Thesis Sodium Potassium Niobate Based Piezoelectric Ceramics

SODIUM POTASSIUM NIOBATE
BASED PIEZOELECTRIC CERAMICS
A thesis submitted to
The University of Manchester
for the degree of
Doctor of Philosophy
in the Faculty of Engineering and Physical Sciences
Year of Submission: 2012
Margaret Wgrzyn
School of Materials
CONTENTS
Contents .............................................................................................................................................................................. 2
Abbreviations .................................................................................................................................................................. 5
Abstract............................................................................................................................................................................... 6
Declaration ........................................................................................................................................................................ 7
Copyright Statement .................................................................................................................................................... 7
Acknowledgements ...................................................................................................................................................... 8
1 Introduction ........................................................................................................................................................... 9
1.1 General Introduction ............................................................................................................................... 9
1.2 Aims and Objectives of this Investigation.................................................................................. 11
2 Literature Review............................................................................................................................................. 12
2.1 Electroceramic Properties ................................................................................................................. 12
2.1.1 Dielectric Properties ................................................................................................................... 12
2.1.2 Piezoelectric Properties............................................................................................................ 16
2.1.3 Ferroelectric Properties ........................................................................................................... 19
2.1.4 Impedance Spectroscopy ......................................................................................................... 24
2.2 Piezoelectric Materials and their Properties ........................................................................... 26
2.2.1 Lead Zirconium Titanate (PZT) ............................................................................................ 27
2.2.2 Barium Titanate (BT) ................................................................................................................. 28
2.2.3 Potassium Niobate, KNbO3 [KN] ........................................................................................... 31
2.2.4 NaNbO3 [NN] ................................................................................................................................... 32
2.2.5 Lithium Niobate, LiNbO3 [LN] and Lithium Tantalate [LT] .................................... 34
2.2.6 Strontium Barium Niobate (SBN) ........................................................................................ 34
2.3 Sodium Potassium Niobate (NKN) ................................................................................................ 35
2.3.1 Recent Pure NKN investigations .......................................................................................... 35
2.3.2 NKN Doping for Enhanced Properties............................................................................... 39
2.4 Texturing .................................................................................................................................................... 48
2.4.1 Introduction to Texturing ........................................................................................................ 48
2.4.2 Texturing of Polycrystalline Ceramics .............................................................................. 50
2.4.3 Texturing of NKN.......................................................................................................................... 54
2.4.4 Summary of Texturing Piezoelectric Ceramics............................................................. 58
3 Experimental Procedures............................................................................................................................. 60
3.1 Raw Powders ............................................................................................................................................ 60
3.2 Sample Preparation ............................................................................................................................... 60
3.2.1 Mixed Oxide Processing Route .............................................................................................. 60
3.2.2 Orientation Casting ..................................................................................................................... 62
3.3 Characterisation Techniques ........................................................................................................... 68
3.3.1 Density Measurement ................................................................................................................ 68
3.3.2 X-Ray Diffraction (XRD) Procedures .................................................................................. 69
3.3.3 Synchrotron Energy Dispersive Powder Diffraction ................................................. 71
Margaret Wgrzyn Sodium Potassium Niobate Based Piezoelectric Ceramics Page 2

3.3.4 Rietveld Refinement ................................................................................................................... 75
3.3.5 Scanning Electron Microscopy (SEM) and EDAX......................................................... 77
3.3.6 Electrical Property Measurements ..................................................................................... 78
4 The Effect of Temperature on NKN-based Formulations ............................................................ 81
4.1 Introduction .............................................................................................................................................. 81
4.1.1 Background and Objectives .................................................................................................... 81
4.1.2 Methodology ................................................................................................................................... 81
4.1.3 Materials Selection ...................................................................................................................... 82
4.2 Niobium and Copper Doped NKN .................................................................................................. 82
4.2.1 Diffraction data for the sintered pellet ............................................................................. 82
4.2.2 Powder diffraction analysis for Copper and Niobium Doped NKN .................... 88
4.2.3 Electrical Properties of Copper and Niobium Doped NKN ..................................... 95
4.3 Synchrotron XRD Study of Lithium Tantalate Doped NKN............................................... 95
4.4 Summary .................................................................................................................................................. 102
4.4.1 Copper and Niobium Doped NKN (Sintered Pellet) ................................................ 102
4.4.2 The Copper and Niobium Doped NKN (Crushed Powder) .................................. 103
4.4.3 Lithium and Tantalum Doped NKN (Crushed Powder) ........................................ 103
5 Doping NKN with Piezoelectric SBN .................................................................................................... 104
5.1 Introduction ........................................................................................................................................... 104
5.2 Characterisation of Starting Powders....................................................................................... 104
5.2.1 Sodium Carbonate .................................................................................................................... 104
5.2.2 Potassium Carbonate .............................................................................................................. 105
5.2.3 Niobium Oxide ............................................................................................................................ 106
5.2.4 Strontium Carbonate ............................................................................................................... 106
5.2.5 Barium Carbonate ..................................................................................................................... 107
5.2.6 Iron Oxide...................................................................................................................................... 107
5.3 Densification of Ceramics in the NKN-SBN System ........................................................... 108
5.4 X-ray Diffraction Analysis ............................................................................................................... 111
5.4.1 Undoped xSBN ............................................................................................................................ 111
5.4.2 xSBNF Samples ........................................................................................................................... 112
5.5 SEM Investigation ............................................................................................................................... 113
5.6 Electrical Properties .......................................................................................................................... 115
5.6.1 Dielectric Properties ................................................................................................................ 115
5.6.2 Field Response Hysteresis Loops ..................................................................................... 118
5.6.3 Impedance Spectroscopy ...................................................................................................... 123
5.7 Chapter Summary ............................................................................................................................... 129
6 Synchrotron Analysis of xSBNF Formulations ............................................................................... 131
6.1 Introduction ........................................................................................................................................... 131
6.2 Synchrotron Data Analysis ............................................................................................................. 132
6.2.1 NKNF Refinement ..................................................................................................................... 133

