BaTiO3 A) Cubic lattice (above Curie temperature,
120°C) B) Tetragonal lattice (below Curie temperature, 120°C) [D. W. Richerson, 1992]

In Figure (6), 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
18
constant [D. W. Richerson, 1992]. 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 [S. Luo et al., 2003]. 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 BaTiO 3 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 (as shown in Figure.7-A). The thermal vibration is high enough to result in the random
orientation of the titanium ions in its octahedral interstitial position in BaTiO 3. 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 BaTiO 3 is lowered slightly below 120°C
(Curie temperature), a displacive transformation occurs in which the structure of the BaTiO 3
changes from cubic to tetragonal (Figure.7-B). 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. This is - 21 - illustrated in Figure (7-a).
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
is shown in Figure (7-b). This results in a reversal polarization, hysteresis in the E versus P curve,
and ferroelectricity [D. W. Richerson, 1992].

(Fig.7. Reversal in the direction of spontaneous polarization in BaTiO 3 by reversal of the

direction of the applied field)

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 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

19
between 3500-6000. This is because the internal stresses in fine grained BaTiO 3 are greater than
in the coarse grained material, which leads to a higher permittivity at room temperature [12-14].

2.2 MOTIVATION
Transition metal oxides are normally used as doping materials for BaTiO3 ceramics in order to
achieve a high dielectric performance and low dissipation factor of the capacitors. The merging
of trivalent cations such in the perovskite lattice of BaTiO3, modifies the structural and electrical
properties of doped BaTiO3. The smaller ionic size transition metal ions (Bi) predominantly
dissolve in A-sites, and act as donors depending on their concentration. The substitution of Bi
ions on Ba2+ sites requires the formation of negatively charged defects. There are three possible
compensation mechanisms: barium vacancies, titanium vacancies and electrons (e -). For samples
sintered in air atmosphere, which are electrical insulators, the principal doping mechanism is the
ionic compensation mechanism. So in my project work I have doped the Ba-site of Batio3
pervoskite with Bi-ion to study its effect on structural and electrical properties.

2.3 PROJECT OBJECTIVE

• To synthesis the high dielectric constant material (BaTiO3) by solid state route.
• To characterize the synthesized materials like XRD for phase formation.
• Electrical study for dielectric constant and loss tangent.

20
 CHAPTER 3
3. SAMPLE PREPARATION
3.1 General methods of preparing ceramic samples:
Ferroelectrics in general and multiferroics in particular can be obtained in many forms like single
crystals, ceramics (an assembly of small single crystals oriented with respect to each other in a
more or less completely random way) and thin films [1-3]. Ceramic processing is a sequence of
operations like mixing, calcination, sintering etc. that intentionally and systematically changes
the chemical and physical properties of materials.

3.2 Solid state reaction method / Mixed oxide method:

In the present study solid state reaction technique has been employed for the preparation of
polycrystalline samples. This is a conventional method in which oxides and carbonates are used.
These chemicals have to meet a certain application dependent specification with respect to their
purity and grain distribution.

3.3 Preparation of the ceramics:

The polycrystalline samples of( Ba1-xBixTiO3)and x=0.1 and 0.2were prepared by a solid-state
reaction method using Barium Carbonate (BaCO3), Titanium dioxide (TiO2) and Bismuth Oxide
(Bi2O3).These ingredients were mixed in agate-mortar for 2 hours. It was again mixed in a wet
(methanol) atmosphere for 3h to get homogeneous mixtures. These mixtures were then calcined at
different temperatures in alumina crucibles. The process of grinding and calcination was repeated
until the formation of the compounds is confirmed. The formation of the samples was checked by
X-ray diffraction (XRD technique. The calcined powders were then mixed with PVA (binder), and
were used to make cylindrical pellets of diameters of 10 mm and thickness of 1-2mm under a
uniaxial pressure of 5x106 N/m2 using a hydraulic press. The pellets were then sintered at different
temperatures for different compounds.

21
(Fig.8 Flowchart for the preparation of sample)

22
The calcination and sintering temperatures of the compounds are shown in Table 3.1. The binder
was burnt out during high-temperature sintering. Using scanning electron microscope, the surface-
morphology of gold-plated pellets samples was recorded. The The sintered pellets were the
polished with fine emery paper in order to make both the faces flat and parallel. These polished-
sintered pellets were then coated with high-purity silver paste. The pellets were dried at 150oC for
5 hrs to remove moisture before taking any electrical measurements.

