University of Engineering & Technology Lahore

Department of Metallurgical & Materials Engineering

Synthesis and Characterization of lead zirconium titanate

SUPERVISOR
Dr Muhammad Asif Rafiq

AUTHORS
Faran 2015-MM-10
M Ahmad 2015-MM-18
Imtiaz Dashti 2015-MM-40
 Synthesis and Characterization of lead zirconium titanate

This Thesis is submitted in partial fulfillment of the requirement of the degree of Bachelors of
Science (BS) in Metallurgical & Materials Engineering.

Internal Examiner (Advisor) External Examiner

Signature: ___________________ Signature: __________________

Name: ______________________ Name: _____________________

Chairman

Signature: ________________________

Department of Metallurgical & Materials Engineering, University of

Engineering & Technology, Lahore.
 ABSTRACT

Lead zirconium titanate is an inorganic compound which shows

exceptional piezo-electric effect. It is a ceramic perovskite that shows
some electrical properties when mechanical load is applied. It has a
number of applications as transducers, sensors etc. In this study
electrical properties of PZT were investigated after its synthesis, we
had used PZT with different percentage of doped zirconia as 50%,
55%,60%. For its application we took a initiative of coating it with
tire of bicycle so the stresses induced could cause some mechanical
load on PZT and by storing this energy, we can drive off bicycle upto
couple of km’s
 DEDICATION

To our beloved parents & teachers

 ACKNOWLEDGMENTS
In the name of ALLAH, the most beneficent and merciful who gave us the strength and
knowledge to carry out this research and complete the project “Synthesis and
Characterization of lead zirconium titanate” Our research work would not have been
completed without the provision and assistance of many people. This is a best time to pay our
gratitude to them for their cooperation in this work.

Our deep gratitude and appreciation goes to my thesis advisor and mentor Associate Prof.
Dr. Muhammad Asif Rafiq for his constant guidance, motivation and support during the
course of our studies. His valuable suggestions broadened horizon and made this research
work interesting and challenging for. We also wish to acknowledge the contributions made
by our fellows from whom we have learned so much, those whose books we have read.

There are many other people to thank who guided us throughout this research. Since some
have chosen to remain anonymous, and I could easily overlook someone. I‟ve thought it best
not to write names.

To the many friends and colleagues who gave feedback, offered suggestions, shared their
stories, gave technical help and provided much needed moral support. We want you to know
that we could not have done this without you. Your help has been invaluable and we are
deeply grateful.

Our deepest gratitude is extended to our family members, especially to our parents who have

been giving us endless care and are always supportive in our education.

Declaration
It is hereby declared that this research, entitled “Synthesis and Characterization of lead
zirconium titanate” is an original and authentic work of the author. It is further guaranteed
that current work is not submitted for the acquisition of any degree or qualification at any
 other institute besides University of Engineering & Technology, Lahore for the partial
fulfilment of BSc. in Metallurgical and Materials Engineering degree requirement. It is
assured that; this thesis does not contain any formerly published data except where the
references are quoted.

Table of Contents
Chapter 1 ................................................................................................................................................ 1
Introduction ........................................................................................................................................... 1
1. Introduction: ................................................................................................................................... 2
1.2 The Scope of Thesis ....................................................................................................................... 3
1.3 Organization of Thesis ...................................................................................................................
3
Chapter 2 ................................................................................................................................................. 4
Literature Overview ................................................................................................................................ 4
2.1 Piezoelectricity .................................................................................................................................. 5
2.1.1 Piezoelectric Effect ................................................................................................................. 5
2.1.2 Crystal Symmetry ................................................................................................................... 7
2.2 Curie temperature (TC) ................................................................................................................. 9
2.3. Hysteresis loop ........................................................................................................................... 10
2.4 Ferroelectricity ............................................................................................................................ 13
2.4.1. Ferroelectric Ceramics Crystal Structure/Perovskite structure: ......................................... 13
2.5 BaTiO3-based Ceramics .............................................................................................................. 13
2.5.1 BaTiO3-BaZrO3-CaTiO3 (BCZT) ............................................................................................... 16
2.6 Bismuth ferrite ................................................................................................................................ 17
2.6.1 Structure and properties of BiFeO3 ..................................................................................... 18
2.6.2 Effect of Dopants .....................................................................................................................
19
BCZT-BiFeO3 .......................................................................................................................................... 20
Chapter 3 ............................................................................................................................................... 21
Experimental Work ............................................................................................................................... 21
3.1. Calculations ....................................................................................................................................
22
3.2. Procedure: .................................................................................................................................. 24
3.2.1. Ball Mill................................................................................................................................ 24
3.2.2. Drying .................................................................................................................................. 25
3.2.3. Calcination .......................................................................................................................... 25
3.2.4. Doping /Mixing ....................................................................................................................
25
3.2.5. Pressing ............................................................................................................................... 25
3.2.6. Sintering .............................................................................................................................. 26
3.3. Characterization Techniques ......................................................................................................... 27
3.3.1. XRD Analysis ........................................................................................................................ 28
3.3.2. Scanning Electron Microscope (SEM) ................................................................................. 29
3.3.3. Energy Dispersive X-ray Spectroscopy (EDS or EDX) ........................................................... 30
3.3.4. LCR (for electrical properties) ............................................................................................. 31
Chapter 4 ............................................................................................................................................... 34
Results and Discussions ........................................................................................................................ 34
4.1. XRD
................................................................................................................................................
. 35
 4.2. SEM
................................................................................................................................................
36
.......................................................................................................................................................... 36
4.3. Complex Impedance Spectroscopy
................................................................................................ 37
4.4 Conductivity .................................................................................................................................... 42
Conclusion ............................................................................................................................................. 44

LIST OF FIGURES
Figure 2.1 Simple molecular model for explaining the piezoelectric effect: (a) unperturbed
molecule; (b) molecule subjected to an external stress; (c) electric field generated on the
material surfaces. 5
Figure 2.2 Schematic representation of the longitudinal direct (a), converse (b), and shear (c)
piezoelectric effects 6
Figure 2.3 Interrelationship of piezoelectric and subgroups on the basis of symmetry 7
Figure 2.4 Idealized permittivity of ferroelectric material as a function of temperature. 9
Figure 2.5 A typical hysteresis loop in ferroelectrics and corresponding domain reversal
(polarization rotation) and strain–electric field curve 12
Figure 2.6 Room-temperature P–E hysteresis loops for BT single crystal and ceramics with
different grain size. (a) BT single crystal, (b) BT ceramics with coarse grain, (c) BT ceramics
with fine grain 12