6.2.2 0.5 and 1SBNF Refinement .................................................................................................. 134
6.2.3 2-3 SBNF Refinements ............................................................................................................ 134
6.2.4 4 SBNF Refinement .................................................................................................................. 135
6.3 Summary of Data from Refinements ......................................................................................... 136
6.3.1 Phase Content ............................................................................................................................. 136
6.3.2 Lattice Parameters ................................................................................................................... 137
6.4 Chapter Summary and Conclusions ........................................................................................... 140
7 Development of a Route to Produce Oriented NKN Thick Films .......................................... 141
7.1 Introduction ........................................................................................................................................... 141
7.2 The Production of BNN Particles................................................................................................. 142
7.2.1 Crucible Selection...................................................................................................................... 142
7.2.2 Preparation of BNN particles .............................................................................................. 143
7.2.3 The Effect of Salt to Oxide Ratio ........................................................................................ 145
7.3 The Production of NN Particles .................................................................................................... 146
7.4 Development of Tape Casting Procedure ............................................................................... 148
7.4.1 Tape Casting Method Development................................................................................. 148
7.4.2 Slurry Development ................................................................................................................. 150
7.4.3 Cast Tape Quality Control ..................................................................................................... 151
7.5 Doping NKN with LiNbO3 (LN) ..................................................................................................... 152
7.6 Tape Casting of Copper-Doped 5LN and 6LN Compositions ........................................ 153
7.7 Film Thickness ...................................................................................................................................... 155
7.8 Tape Casting Oriented 94NKN-6LN Tapes using NN particles .................................... 157
7.8.1 Preparation of Tapes with Addition of 10% NN Particles ................................... 157
7.8.2 Adding 15% NN Particles...................................................................................................... 166
7.9 Summary and Chapter Conclusions ........................................................................................... 169
8 Conclusions ....................................................................................................................................................... 170
8.1 SBN doping of NKN ............................................................................................................................. 170
8.2 Synchrotron Analysis of NKN-based Formulations ........................................................... 171
8.2.1 Synchrotron Analysis for Cu and Nb doped NKN ..................................................... 171
8.2.2 Synchrotron Analysis of 94NKN-6LT.............................................................................. 172
8.3 Tape Casting of LN-doped NKN.................................................................................................... 172
8.3.1 Tape Casting Procedure Development........................................................................... 172
8.3.2 Orientation using NN Template Particles ..................................................................... 172
8.3.3 CuO doped NKN-LN Tape Casting Development ...................................................... 173
9 Recommendations for Further Study ................................................................................................. 174
9.1 NKN-SBN System ................................................................................................................................. 174
9.2 NKN-LN System .................................................................................................................................... 175
References ................................................................................................................................................................... 176
Appendix 1 - Figures .............................................................................................................................................. 191
Appendix 2 - Tables ................................................................................................................................................ 200