Table 2: Calcination and sintering temperature of the compounds

Materials Compositions Calcination Sintering temperatures(oC)

temperatures (oC)
Ba1-xBixTiO3 x=0.1 1150 1170

x=0.2 1150 1170

3.4 WORKING FORMULA:

3.4.1 Stoichiometric Calculation:

The calculated equation is

1.2BaCO3+2TiO2+Bi2O3 → 2BaTiBiO3 +2CO2+O2+[O]

2. (1-x)2BaCO3+2TiO2+xBi2O3→2Ba1-xTiBixO3+2CO2+O2+[O]

( I have prepared sample for x= 0.1 & 0.2 )

23
 Table 3: Weight of the sample

SAMPLE MOLECULAR WEIGHT(g/mol)

BaCO3 197.34

TiO2 79.866

Bi2O3 465.96

X=0.1

(FOR 1gm PRODUCT)

Weight of BaCO3:0.9×197.34=177.606

Weight of TiO2: 79.866

Weight of Bi2O3:0.1×465.96=46.596

Total weight= A=A1+A2+A3=177.606+177.606+46.596=304.068 g/mol

(FOR 10gm PRODUCT)

Amount of BaCO3 needed = (A1/A)×10=5.84099 gm

Amount of TiO2 needed = (A2/A)×10=2.62658gm

Amount of Bi2O3 needed = (A3/A)×10=1.53242 gm

X=0.2

(FOR 1gm PRODUCT)

Weight of BaCO3:0.8×197.34=157.872

Weight of TiO2: 79.866

Weight of Bi2O3:0.2×465.96=93.192

Total weight= A=A1+A2+A3 =157.872+79.866+93.192=330.93 g/mol

24
(FOR 10gm PRODUCT)

Amount of BaCO3 needed =(A1/A)×10=4.77055 gm

Amount of TiO2 needed = (A2/A)×10=2.41338gm

Amount of Bi2O3 needed = (A3/A)×10=2.81606 gm

Table 4.Amount of the sample:

composition BaCO3 TiO2 Bi2O3

X=0.1 5.84099 gm 2.62658gm 1.53242 gm

X=0.2 4.77055 gm 2.41338gm 2.81606 gm

3.5 PROCEDURE:

3.5.1 Weighing of Sample:

The weight of different samples is taken by using a digital weight balance. Generally tracing paper
are used for weighing samples (pouring sample on that) for less sample wastage. The mass of trace
paper is neglected by using tare button then weight is taken on that paper carefully.

( Fig. 9 Weight balance)

25
3.5.2 Grinding:
The sample that we have weighed are all mixed mechanically to get homogeneous mixture by
using an Agate mortar and pestles in dry medium for 2 hours and then in wet (Methanol) medium
for 3 hours. The sample should be grinded carefully so that no sample particles will come out of
the mortar for perfection. The grinding should be done in circular motion comprising both
clockwise and anticlockwise motion for uniform mixing of sample. The process will continue until
we get fine dry powder sample. After grinding if we take some time to proceed for next step then
sample was kept in an air tight container.

( Fig.10 Agate motor ) ( Fig.11 Mixture of Powder)

3.5.3 Calcination:
Calcination is done by heating a sample at high temperature below its melting point to produce
pure powders by eliminating the undesirable compositions. The homogeneous mixtures that we
have prepared are ready for calcination and were calcinated or preheated in high purity (99.9%
pure) crucible at 1150 degree Celsius for 4 hours in a furnace.

( Fig.12 Muffle Furnace ) (Fig.13 Crucible)

26
3.5.4 PVA Preparation:
It is prepared by using a magnetic stirrer. First of all water was taken in a beaker and heated upto
30 minutes at 100 degree Celsius temperature. The PVA powder was added to it. Magnetic stirrer
was not put inside the beaker and again heated upto 30 minutes to prepare PVA solution.

3.5.5 Grinding with PVA and pellet preparation:

The calcinated powder was grounded and again milled with addition ofd PVA which is a
binder. This powder was uniaxially pressed into pellets with a diameter of 10mm and thickness of
1-2mm with the help of pellet maker at a pressure of about 5-10 pascal (using hydraulic press).
Some amount of calcinated powder was kept for XRD analysis in an air tight container.

(Fig.14 Pellet maker) (Fig.15 Apparatus used in (Fig.16 Pellet )

Making pellets )

3.5.6 Sintering:
The pellets prepared are now ready for sintering. For sintering process we adopted a higher heating
as well as cooling rate rather than the conventional solid state reaction method. In order to get high
cooling rate, the furnace door was opened as soon as the sintering process had finished. Sintering
was done at an optimized temperature in the range of 1170 degree Celsius for 4 hours.