Figure 2.7 Schematic view of the perovskite ABO3 unit cell for cubic BaTiO3 ceramic with
the space group (Pm3m) and lattice constant ~4Å 14
Figure 2.8 various phases of BaTiO3 14
Figure 2.9. Various lattice parameters, spontaneous polarization and dielectric constant in
different phases of BaTiO3 16
Figure 2.10. Ternary diagram for the system BaTiO3-BaZrO3-CaTiO3. Piezoelectric d33
coefficient values for studied compositions are shown. The corresponding references are
also shown in brackets 17
Figure 2.11 Structure of a perovskite with chemical formula ABX3. The red spheres are X
atoms (usually oxygen), the blue spheres are B-atoms and the green spheres are A atom.
18
Figure 3.1: Ball Mill 24
Figure 3.2: shown the basic phenomenon of pressing powder in metal die 26
Figure 3.3: Hydraulic Press for pellets making 26
Figure 3.4. Sintering and Calcination furnace 28
Figure 3.5. Different beams of crystalline materials 29
Figure 3.6 Principle of EDS 30
Figure 3.7: LCR meter 32
Figure 3.8: Methodology applied for experimental work 33
Figure 4.1: X-ray diffraction of patterns of BCZT (Ba0.85Ca0.15Zr0.1 (TiO3)0.9) BFO (BiFeO3)
doped with 0%, 2%, 4%, 6%, 8% and 10% CuO. 35
Figure 4.2: SEM images showing increase in particle size with CuO addition as represented
by a) pure BCZT b) 2% CuO doped BCZT c) 4% CuO doped BCZT d) 6% CuO doped
 BCZT e) 8% CuO doped BCZT f) 10% CuO doped BCZT 36
Figure 4.3:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 2% CuO 37
Figure 4.4:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 4% CuO 38
Figure 4.5:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 6% CuO 39
Figure 4.6:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 8% CuO 40
Figure 4.7:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 10% CuO 41
Figure 4.8: Graph between frequency and conductivity of CuO doped with BCZT-BFO,
(a)
2% CuO; (b) 4% CuO; (c) 6%CuO; (d) 8% CuO; (e) 10% CuO 42

LIST OF TABLES

Table 1.1 Piezoelectric devices applications 2

Nomenclature
PZT Lead zirconium Titanate
BT Barium Titanate
BZT Barium Zirconium Titanate
BCZT Barium Calcium Zirconium Titanate
CuO Copper Oxide
Tc Curie Temperature
LCR Inductance, Capacitance, Resistance meter
CIS Complex Impedance Spectroscopy
XRD X-Ray Diffraction Analysis
SEM Scanning Electron Microscopy
D33 Dielectric Constant
DF Dielectric Loss
Z Impedance
Z’ Real component of Impedance
Z” Imaginary component of Impedance
kB Boltzmann constant
A.E Activation Energy
eV Electron volt
BFO Bismuth Ferrite
I Current
V Voltage
Chapter 1
Introduction

1. Introduction:
Piezo-electric substances are of great interest in today’s world. By applying stress,
electric current is produced which can be made more efficient to be a part of total energy
consumption. This effect can also be reversed as by providing electric charge result in
mechanical energy. There are several materials that exhibit piezo-electric effect such as
bones, quartz and ceramics(PZT)

You can imagine its importance by thinking of walking down the street and charging
your phone or driving off electrical energy as you pedal your cycle

1
 Piezoelectricity is the ability in certain crystalline materials to develop an electric
charge from a mechanical stress, or vice versa . Based on the unique properties, piezoelectric
materials have been utilized to fabricate various types of electronic devices, including
piezoelectric sensors, piezoelectric actuators, piezoelectric transducers, and so on . The
piezoelectric devices have found a wide range of applications from consumer products to
scientific equipment.

Piezoelectric sensors find their application in microphones, force sensors, strain

sensors, pressure sensors, microbalances. Similarly, piezoelectric actuators are used in
loudspeaker, piezo-electric motors, Atomic force microscope, STM, MRI scanners. Piezo-
electric transducers are used in non-destructive testing, mega sonic cleaning, vibration
monitoring

Lead zirconium titanate PbZr1−xTixO3 (abbreviated as PZT) is a solid solution of

PbTiO3 and PbZrO3 compounds. As is the case for most ferroelectric materials, it has an
ABO3 type perovskite structure where A is a metal ion with a +2 valency (e.g., Pb) and B is a
metal ion with a +4 valence (e.g., Ti,,Zr). In the case of PZT, the A positions (corners of the
cube) are occupied by Pb2+ ions, B positions (body center) by Zr4+ or Ti4+ions, and O−2 ions
occupy the face centers. The electrical output obtained from piezo-ceramic is determined
mainly by the product of piezoelectric charge constant and voltage constant (d33 × g33) known as
figure of merit for power harvesting S(Material with higher d33 and g33 leads to
higher d33 × g33that offers higher electrical output and hence is the essential criteria for the
material intended to be used for energy harvesting applications

PbTiO3 has a Curie temperature of 490°C, at which it undergoes a first-order phase

transition from cubic Para-electric phase to tetragonal ferroelectric phase with lattice
parameters c = 4.153 Å and a = 3.899 Å.

1.2 The Scope of Thesis

The objective of the present research is to design piezoelectric materials with perovskite
structure suitable for high performance piezoelectric devices. In particular, the PZT being the

2
most efficient piezoelectric material was prime focused In this study, the phase structure,
microstructure, dielectric properties, piezoelectric properties, and ferroelectric properties
were investigated.

1.3 Organization of Thesis

The thesis is organized as follows:

Chapter 1 mainly concentrates on the introduction to the background, the research motivation,
and the scope of this study.

Chapter 2 reviews the fundamentals of piezoelectricity and piezoelectric devices, the

problems of the current piezoelectric materials (especially lead-free piezoelectric materials),
recent development and their trend in the future.

Chapter 3 introduces the experimental approaches which were employed in this research.

Chapter 4 investigates the results and discussion about the doping effect of CuO on
BCZTBiFeO3

Chapter 2
Literature Overview

3
2.1 Piezoelectricity
2.1.1 Piezoelectric Effect
Piezoelectricity is the ability of certain crystalline materials to convert mechanical
energy to electrical energy and vice versa. When a stress is applied on the material, an electric
charge is generated. This is the direct piezoelectric effect which was discovered by the
brothers Jacques and Pierre Curie in 1880 [1]. Figure 2.1 shows a simple molecular model for
explaining the direct piezoelectric effect. Without external stress, the centers of the positive
and negative charges of the material coincide. The positive and negative charges are
reciprocally cancelled, so the material represents electro neutrality (Fig. 2.1a). When an
external stress is applied on the material, the separation of the positive and negative centers
occurs and little dipoles are generated (Fig. 2.1b). The charges inside the material will
mutually cancel and the positive charges and negative charges will accumulate in two parallel
surfaces of the materials which is the generated electric field (Fig. 2.1c).

4
 Figure 2.1 Simple molecular model for explaining the piezoelectric effect: (a) unperturbed
molecule; (b) molecule subjected to an external stress; (c) electric field generated on the
material surfaces [9].

The converse piezoelectric effect (the production of stress and/or strain when an electric field
is applied) was later discovered and the existence of coverse piezoelectric effect was
confirmed immediately. Moreover, the electric charge will reverse its sign when the stress is
changed from tensile to compressive for direct piezoelectric effect; while the strain will
reverse its sign when the direction of electric field is changed for converse piezoelectric
effect. Shear piezoelectric effect also exist if the shear mechanical stress and strain couples
with the electric charge. Figure
2.2 demonstrates the phenomena of the direct, converse, and shear piezoelectric effects.