ABBREVIATIONS
BiT Bismuth Titanate, Bi4Ti3O12
BKNT Bismuth Sodium Potassium Niobate (Bi, K, Na)TiO3
BKT Bismuth Potassium Titanate, Bi0.5K0.5TiO3
BLSF Bismuth Layered-Structured Ferroelectric
BNN Bismuth Sodium Niobate, Bi2.5Na3.5Nb5O18
BNT Bismuth Sodium Titanate, Bi0.5Na0.5TiO3
BT Barium Titanate, BaTiO3
CAS Chemical Abstracts Service
d33 piezoelectric constant
EC coercive field
EC Enzyme Commission
EDAX Energy Dispersive X-ray Spectroscopy
ELV End of Life Vehicles
EU European Union
FCC Face Centred Cubic
GOF Goodness of Fit
HATSAXS High Automated Throughput Small Angle X-ray Scattering
ICDD International Centre for Diffraction Data
ICSD Inorganic Crystal Structure Database
KN Potassium Niobate, KNbO3
kp planar electromechanical coupling coefficient
kt thickness coupling coefficient
LBT Lithium Bismuth Titantate, Li0.5Bi0.5TiO3
LN Lithium Niobate, LiNbO3
LT Lithium Titanate, LiTaO3
MPB Morphotropic Phase Boundary
MRI Materials Research Instruments
MSS Molten Salt Synthesis
NKN Sodium Potassium Niobate, (Na0.5K0.5)NbO3
NKNF NKN + 0.45 wt% Fe2O3
NN Sodium Niobate, NaNbO3
OPS Oxide Polishing Suspension
ortho orthorhombic
Pr remnant polarisation
Psat saturated polarisation
PVB Polyvinyl Butyral
PZT Lead Zirconium Titanate, (Pb, Zr) TiO3
RoHS Restriction of Hazardous Substances
RTGG Reactive Templated Grain Growth
SBN Strontium Barium Niobate, (Sr0.5Ba0.5)Nb2O6
SBNF SBN + 0.45 wt% Fe2O3
SEM Scanning Electron Microscopy
SiC Silicon Carbide
SRS Synchrotron Radiation Source
ST Strontium Titanate, SrTiO3
TBT Tungsten Bronze Type
TC Curie temperature
TEM Transmission Electron Microscopy
tet tetragonal
TO-T orthorhombic to tetragonal transition temperature
WEEE Waste from Electrical and Electronic Equipment
XRD X-Ray Diffraction

ABSTRACT
NKN doped samples, (100-x)NKN-xSBN (0 x 10) were produced using the
conventional mixed oxide route with 0.45 wt% Fe2O3 sintering aid (xSBNF). After
20-24 hours mixing, samples were calcined at 850C and sintered at 11001140C
( 180C/hour) for 4 hours. By XRD 4 mol% SBN was found to be the solubility
limit for single phase structure. By SEM, second phases were visible when 2 x
4; their structure was subsequently shown to be tungsten bronze type (TBT).
2-4 SBNF samples were high density, over 96% theoretical. For x = 0, TC =
457C, TO-T = 234C, Pr = 22 C/cm2 and EC = 16.5 kV/cm. TC was found to
decrease by 14.7C and TO-T by 9.0C per 1 mol% addition SBN. 2SBNF was the
optimal formulation in terms of microstructure and electrical properties, with
average grain size 3 m, Pr = 25 C/cm2 and EC = 8.8 kV/cm, = 4.7 km and Q =
1.16 eV. This material comprised approximately 90% orthorhombic and 10%
tetragonal phases coexisting. Pseudo-cubic lattice parameters are a = c =
3.947180 , and b = 3.999996 for orthorhombic phase; the tetragonal has a = c
= 3.989798 , and b = 3.975777 .
Synchrotron XRD studies were undertaken as a function of temperature on

99.5NKN-0.5CuO + 0.6 wt% Nb2O5 solid and powder samples. The data were
Rietveld refined. The solid sample underwent two polymorphic phase transitions
at 300C and 515C; the latter was between two tetragonal phases: lattice
parameters for the tetragonal phase (300-520C) were a = c = 4.99557 , and b =
4.0363 ; high temperature tetragonal (>500C) exhibited a = c = 4.9519 , and b
= 4.4941
The powder sample of the same formulation exhibited more, smaller
transformations. It was only orthorhombic at temperatures <140C with a = c =
4.10680 , and b = 4.02620 . Above 140C both orthorhombic and tetragonal
phases were present. Another significant transformation occurred at 360C where
the structural unit cell parameters changed significantly. Parameter lengths are
provided. P-E data was characterised by Pr = 19.9 C/cm2 and EC = 13.5 kV/cm.
Synchrotron X-ray diffraction analysis of 94 NKN-6LiTaO3 showed that tetragonal