The sintered pellets are now ready for further analysis.

27
 CHAPTER – 4

4. CHARACTERRIZATION TECHNIQUES
4.1 X-ray Diffraction (XRD):
One of the most fundamental questions that we can ask of a material is simply what is it? X-ray
diffraction provides the answer.
X-ray diffraction (XRD) relies on the dual wave/particle nature of X-rays to obtain information
about the structure of crystalline materials. A primary use of the technique is the identification and
characterization of compounds based on their diffraction pattern.
The properties of a material can often be linked back to the arrangement of atoms in its crystal
structure. X-ray diffraction is a non-destructive analytical technique which can yield the unique
fingerprint of Bragg reflections associated with a crystal structure.
In materials with regular structure (i.e. crystalline), the scattered X-rays undergo constructive and
destructive interference. This is the process of diffraction. The diffraction of X-rays by crystals is
described by Bragg’s Law,
2dsinθ = nλ
The directions of possible diffractions depend on the size and shape of the unit cell of the material.
The intensities of the diffracted waves depend on the kind and arrangement of atoms in the crystal
structure. The atomic planes in a crystal are arranged in a periodic array and thus can diffract light.
The atomic planes cause an incident beam of X – rays to interfere with one another as they leave
the crystal. The wavelength of X-rays is similar to the distance between atomic planes. The
positions of Bragg’s reflections tell us about the inter-layer spacing’s of atoms in the crystal
structure, thanks to Bragg´s Law.
POWDER DIFFRACTION
Most materials are not single crystals, but are composed of many tiny crystallites in all possible
orientations called a polycrystalline aggregate or powder. When a powder with randomly oriented
crystallites is placed in an X-ray beam, the beam will see all possible interatomic planes. If the
experimental angle is systematically changed, all possible diffraction peaks from the powder will
be detected.
The sample used for this process may be powder, sintered pellets etc. The ideal powder sample
contains thousands of randomly oriented crystallites. When X- rays are incident on that sample
then diffraction occurs and only a small fraction of the crystallite contribute to the measured
diffraction pattern. Every diffraction peak is the product of X-rays scattering from an equal number
of crystallites.

Instrumentation:

X-ray diffractometer consists of three basic components

• X ray tube
28
 • A sample holder
X-ray detector

(Fig.17 XRD JASCO V-750 UV-VIS image )

Working:

X rays are generated in a cathode ray tube by heating a filament to produce electrons, accelerating
the electrons towards the target by applying a voltage and bombarding the target material with
electrons. When electrons have sufficient energy to dislodge inner shell electrons of the target
material characteristic X-rays are produced.

The X-rays are collimated and directed onto the sample and detector are rotated, the intensity of
the reflected X-ray beam is recorded. When the geometry of the incident X-rays impinging the
sample satisfies the Braggs equation, constructive interference takes place. A detector records and
processes this signal to a count rate which is then output to a device such as printer or computer
monitor. This data are collected as 2θ versus absolute intensity.

29
Applications

X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials (e.g. minerals, inorganic compounds). Determination of unknown solids is critical to
studies in geology, environmental science, material science, engineering and biology.
Other applications include:

• characterization of crystalline materials

• identification of fine-grained minerals such as clays and mixed layer clays that
are difficult to determine optically
• determination of unit cell dimensions
• measurement of sample purity
With specialized techniques, XRD can be used to:
• determine crystal structures using Rietveld refinement
• determine of modal amounts of minerals (quantitative analysis)
• characterize thin films samples by:
✓ determining lattice mismatch between film and substrate and to inferring stress and strain
✓ determining dislocation density and quality of the film by rocking curve measurements
✓ measuring superlattices in multilayered epitaxial structures
✓ determining the thickness, roughness and density of the film using glancing incidence X-ray
reflectivity measurements
✓ make textural measurements, such as the orientation of grains, in a polycrystalline sample
Strengths
• Powerful and rapid (< 20 min) technique for identification of an unknown mineral
• In most cases, it provides an unambiguous mineral determination
• Minimal sample preparation is required
• XRD units are widely available
• Data interpretation is relatively straight forward
30
Limitations
• Homogeneous and single phase material is best for identification of an unknown
• Must have access to a standard reference file of inorganic compounds (d-spacings, hkls)
• Requires tenths of a gram of material which must be ground into a powder
• For mixed materials, detection limit is ~ 2% of sample
• For unit cell determinations, indexing of patterns for non-isometric crystal systems is
complicated
Peak overlay may occur and worsens for high angle 'reflections.[15-17].