5
 Figure 2.2 Schematic representation of the longitudinal direct (a), converse (b), and shear (c)
piezoelectric effects [10]

For the direct piezoelectric effect, an applied stress creates an electric charge. This
relationship can be formulated as follow:

D = Q/A = dT (2.1)

where D is the dielectric displacement, Q is charge, A is area, d is the piezoelectric charge

constant expressed in C/N, and T is stress.

6
For the converse piezoelectric effect, an applied field produces a proportional strain. This
relationship can be formulated as follow:

S = dE (2.2)

where S is strain, d is the piezoelectric charge constant expressed in m/V, and E is the electric
field.

2.1.2 Crystal Symmetry

Crystals are classified into 32 point groups based on their symmetry. These 32 point
groups are subdivisions of 7 basic crystal systems that in ascending order of symmetry
include; triclinic, monoclinic, orthorhombic, tetragonal, rhombohedral (trigonal), hexagonal
and cubic. These point groups are divided into two classes which include a centre of
symmetry and without centre of symmetry. There are 21 non-centrosymmetric point groups,
20 (except point group 432) of which exhibit piezoelectricity. Fig. 2.3 shows that there are 10
crystal classes out of a possible 20 that are designated as pyroelectric. This group of materials
possess the unusual characteristic of being permanently polarized within a given temperature
range. Unlike the more general piezoelectric classes that produce a polarization under stress,
the pyroelectrics develop this polarization spontaneously and form permanent dipoles in the
structure. This polarization also changes with temperature hence, the term pyroelectricity. A
subgroup of the spontaneously polarized pyroelectrics is a very special category of materials
known as ferroelectrics. Similar to pyroelectrics, materials in this group possess spontaneous
polarization; however, unlike pyroelectrics, the direction of the spontaneous polarization is
orientable by an electric field of some magnitude less than the dielectric breakdown of the
material itself. As all pyroelectric materials are polar, and ferroelectrics are a sub-group of
these pyroelectric materials; all ferroelectrics are pyroelectrics and piezoelectrics both. These
crystals show large dielectric constant and high electro-mechanical coupling factor.
Polycrystalline ceramics of these materials also show the ferroelectric effect after poling.
Ferroelectric materials have four subcategories: the perovskite (ABO3) group, the pyrochlore
group (A2B2O7), the tungsten-bronze group (AB2O6), the bismuth layer structure group
(A4B3O12), among which the perovskite group is the most important and thus the most widely
studied. The ABO3 type ferroelectric ceramics are further divided into BaTiO3, Pb(ZrxTi1-
x)O3, (Bi0.5Na0.5)TiO3 and (KxNa1-x)NbO3 family of compositions [1,11]

7
 Figure 2.3 Interrelationship of piezoelectric and subgroups on the basis of symmetry [11].

Below the Curie temperature, ferroelectric crystals generally develop a random

domain structure, leading to a net zero polarization of each crystal. Within each ferroelectric
domain the polarization is in the same direction with a domain wall separating regions with
different polarization directions. This structure is necessary to minimize free energy due to
the development of anisotropic strains and depolarization fields below TC. Domain walls are
characterized by the angle between the polarization directions on either side of the wall. Thus
a 180o domain wall demarks a boundary between antiparallel domains, while a 90o wall
would be formed at the boundary between domains pointed “up” and “left”, for example. The
allowed angles for domain walls depend on the orientation of the spontaneous polarization
allowed by symmetry. Thus in rhombohedrally distorted perovskites, there are no 90o domain
walls like a tetragonal perovskite, but instead 71o and 109o walls. A more complete picture of
the way the polarization changes as a domain wall is crossed is given by Cao and Cross [12].

8
2.2 Curie temperature (TC)
Ferroelectric crystals exhibit electric dipole moments even in the absence of an
external electric field below a certain temperature and a paraelectric behavior above this
temperature. This temperature of structural phase transition from a high-temperature non
ferroelectric paraelectric phase to a low-temperature ferroelectric phase is called the Curie
temperature (Tc). This polarization can be reoriented or reversed fully or in part by applying
an electric field. The spontaneous polarization in a ferroelectric material is usually not
uniformly aligned throughout the whole material along the same direction. The regions in the
material with uniformly oriented spontaneous polarization are called ferroelectric domains
and the region separating two domains is called a domain wall. Ferroelectric domains form to
minimize the electrostatic energy of depolarizing fields and the elastic energy associated with
mechanical constraints to which the ferroelectric material is subjected as it is cooled through
paraelectric - ferroelectric or ferroelectric - ferroelectric phase transition. Types of domain
walls that can occur in a ferroelectric crystal depend on the symmetry of both non-
ferroelectric and ferroelectric phases of the crystal. The domain walls are usually labeled by
the angle between the spontaneous polarization vectors in the domains that these walls
separate. For example, 90°-walls are those which separate regions with mutually
perpendicular polarization (although the angle between polarization directions on each side of
a 90° domain wall is slightly smaller than 90◦) [13, 14].

Figure 2.4 Idealized permittivity of ferroelectric material as a function of temperature.

In ferroelectrics dominated by a displacive phase transition, such as perovskite materials, the
temperature dependence of the permittivity varies for 1st and 2nd order phase transitions. Fig.
2.4 illustrates the temperature dependence of the permittivity for displacive ferroelectric
materials exhibiting first or second order phase transitions. Second order phase transitions,

9
which are common for rhombohedral compositions, are generally characterized by a broad
peak in permittivity. Ferroelectrics undergoing first order phase transitions, typical of
tetragonal perovskite materials, however show a fairly flat permittivity with increasing
temperature right up to the Tc.

The reciprocal permittivity 1/ε is known to be linear with respect to the temperature in a wide
range in the para electric phase (so-called Curie-Weiss law), stated as

𝜖= 𝐶 (2.3)
𝑇−𝑇𝑜

where C is the Curie-Weiss constant and T0 the Curie-Weiss temperature. T0 is slightly lower
than the exact transition temperature Tc. For displacive transitions (e.g., BaTiO3, PbTiO3,
KNbO3), the Curie Constant is very high (~ 104 – 105K) and the paraelectric phase is
microscopically nonpolar. For order-disorder transition (e.g., TGS, KH2PO4), the Curie
constant is of the order of T0 and the paraelectric phase is nonpolar on macroscopic or
thermally averaged sense. The reorientable component of the spontaneous polarization of
ferroelectric materials falls to zero at the Curie temperature.

2.3. Hysteresis loop

Hysteresis loop, as a simple and effective tool, is the most accepted method to
understand ferroelectric materials [15]. In principle, every ferroelectric material has its own
unique hysteresis loop, as a fingerprint. Through the hysteresis loops, the ferroelectricity
could be identified directly. Fig.2.3 is a typical ferroelectric hysteresis loop, through which
the characteristic parameters, such as spontaneous polarization (Ps), remnant polarization (Pr)
and coercive field (Ec) can be determined. Owing to the requirement of the energy minima,
the grains in polycrystalline materials are always splitting into many domains. The directions
of the domains are randomly distributed in such a way to lead to zero net macroscopic
polarization. When the external field exceeds the Ec, the polycrystalline ferroelectric ceramic
may be brought into a polar state. As shown in Fig.2.5, a macroscopic polarization is induced
gradually by increasing the electric field strength. The drastic variation in the polarization in
the vicinity of Ec is mainly attributed to the polarization reversal (domain switching), while at
high field end, the polarization is saturated and the material behaves as a linear dielectric.

10
 When the electric field strength starts to decrease, some domains would back-switch,
but at zero field the net polarization is nonzero, leading to the remnant polarization Pr. To
obtain a zero polarization, an electric field with opposite direction is needed. Such field
strength is called the coercive field (or coercivity). With increasing the opposite field
strength, a similar rearrangement of the polarization is observed in the negative field part. For
ferroelectric materials, the spontaneous polarization Ps may be estimated by intercepting the
polarization axis with the extrapolated linear segment, as shown in Fig. 2.5. Since
ferroelectrics usually possess ferroelastic domains (with the exception of LiNbO3 which only
has 180° ferroelectric domains), spontaneous strain is also induced with the external electric
field simultaneously. Therefore, if the strain is monitored as well as the polarization, a strain–
electric field curve, like “butterfly,” can be observed.

For ideal ferroelectric system, the observed hysteresis loops should be symmetric. The
positive and negative Ec and Pr are equal. In reality, the shape of the ferroelectric hysteresis
loops may be affected by many factors, such as thickness of the samples, material
composition, thermal treatment, presence of the charged defects, mechanical stresses,
measurement conditions and so on. Their effects on material properties could be well
reflected through the loops. For the same material system, ferroelectric hysteresis loops of
single crystalline and polycrystalline ceramic samples show a large difference. This is mainly
attributed to the clamping effect of domains with respect to grain boundaries. It can be seen in
Fig.2.6, the shape of the P–E loop for BaTiO3 (BT) crystal is rather square, whereas for BT
ceramics the loop is slanted at a certain degree. By applying the same electric field, saturated
polarization can be induced in BT crystal instead of ceramic, suggesting that the polarization
switching in crystal is much easier than that in ceramic, owing to the absence of grain
boundary. In addition, due to the crystal symmetry, domains in tetragonal BT single crystal
could be switched completely with respect to the external field applied along [001] direction.
In contrast, because of the random distribution of the grains, maximum 83% polarization can
be switched in ceramics without considering the clamping effect by adjacent grains. This
partially explained the lower spontaneous polarization observed in BT ceramic. Thus, BT
single crystal was found to possess a lower Ec with a higher Pr, when compared to those of
BT ceramics. Fig.2.6 shows ferroelectric hysteresis loops for BT crystal, coarse grain and fine
grain ceramics, exhibiting a transition from square loop to slim loop with decreasing the grain
size. Here, crystal sample can be considered as a very large grain without grain boundary.
Therefore, the clamping effect due to the neighbouring grains is absent in crystals.

11
 Figure 2.5 A typical hysteresis loop in ferroelectrics and corresponding domain reversal
(polarization rotation) and strain–electric field curve [16].

Figure 2.6 Room-temperature P–E hysteresis loops for BT single crystal and ceramics with
different grain size. (a) BT single crystal, (b) BT ceramics with coarse grain, (c) BT ceramics
with fine grain [17].

2.4 Ferroelectricity
It was J.Valasek who discovered the ferroelectricity phenomenon in 1921 while studying
the dielectric properties of Rochelle salt (NaKC4H4 O6.4H2O) [12]. Another material
potassium di hydrogen phosphate (KH2PO4), KDP was reported as ferroelectric material after

12
almost one and half decade [5]. During World War II (1944) Arthur R. von Hippel discovered
Barium Titanate (BaTiO3 or BT) which brings a revolution in ferroelectric class of materials.
There are over 250 materials that exhibit ferroelectric properties [16]. Some of the chief
materials include:
• Strontium Titanate (ST)

• Barium Zirconate Titanate (BZT)

• Potassium Sodium Niobate (KNN)

Ferroelectric materials possess a unique axis where the dipole moment is oriented even in
the unstrained condition which means they exhibit spontaneous polarization (ferroelectricity).
In other word Ferroelectricity could be defined as the reversibility of the direction of the
electric dipoles in a polar crystal by means of an applied electric field. These materials are
named ferroelectrics. Complete reversing of spontaneous polarization is termed as Switching.
Another distinguishing feature of ferroelectrics is the presence of Domains which are due to
the alignment of dipole moments within the grain of the material. These (ferroelectric)
materials are principally noncentrosymmetric, chief ferroelectric materials have perovskite
(ABO3 type) structure for example, Barium Titanate (BT) or Barium Zirconium Titanate
[BaZrxTi(1−x)O3](BZT), the material of curiosity in this work.

2.4.1. Ferroelectric Ceramics Crystal Structure/Perovskite structure:

Ferroelectric ceramics has perovskite i.e. ABO3 type crystal structure. The A-site could be
either M1+ (K,Na, etc.), M2+ (Sr, Ca, Ba, etc.), or M3+ (Fe, La, etc.) and the B-site could be
occupied by M5+ (Sb,Nb, etc.), M4+ (Ti, Ce, etc.), or M3+ (Fe, Mn, etc.).

2.5 BaTiO3-based Ceramics

Barium titanate is the first ferroelectric ceramic material which was described by Wul
and Goldman in 1946 [18]. It is isostructural with the mineral perovskite (CaTiO3) and so is
referred to as ‘a perovskite’. The generalized perovskite structure ABO3, is visualized as
based on a cubic close-packed assembly of composition AO3 with the A-ion cordinated with
12 oxygen ions and the B-ion in the octahedral interstices are shown in Fig. 2.7. In the ABO3
structure, the large cation (A) is at the corners while the small cation (B) is at the body center
and oxygen is located at the center of the faces.

13
 Figure 2.7 Schematic view of the perovskite ABO3 unit cell for cubic BaTiO3 ceramic with
the space group (Pm3m) and lattice constant ~4Å [19].

For BaTiO3, above its Curie point (approximately 130oC) the unit cell is cubic. Below the
Curie point the structure is slightly distorted to the tetragonal form with a dipole moment
along c direction. Other transformations occur at temperatures close to 0oC and -90oC: below
5oC the unit cell is orthorhombic with the polar axis parallel to a face diagonal and below -
90oC it is rhombohedral with the polar axis along a body diagonal. The various phases of
BaTiO3 is shown in fig 2.8

Figure 2.8 various phases of BaTiO3 [1].