4.2. Goldschmidt's tolerance factor:

Goldschmidt's tolerance factor is an indicator for the stability and distortion of crystal
structures. It was originally only used to describe perovskite structure, but now tolerance factors
are also used for ilmenite.
Alternatively the tolerance factor can be used to calculate the compatibility of an ion with a
crystal structure.
The first description of the tolerance factor for perovskite was made by Victor Moritz
Goldschmidt in 1926.[18]
Mathematical expression

The Goldschmidt tolerance factor (t) is a dimensionless number that is calculated from the ratio
of the ionic radii

4.3 Dielectric Material Properties Using LCR Meters

Impedance measurements are a basic means of evaluating electronic components and materials.
Every material has a unique set of electrical characteristics that are dependent on its dielectric or
insulation properties. Accurate measurements of these properties can provide valuable information
to ensure an intended application or maintain a proper manufacturing process. And so what are
these measurements and how are they made?

4.3.1 Dielectric Constant

The dielectric constant measurement, also known as relative permittivity, is one of the most
popular methods of evaluating insulators such as rubber, plastics, and powders. It is used to

31
determine the ability of an insulator to store electrical energy. The complex permittivity can be
written as

ε*= k′ - iD

The real part of the complex permittivity, the dielectric constant (k’), represents the storage
capability and imaginary part of the complex permittivity, the dielectric loss (D), which represents
the loss.

Dielectric constant measurements can be performed easier and faster than chemical or physical
analysis techniques making them an excellent material analysis tool. The dielectric constant is
defined as the ratio of the capacitance of the material to the capacitance of air,

Cx
or k ' =
Co

Where Cx = capacitance with a dielectric material and Co = capacitance without material, or

vacuum. The k’ value of dry air is 1.00053, which for most measurement applications is usually
close enough to the value of a vacuum, which is 1.0000. Thus if a material is to be used for
insulating purposes only, it would be better to have a lower dielectric constant, or as close to air
as possible. To the contrary, if a material

is to be used in electrical applications for storage of electrical charge, the higher the dielectric
constant the better. More charge is stored when a dielectric is present than if no dielectric (air) is
present. The dielectric material increases the storage capacity of the plate capacitor, hence the
dielectric constant of any solid or liquid would be greater than 1.

Dielectric constants of common material

Vacuum 1.0

Air 1.00053

4.3.2 Dielectric Loss

Dielectric loss or Dissipation factor (D) is defined as the ratio of an insulating materials resistance
to its capacitive reactance at a specified frequency. It measures the inefficiency or loss of the
material, is always greater than 0, but usually much smaller than the dielectric constant. D
measurements are an excellent means of quality control which can yield indication of
contamination or deterioration. For example, if we wanted to check the purity of epoxy or some
raw material for consistency in a production run why not just measure the D. Excessive moisture
would increase the dissipation factor value telling us something has changed as compared to
previously established values.

32
Dielectric loss (D), at the various frequencies is calculated using the measured conductance values
from the relation:

D = G/ωCi = Gdi / ε0ωA

Where G is the conductance of the device and ω is the angular frequency.

The tangent loss (tanδ)

D
tan δ = 𝑘′

The ac electrical conductivity (σac) of the dielectric material can be given by the following
equation σac = ωC tan δ (di/A)= ε''ω ε0

How can these measurements be made?

The pallet made earlier is kept in a parallel plate capacitor which is connected to the LCR meter.
Before putting different samples within two parallel plates, both

Plates and the sample surfaces should be cleaned using sandpaper. Also the conductivity of
samples are tested.

When connected to an automatic LCR meter, the capacitance (C) and loss (D) measurements can
be readout directly yielding fast, reasonable results.

LCR Meters and specimen cells are readily available that make it easy to perform impedance
measurements on materials. A measuring instrument with a wide programmable frequency range
is important since the insulation properties can vary substantially with frequency. Accuracy of
results can be enhanced by averaging several measurements and calculating results can be
simplified through computer programs, all of which leads to better process control, increased
efficiency and superior products.[19].