BaTiO3 is tetragonal (4mm) which is ferroelectric. The tetragonal unit cell results
from the distortion of the original cubic cell. Ferroelectricity arises due to the off-centre
displacement of the oxygen (at face centers) and titanium (at body centers) in opposite
directions along <100>. As a result, one of the cube edges is elongated to become polar c axis

14
of the tetragonal phase. Since there are six equivalent<100> directions in the cubic phase, the
polar axis can be parallel to any one of these directions. This leads to the formation of 90
degrees and 180-degree domain walls in the tetragonal phase. In the temperature range of
50°C to –90°C, the structure of BaTiO3 is orthorhombic which is a ferroelectric phase having
the polar axis along one of <110> direction of the original cubic unit cell. There are 12
equivalent <110> directions. The displacement of titanium and oxygen ions along one of the
<110> cubic direction leads to an elongation of the face diagonals of the original cubic unit
cell, producing shear of the original cube. Below -90°C, a new ferroelectric phase of BaTiO3
appears with a rhombohedral structure (3m). The polar axis for this phase lies along one of
the 8 equivalent original cubic <111> directions. The rhombohedral distortions can be
visualized as the stretching of the original cubic cell along one of the body diagonals.
Variation of dielectric constant, spontaneous polarization and lattice parameter in different
phases of BaTiO3 is shown in the Fig.2.8. The tetragonal phase of BaTiO3 has been the
object of most investigations as this phase is stable at and above room temperature. Due to the
presence of 90° and 180° domains, macroscopic spontaneous polarization is not observed
even for a single crystal of tetragonal phase, in the absence of the DC electric field.
Application of a DC field may result in merging of these domains to give monodomain
crystal with measurable spontaneous polarization. The orientation of all the domains along
applied external DC field is not possible for BaTiO3 ceramic. This results in low value of
saturation and remnant polarization for ceramic samples in comparison to single crystals.

15
 Figure 2.9. Various lattice parameters, spontaneous polarization and dielectric constant in
different phases of BaTiO3 [20-22].

2.5.1 BaTiO3-BaZrO3-CaTiO3 (BCZT)

To enhance the piezoelectric and dielectric properties, many BaTiO3-based solid
solutions with different A-site and B-site dopants (where, typically, A = Ca, Sr, La; B = Nb,
Ta, Zr) are used. Especially Ca2+ and Zr4+ doping, hereinafter called Ba1-xCaxTi1-yZryO3 ,
have been the focus of numerous publications after a high piezoelectric coefficient (d33 = 620
pC/N) was reported for Ba0.85Ca0.15Ti0.90Zr0.10O3, i.e., within the pseudo-binary solid solution
system (1-w)Ba(Ti0.80Zr0.20)O3-w(Ba0.70 Ca0.30)TiO3 for w = 0.50 [23] (Figure 2.10). This
composition stays at the vicinity of a tricritical point of this system, in the frontier of the high
temperature cubic non-ferroelectric phase, with the two ferroelectric ones, rhombohedral and
tetragonal phases. It has been shown that cubic phase coexists with the two ferroelectric ones,
greatly enhancing the polarizability of the ceramic. The low TC « 93 ˝C, high synthesis (1300
˝C for 2 h) and sintering (1450 ˝C for 3 h) conditions, not suitable for industrial production,
and the subsequently large grain structures are among the drawbacks that exist in this
composition. Microstructures with average grain size > 10 µm obtained to date are not

16
optimized for the present trend of device miniaturization. This feature is therefore important
in order to increase the frequency range of the ultrasonic transduction. Therefore, strategies to
reduce the synthesis and sintering temperatures are needed for processing routes towards sub-
10 µm grain size ceramics. Most of the work has been carried out following the solid state
synthesis route, and the role of dopants and substitutions [23-25], the processing related
ceramic microstructure [26-29], resulting in strong changes in the piezoelectric coefficient for
the same composition (Figure2.10), and the poling process [30] have been current topic for
research line.

Figure 2.10. Ternary diagram for the system BaTiO3-BaZrO3-CaTiO3. Piezoelectric d33
coefficient values for studied compositions are shown. The corresponding references are also
shown in brackets.

As for BaTiO3-CaTiO3 binary system, the addition of Ca2+ into the site A of BaTiO3
increses the stability temperature range of the tetragonal phase [31]. As for the BaTiO3-
BaZrO3 binary system, the substitution of Zr4+ into the B site produces an undesired reduction
of Tc, while T1 and T2 increase at different rates.

2.6 Bismuth ferrite

Perovskite and perovskite-like structures due to the simplicity of their crystal structure
and a large variety of compositions have become the basis for the creation of numerous
functional materials. Bismuth ferrite (BiFeO3) was one of the first studied multiferroics with
the perovskite structure. It was also found that it possesses record-breaking ferro- electric

17
(TC=1103 K) and antiferromagnetic (TN=643 K) ordering temperatures (TC is the Curie
temperature, TN is Neel temperature), but the maximum value of the polarization (P) in the
single-crystal BiFeO3 turned out to be very small (3 ± 6 mC cm2). In disparity to the single
crystals, the measurements of the pyroelectric current in the thin epitaxial films of bismuth
ferrite have shown high polarizability, reaching values of 60 ± 100 m C cm2. The main
reason for such small polarization in the previously investigated bulk crystals is the leakage
current caused by non-stoichiometry and defects, which was eliminated in the thin film state
and later in the high-quality single- and polycrystals17 ± 19. The synthesis of the BiFeO3
phase is complex, on one hand, by high probability of the formation of impurity phases such
as sillenite Bi25FexO20 (isostructural to the meta- stable g-Bi2O3) and Bi2Fe4O9 at the
grain boundaries of polycrystalline ceramics and, on the other hand, by the strong dependency
of the physical properties on the oxygen stoichiometry and crystal perfection. Low leakage
currents and the presence of magnetic moment in the crystal both are required for the
practical application of bismuth ferrite, therefore, special attention has been paid to the
improvement of the ferroelectric characteristics and the destruction of the cycloidal
antiferromagnetic order in BiFeO3. The local spin structure in bismuth ferrite is of the G type
(every Fe3+ ion is surrounded by six Fe3+ ions with the opposite spins. [31]

2.6.1 Structure and properties of BiFeO3

The perovskite BiFeO3 (BFO) was first produced in the late 1950s. BFO has long
been known to be, in its bulk form, an antiferromagnetic, ferroelectric multi-ferroic with an
antiferromagnetic Neel temperature of TN=643K and a ferroelectric Curie temperature of
TC=1103K. We note that BiFeO3 adopts the perovskiteas shown in figure 14 and not the
„ferrite‟structure, regardless of its nomenclature.

Figure 2.11 Structure of a perovskite with chemical formula ABX3. The red spheres are X
atoms (usually oxygen), the blue spheres are B-atoms and the green spheres are A atom.

18
 Bulk bismuth ferrite can be defined as a rhombohedral distorted ferroelectric
perovskite with the space group R3c as shown in figure 15. The lattice parameters of the
rhombohedral unit cell are a = 5.59 Å and α = 60.68°. In such a distorted structure, the R3c
symmetry authorities the development of spontaneous polarization (Ps) along the pseudo
cubic [111] direction. In Figure 15, the unit cell of BiFeO3 is shown in its hexagonal
representation ([001] hex, [100] hex, [110] hex, [010] hex are hexagonal axis). On the other
hand, in some cases, a pseudo cubic representation has been used, where [111]c is equivalent
to [001] hex. Oxygen atoms exist at face-centred sites of the Bi cubic structure. BiFeO3 has
been shown to be ferroelectric with polarization direction along the rhombohedral c-axis (i.e.,
[111]c) due to the displacement of Bi and Fe, O relative to each other. [32]

2.6.2 Effect of Dopants

i. Effect of Neodymium (Nd) and Cobalt (Co):

Effect of Nd and Co co doping aremany. They were successfully prepared by the solid state
mixed-oxide method. Increasing Co-doping content decreases the grain size and increase
density of the ceramics. The remanent magnetization was found to increase while the
coercive magnetic field decreased with increasing of Co-doping content. [33] ii. Effect of
manganese:

Manganese doping gave rise to a gradual increase of spontaneous magnetization along with
the clarity of magnetic hysteresis. This improved magnetization can be understood by the
modification of the long-range spiral G-type antiferromagnetic ordering to a collinear G-type
antiferromagnetic ordering, in which the canted component of the anti- ferromagnetically
ordered spins becomes measurable for the latter magnetic structure [34] iii. Effect of
strontium

The magnetic properties of BiFeO3 have been enhanced by the chemical manipulation. One
of the important aims of multiferroics material is to establish strong coupling of magnetic
ordering at room temperature, which can be achieved by chemical substitutions at both the Bi
and Fe sites. Sr doping (at the Bi site) resulted in samples being oxygen sub-stoichiometric
and with the increasing Sr concentration transition to SrFeO3 phase accompanied by a
decrease in magnetization.

iv. Effect of barium (Ba) and calcium (Ca)

19
Barium substituted BiFeO3 exhibited ferromagnetism and ferroelectricity simultaneously. Ca

doped bismuth ferrite material shows coupling of ferromagnetism and ferroelectricity. v.

Effect of copper (Cu)

As a result of addition of Cu to Bismuth ferrite, the density and the electrical properties
improved. Due to Cu doping, dielectric constant increases and the dielectric loss which is also
known as loss tangent decreases. Cu acts as a sintering aid for BiFeO3 [33] vi. Effect of
Titanium (Ti)

The magnetic and electric properties are improved by co-doping of BFO with Ti. The
remanent magnetization increases by the substitution of Ti to BFO. The magnetization
increases due to the structural distortion and the partial destruction of spin cycloid by co-
doping of BFO.

BCZT-BiFeO3:
BiFeO3 (BFO) content effects the microstructure and electrical properties of
Ba0.85Ca0.15Ti0.90Zr0.10O3 (BCTZ). For prepreation of BCZT-BeFiO3 a stable solid solution is
formed between BCTZ and BFO. The grain size gradually becomes smaller, and the ceramics
become denser with increasing the BFO content. The Curie temperature, dielectric constant,
and dielectric loss of BCTZ ceramics decrease simultaneously with the introduction of BFO.
Moreover, the remanent polarization reaches a maximum at x = 0.2 mol%, and the coercive
field continuously increases with increasing the BFO content due to the introduction of BFO
with a higher coercive field. Improved piezoelectric properties (d33 405 pC/N and kp
0.44) are demonstrated for the BCTZ ceramic with x = 0.2 mol%. [35]

20
Chapter 3
Experimental Work

3.1. Calculations
The basic calculations for the precursors used are as follows:

Precursors calculations

PbCO3 +0.52ZrO2 + 0.48TiO2 PbZr0.52Ti0.4803 + CO2

21
Masses of Chemicals

Molar mass (PbCO3) = 207.2 + 12 + 48

= 267.21 g/mol

Molar mass of 0.52ZrO2 = 0.52(91.22 + 32 )

= 64.08 g/mol

Molar mass of 0.48 TiO2 = 0.48 (47.867 + 32)

= 38.34g/mol

Molar mass of PbZr0.52Ti0.4803 = 207.2 + 47.436 + 22.967

= 277.61g/mol

As by balancing the equation on both sides we use the law of conversation of mass so from
this:

277.61g PZT contains PbCO3 = 267.21 g

For 10g of the sample the amount of PbCO3 required will be = (267.21/277.61) x10

= 9.62 g

So the amount of PbCO3 required for the preparation of the PZT will be 9.62g

277.61g PZT contains Zirconia = 64.0764g

For 10g of the sample the amount of zirconia required will be = (64.07/277.61)10

= 2.308g

For 10g of the sample the amount of Titania required will be = (38.3361/277.61)10

= 1.3809g

Precursors for Lead zirconium Titanate

• Lead carbonate (PbCO3) = 9.62g

• Zirconium oxide (ZrO2) = 2.308 g

• Titanium oxide (TiO2) = 1.3809 g

3.2. Procedure:

22
3.2.1. Ball Mill
A ball mill is a type of grinder used to grind materials into extremely fine powder for use in
mineral dressing processes, paints, pyrotechnics, and ceramics. Ball mills rotate around 200
rpm at horizontal axis, partially filled with the material to be ground plus the grinding
medium. Different materials are used as media, including ceramic balls, flint pebbles and
stainless-steel balls. An internal cascading effect reduces the material to a fine powder. The
difference in speeds between the balls and grinding jars produces an interaction between
frictional and impact forces, which releases high dynamic energies. The interplay between
these forces produces the high and very effective degree of size reduction of the planetary
ball mill.

Milling of the precursors i-e (PbCO3+ ZrO2+TiO2) for PZT were done for four hours using
zirconia balls in Teflon jars place in a planetary mill in metallurgical and materials
engineering department. The media used for milling was ethanol and the milling was done at
200 rev/min.

Figure 3.1: Ball Mill

3.2.2. Drying
Milled powders were dried at 100℃ for one hour. Drying process was done to evaporate the
ethanol from the jars and the remaining powers were clean from the zirconia ball for the
process of calcination.

3.2.3. Calcination
Calcination is the process in which a material is heated to a temperature below its melting
point to affect the thermal decomposition or the phase transition other than melting point, or
removal of a volatile fraction. Calcination is to be distinguished from roasting, in which more

23
complex gas-solid reactions take place between the furnace atmosphere and the solids.
Calcination reactions usually take place at or above the thermal decomposition temperature or
the transition temperature (for phase transitions). This temperature is usually defined as the
temperature at which the standard Gibbs free energy for a particular calcination reaction is
equal to zero.

Calcination of the milled BCZT was done in furnace at 850℃ for two hours. .

3.2.4. Mixing
The powder of PZT was milled for two hours in the same planetary mill at 200 rev/min using
an ethanol media with zirconia balls in Teflon jars. The samples were dried after this in oven
for one hour at 100℃. After drying the powders were cleaned for pressing operations.

3.2.5. Pressing
Dry pressing is the technique of fabricating ceramic components by the compaction of
powders in a metal die set. This fabrication technology enables the manufacture of parts to
accurate dimensional specifications and enables high volume production.