33
 CHAPTER-5
5. RESULT AND DISCUSSION:
5.1. Structural Characteristics :

(1 0 1) BaTiO3
Intensity (arb. Unit)

(1 1 2)
(1 1 1 )

(2 0 2)
(0 0 1)

(2 2 0)

(1 0 3)
(1 1 0)
(1 0 2)

20 30 40 50 60 70 80
Bragg Angle (2)

Fig. 18(a) X-ray diffraction pattern of BaTi03 sample

10% Bi doped BaTiO3

Intensity (arb. Unit)

20 30 40 50 60 70 80
Bragg Angle (2)

Fig. 18(b) X-ray diffraction pattern of Ba0.9Bi0.1Ti03 sample

34
 20% Bi doped BaTiO3
Intensity (arb. Unit)

20 30 40 50 60 70 80
Bragg Angle (2)

Fig. 18(c) X-ray diffraction pattern of Ba0.8Bi0.2Ti03 sample

Table 5. Comparision of tolerance factor, average crystallite size, lattice parameters,

tetragonality and volume of Ba1-xBixTiO3 (x=0.0, 0.1, 0.2) samples.

Sample tolerance Average Structure a (Å) c(Å) c/a Volume

factor Crystallite (Å)3
Size (nm)
BaTi03 0.9698 24.930 tetragonal 4.0138 4.0356 1.0055 64.92

Ba0.9Bi0.1Ti03 0.9586 28.232 tetragonal 4.0097 4.0351 1.0063 64.88

Ba0.8Bi0.2Ti03 0.9473 30.749 tetragonal 4.0064 4.0343 1.0070 64.75

Figure 5(a-c) shows the XRD pattern of sample with general Ba1-xBixTiO3 (x=0.0, 0.1, 0.2). The
spatial position (in angle) and intensity of the peaks were used to analyze crystal system. All the
peaks of the patterns were indexed using standard computer software POWDMULT [20]. Based
on the least difference between the observed and calculated value of the inter-planner distance (d),
the unit cell lattice parameters and crystal system were selected, and found to be tetragonal. It is
35
noticed that on increasing Bi concentration in BTO, the diffraction peaks shift towards the lower
Bragg angle .Thus, increasing Bi content leads to increase in the unit cell volume which can be
related to the Bi substitution (mentioned in table 5). These observations can be explained by the
fact that for x = 0.1 and 0.2, the comparatively smaller Bi2+ (rion = 118 pm) ions substitute the Ba2+
(rion = 149 pm) ions at the tetragonal sites of BaTiO3. From Table 1, it is observed that, there is a
tendency of the cell parameters to decrease with increase in x resulting in a peak shift of the
corresponding X ray peaks.

5.2 Analysis of Dielectric properties using LCR meter :

o
8000 25 C x=0
=0.10
=0.20
6000
r

4000

2000

1 10 100 1000
Frequency (kHz)

Fig-19: Dielectric constant vs Frequency

Fig-19 shows the frequency dependence of relative dielectric constant (ε r) at room temperature

for Ba1-xBixTiO3 (x=0.0, 0.1, 0.2). As the graph shows in the low frequency range about 10 kHz

the value of εr is comparatively smaller at lower frequency-region. The increase in the value of εr

can be ascribed to the electron-phonon interaction and grain boundary sliding effect at higher

temperature [21]. The dielectric constant decreases smoothly on increasing the frequency which

indicates the dielectric behaviour of the sample. This is because with increase in frequency, the

contribution of interfacial, dipolar, ionic and atomic polarizations decreases and finally vanish

[22] at very high frequency.

36
 o
1.6 25 C
x=0
1.4 =0.10
=0.20
1.2

1.0
tan

0.8

0.6

0.4

0.2

0.0
1 10 100 1000
Frequency (kHz)

Fig-20: Dielectric loss vs Frequency

Fig-20 shows the variation of tanδ with frequency at room temperature for all the samples

Ba1-xBixTiO3 (x=0.0, 0.1, 0.2). The figure indicates that at low frequency range the dielectric loss,

is more at higher temperatures which is due to the high leakage current because of space charges

generated due to thermal excitation( as per literature review). With increase in frequency the

dielectric loss decreases for all the doped samples at room temperature.

37
 CHAPTER - 6

6. CONCLUSIONS:

Finally it was concluded that

• The densely covered microstructures( Bi doped BaTiO3 ) are prepared by solid

state reaction method which comprises of processes like selection of raw
material, weighing , grinding, calcinating, pellet preparation, sintering.

• These materials are characterized by using 2 techniques like X-ray

diffractometer and dielectric properties using LCR Meter.

• From XRD analysis it was observed that material is Tetragonal structure.

• From study of dielectric properties it was concluded that doping of Bismuth

to Barium Titanate reduces the dielectric loss of the material and it enhances
the dielectric constant of the material.

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40