Pressing of the samples of powder 10g each were done in a hydraulic press by applying 6000
lbs. pressure and the size of the pallets made were of 10mm in diameter and 2mm in
thickness.

Figure 3.2: shown the basic phenomenon of pressing powder in metal die

24
 Figure 3.3: Hydraulic Press for pellets making

3.2.6. Sintering
When thermal energy is applying to powder compact, the compact is densified and the
average grain size is increases, this process is called sintering and the basic phenomena
occurring form this process is densification and grain growth. This is process used to
produced density control materials or compound from metal or ceramic powder by applying
thermal energy. Sintering aims to produce sintered part with reproducible and if possible
designed a microstructure through control the sintering variables.

Microstructural control means control of gain size, sintered density, and size and distribution
of other phases including pores. In most of the cases microstructural control prepare a full
dense body with fine grain structure. Due to the presence of dopant the sintering temperature
changed.

Sintering of the ceramic pallets were done in sintering furnace and all the pallets were placed
in the furnace at 1050℃ for four hours for the maximum densification of the ceramics.

25
 Figure 3.4. Sintering and Calcination furnace

3.3. Characterization Techniques

The structure provides a variety of concepts, which describes on various scales; its
mechanical, chemical or electrical may depends strongly on its internal structure. An
understanding of the structure of the material has become essential in the worked of novel
materials. A wide range of experimental methods are available for the evaluation of structure
of material with high accuracy and precision. The structure and morphology studies are
performed by using various techniques such as X-ray diffraction analysis (XRD) and
scanning electron microscopy (SEM). The analysis of the elemental composition present in
the sample is often aided through the use of the diffraction technique with energy dispersive
analysis (EDX). The electrical measurement can be done through LCR meter at different
temperatures.

3.3.1. XRD Analysis

X-ray diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions.
The analyzed material is finely ground, homogenized, and average bulk composition is
determined.

26
X-ray diffraction methods are especially significant for the analysis of solid materials in the
forensic science. When X-rays interact with a crystalline substance (Phase), one gets a
diffraction pattern.

XRD measure the average spacings between layers or rows of atoms, it determines the
orientation of a single crystal or grain, it is used to find the crystal structure of an unknown
material, and it measure the size, shape and internal stress of small crystalline regions. When
X-rays interact with a crystalline substance (Phase), one gets a diffraction pattern. The angle
between the beam axis and the ring is called the scattering angle and in X-ray crystallography
always denoted as 2θ. In accordance with Bragg's law when X-rays hit an atom, they make
the electronic cloud move as does any electromagnetic wave. The interference is constructive
when the phase shift is a multiple of 2π; this condition can be expressed by Bragg's law:

N = 2d sinθ
Where n is an integer determined by the order given, λ is the wavelength of the X-rays d is the
spacing between the planes in the atomic lattice, and θ is the angle between the incident ray
and the scattering planes.

Figure 3.5. Different beams of crystalline materials

An electron in an alternating electromagnetic field will oscillate with the same

frequency as the field. When an X-ray beam hits an atom, the electrons around the atom start
to oscillate with the same frequency as the incoming beam. In almost all directions we will
have interference, that is, the combining waves are out of phase and there is no resultant
energy leaving the solid sample. However, the atoms in a crystal are arranged in a regular
pattern, and in a very few directions we will have constructive interference. The waves will
be in phase and there will be well defined X-ray beams leaving the sample at various

27
directions. Hence, a diffracted beam may be described as a beam composed of a large number
of scattered rays mutually reinforcing one another.
There are many factors that determine the width of a diffraction peak. These include:
Instrumental factors

The presence of defects to the perfect lattice

Differences in strain in different grains

The size of the crystallites

3.3.2. Scanning Electron Microscope (SEM)
The scanning electron microscope (SEM) is a type of electron microscope that images
the sample surface by scanning it with a high-energy beam of electrons in a raster scan
pattern. The electrons interact with the atoms that make up the sample producing signals that
contain information about the sample's surface topography, composition and other properties
such as electrical conductivity. The types of signals produced by an SEM include secondary
electrons, back-scattered electrons (BSE), characteristic X-rays, light (cathodoluminescence),
specimen current and transmitted electrons. The SEM has a large depth of field, which allows
a large amount of the sample to be in focus at one time. The SEM also produces images of
high resolution, which means that closely spaced features can be examined at a high
magnification. Preparation of the samples is relatively easy since most SEMs only require the
sample to be conductive. The combination of higher magnification, larger depth of focus,
greater resolution, and ease of sample observation makes the SEM one of the most heavily
used instruments in research areas today.

3.3.4. LCR (for electrical properties)

An LCR meter is a type of electronic test equipment used to measure the inductance
(L), capacitance (C), and resistance (R) of an electronic component. In the simpler versions of
this instrument the impedance was measured internally and converted for display to the
corresponding capacitance or inductance value. Readings should be reasonably accurate if the
capacitor or inductor device under test does not have a significant resistive component of
impedance. More advanced designs measure true inductance or capacitance, as well as the
equivalent series resistance of capacitors and the Q factor of inductive components. A
dielectric is an electrical insulator that may be polarized by the action of an applied electric
field. When a dielectric material is placed in an electric field, electric charge does not flow
through the material, as in a conductor, but only slightly shift from their average equilibrium

28
positions causing dielectric polarization: positive charges are displaced along the field and
negative charges shift in the opposite direction.

Operation

Usually the device under test (DUT) is subjected to an AC voltage source. The meter
measures the voltage across and the current through the DUT. From the ratio of these the
meter can determine the magnitude of the impedance. The phase angle between the voltage
and current is also measured in more advanced instruments; in combination with the
impedance, the equivalent capacitance or inductance, and resistance, of the DUT can be
calculated and displayed. The meter must assume either a parallel or a series model for these
two elements. An ideal capacitor has no characteristics other than capacitance, but there are
no physical ideal capacitors. All real capacitors have a little inductance, a little resistance, and
some defects causing inefficiency. These can be seen as inductance or resistance in series
with the ideal capacitor or in parallel with it. And so likewise with inductors. Even resistors
can have inductance (especially if they are wire wound types) and capacitance as a
consequence of the way they are constructed. The most useful assumption, and the one
usually adopted, is that LR measurements have the elements in series (as is necessarily the
case in an inductor's coil) and that CR measurements have the elements in parallel (as is
necessarily the case between a capacitor's 'plates'). Leakage is a special case in capacitors, as
the leakage is necessarily across the capacitor plates, that is, in series.

An LCR meter can also be used to measure the inductance variation with respect to the rotor
position in permanent magnet machines. (However, care must be taken, as some LCR meters
will be damaged by the generated EMF produced by turning the rotor of a permanent-magnet
motor; in particular, those intended for electronic component measurements.)

Handhold LCR meters typically have selectable test frequencies of 100 Hz, 120 Hz, 1 kHz,
10 kHz, and 100 kHz for top end meters. The display resolution and measurement range
capability will typically change with the applied test frequency since the circuitry is more
sensitive or less for a given component (ie, an inductor or capacitor) as the test frequency
changes.

Benchtop LCR meters sometimes have selectable test frequencies of more than 100 kHz.
They often include options to superimpose a DC voltage or current on the AC measuring
signal. Lower end meters might offer the possibility to externally supply these DC voltages or

29
currents while higher end devices can supply them internally. In addition, benchtop meters
typically allow the usage of special fixtures (i-e, Kelvin wiring, that is to say, 4-wire
connections) to measure SMD components, air-core coils or transformers.

Figure 3.7: LCR meter

LCR was done on each sample coated with silver paint at the frequency form 100 Hz to
1MHz. the properties obtained from the LCR are capacitance, resistance and the inductance
of the samples.

3.4 Methodology:

Weighing powders (PbC03 +

ZrO2 + TiO2) Ball Milling

Drying Calcination

Pressing Into pellets Sintering

Figure 3.8: Methodology applied for experimental work

30
Chapter 4
Results and Discussions

4.1. XRD
XRD pattern has confirmed the perovskite structure

Figure 4.1: X-ray diffraction of patterns of BCZT (Ba0.85Ca0.15Zr0.1 (TiO3)0.9) BFO (BiFeO3)
doped with 0%, 2%, 4%, 6%, 8% and 10% CuO.

31
4.2. SEM

a b

c
d

\
e f

32
 Figure 4.2: SEM images showing increase in particle size with CuO addition as represented
by a) pure BCZT b) 2% CuO doped BCZT c) 4% CuO doped BCZT d) 6% CuO doped
BCZT e) 8% CuO doped BCZT f) 10% CuO doped BCZT

4.3. Complex Impedance Spectroscopy

(a) (b)

(C)

Figure 4.3:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 2% CuO

33
( a) (b)

(c)

Figure 4.4:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 4% CuO

34
( a) (b)

(c)

Figure 4.5:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 6% CuO

35
( a) (b)

( C)

Figure 4.6:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 8% CuO

36
( a) (b)

( C)

Figure 4.7:(a) Graph between F and Z’, (b) Graph between F and -Z”, (c) Graph between Z’
and -Z” of BCZT-BFO doped with 10% CuO

4.4 Conductivity

37
 (b)
(a)

(c)
(d)

(e)

Figure 4.8: Graph between frequency and conductivity of CuO doped with BCZT-BFO, (a)
2% CuO; (b) 4% CuO; (c) 6%CuO; (d) 8% CuO; (e) 10% CuO

Figure 4.2 (a);(b) ;(c) ;(d) ;(e) ;(f); shows the SEM images of CuO doped BCZT-BFO
sintered at 1075℃ for 4 hours, increasing the amount of copper oxide grain size of BCZT-

38
BFO increases and the density of the grains increases as shown that in fig 4.2 (a) the density
is less where no copper oxide so in fig 4.2 (b) the grains size increase and the overall density.
Moving towards greater amount of dopant as in fig 4.2 (c);(d) ;(e) ;(f) the empty spaces in the
figure become filled this shows that the copper oxide will diffused into BCZT-BFO and the
grain size increases further with increased grain density.

Figures 4.3, 4.4, 4.5, 4.6, 4.7 shows complex impedance spectrum (Nyquist plot, a plot
between the real (Z’) and imaginary (Z’’) of complex impedance Z*) of BCZT-BFO ceramic
sintered at 1075 ℃. The impedance data from room temperature up to about 500℃ showed in
the above figures. The impedance data from room temperature up to about 225℃ is not
illustrated in the figure.

In general, existence of a single semi-circular arc represents the grain interior (bulk) property
of the material. However, in the present case, at temperature of 250℃ or higher, the spectrum
comprises of two semi-circular arcs. The two semi-circular arcs in the Nyquist plot are due to
contributions from the grain interior (bulk) and grain boundary. The arc at high frequency is
ascribed to the grain (bulk) and the one at low frequency to the grain boundary contribution.

Figures 4.3, 4.4, 4.5, 4.6, 4.7 shows typical impedance plot, at temperatures between 225℃
and 500℃ for BCZT-BFO ceramics consisting of two semi-circular arcs along with the
fitting results of impedance data by Z-view software (Ver. 3.2c Scribner Associates, Inc).
Fitting was done by using an equivalent electric circuit consisting of two resistances in series
and capacitive phase element (CPE) in parallel. CPE fitting data was done to remove the non-
linear regularities and the data was make more suitable for the dielectric properties and other
analyzations. Fitting the data showed good and clear results for experimental purpose. The
curves merge at specific frequency for a specific composition of CuO doping.

The variation in real part of impedance (Z’) with frequency at various temperatures is shown
in the figures 4.2-4.7. The magnitude of Zʹ was found to decrease with increase in
temperature which indicated the increase in ac conduction (σac) in the sample. This increase
in ac conduction with temperature might have appeared due to the contribution of defects like
oxygen vacancies in the sample. At elevated temperature, the contribution due to oxygen
vacancies is more dominant in perovskite structures. Higher value of Zʹ at lower frequency
and temperature plus merging of Zʹ at higher frequency for all temperatures, clearly indicates
the presence of space charge polarization [36,37]. At higher temperature, the impedance
seems to be independent of frequency and temperature.

39
Figure 4.8; shows the AC electrical conductivity (σac) as a function of frequency at different
temperatures from 300℃ to 380℃. The plots showed a dispersive nature at lower frequency
regime which became narrowed at higher frequencies. As it could be observed, the slope
change in lower temperature region is more prominent. This may be the indication of
maximum ionic motion taken place, which involves localized hopping with either rotation or
translation of the mobile species.

Conclusion
Successfully synthesized dense CuO doped BCZT-BFO, XRD analysis confirmed the proper
doping of the CuO and the maximum density samples are made by sintering at 1075 ℃. This
temperature is not fixed densification can be obtained more by different sintering
temperatures. Doping radios may be varied for more densification this can be done in further
work. The dopant may be used in other amounts also greater than 10 %. The ratios of BFO
may also be varied for different properties.

Reference:
[1]. B. Jaffe, W.R. Cook, H.L. Jaffe, Piezoelectric Ceramics, Academic Press, London, 1971.

40
[2]. U. Kenji, Piezoelectric Actuators and Ultrasonic Motors, Kluwer Academic Publishers,
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[3]. U. Kenji, Ferroelectric Devices, Marcel Dekker, New York, 2000.

[4]. Z.-G. Ye, Handbook of advanced dielectric, piezoelectric and ferroelectric materials:
Synthesis, properties and applications, CRC Press, Boca Raton, 2008.

[5]. http://en.wikipedia.org/wiki/Piezoelectricity

[6]. S. Park and T. R. Shrout, "Ultrahigh strain and piezoelectric behavior in relaxor based
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[7]. J.N. Gordon, A. Taylor, P.N. Bennett, Br. J. Clin. Pharmacol. 53 (2002) 451- 458.

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[9]. A.A. Vives, Piezoelectric transducers and applications, 2nd ed. ed., Springer, Berlin,
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[10]. A. Safari, E.K. Akdogan., Piezoelectric and acoustic materials for transducer
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