phase was present at 20-390C, although an orthorhombic phase was identified at
20-200C and again at 340-390C just before the cubic transition temperature at
390C. This is a new observation for NKN.
A new and simple method for tape casting was developed to reduce powder
wastage, enabling thick films of 50 m to be cast. The reactive templated grain
growth (RTGG) method was employed to orient 95NKN-5LiNbO3 and 94NKN-
6LiNbO3 samples; CuO was utilised as a sintering aid. Pre-cursor BNN and NN
template particles were produced using the molten salt synthesis (MSS) method,
using a salt to oxide ratio of 1:1. Resulting NN particles were 15 m wide and 0.5
m thick. Eight layered 6LN + 0.4 wt% tapes produced using 10 wt% template
particles resulted in 210 m thick tapes with 67% orientation when sintered at
1150C. Resulting properties include TC = 440C and TO-T = 70C, 25 k resistance
and capacitance 21.6 pF.
Margaret Wgrzyn for Doctor of Philosophy at The University of Manchester

Sodium Potassium Niobate Based Piezoelectric Ceramics
March 2012

DECLARATION
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ACKNOWLEDGEMENTS
I would like to first and foremost like to thank my supervisor Professor Robert Freer
without whom this PhD thesis would not exist. Without his guidance, support and faith I
would not have reached the end of this educational journey. I am truly grateful for his
patience and help with my scientific writing. Alongside him, I must also thank Dr.
Feridoon Azough for his support throughout my four years during my PhD, particularly
with practical work, who can find positive outcomes from any situation.
I would also like to thank the Engineering and Physical Sciences Research Council
and the School of Materials for giving me the funds and facilities to undertake the PhD.
I am indebted to the Functional Ceramics research group for their support and
camaraderie, in particular Dr. Michael Thrall and Colin Norman, whose knowledge and
assistance I could not have done without. Also to Professor R.J. Cernik, whose continuing
support, guidance, exceptional knowledge and witty humour always helped; and to Dr D.A.
Hall for his assistance and direction which aided the success of this research project.
I would like to convey thanks to all those who helped with practical work by training me
on specialist equipment and aiding me in times of complex situations. In particular I have
deepest gratitude to Mike Faulkner whose expertise on SEM machinery makes it look so
simple, who made complex imaging manageable and most importantly had a great sense
of humour that I will never forget. Also to Judith Shackleton and Gary Harrison for their
extensive knowledge of XRD, in aiding my many experimental requirements and the
friendly manner they maintained throughout.
An honourable mention to the administrative staff who were always willing to help, in
particular, Sue Brandreth, Olwen Richert and Sandra Kershaw. Also to the Outreach and
Widening Participation staff who aided me to impart my love of science and engineering to
the public, and helped fund the PhD once the EPSRC funding finished, in particular Emma
Lewis and Karen Donnelly. Huge thanks to the two women in Materials Science Centre
that I could not have succeeded without: Philippa Pip Lee and Dr. Rachel Saunders.
Many thanks to my friends and colleagues in the Materials Science Centre and in the
Widening Participation team, too many to list, but each in their own way an important part
of my postgraduate life in Manchester. Also to all the Polish dancers around the world
who helped keep me going, in particular Orlta and Basia Klimas-Sawyer, who allowed
me to continue to dance with the group even though I was living in a distant city, and
Polonez Manchester who allowed me to participate in their events, performances and
with whom I have made lasting friendships. Most importantly thanks to my friends in
Team GB who were a constant support and provided valuable friendship, in particularly
Tom Pawluczyk.
Finally, my deepest gratitude goes to my parents Robert and Jola Wgrzyn, and my brother
Daniel Vinci, whose undying encouragement, counselling and love made it possible for me
to make it to the end of this experience. From the bottom of my heart I am thankful for
every little thing they have done for me.

1 INTRODUCTION
1.1 General Introduction

Piezoelectric materials are widely used in electronics due to their electronic versatility.
They are mainly utilised as strain gauges, sonar devices, microphones, phonograph
pickups, accelerometer, fuel jet valves, control of oscillator frequencies in communication
equipment, sonic delay lines, and transducers in ultrasonic devices.[1-4] There were
3,500,000,000 piezoelectric devices produced in 2006.[5] In 2008, it was reported that
there were 1012 ferroelectric capacitors produced, and sophisticated piezoelectric systems
were a growing market of 6 billion annually.[6]
The most popular material used for piezoelectric materials around the world is that of PZT
(lead zirconium titanate). However, PZT components contain over 60% lead,[7] which
has, particularly its oxide compound PbO, been found to be toxic and can cause problems
with health and learning abilities, and can even cause death.[8] Most significantly is that
the EU has produced legislation whereby the manufacture of any new electronic
equipment produced after July 1st 2006 do not contain any components of lead (along
with other hazardous substances such as mercury and cadmium).[9] There have also been
directives from the EU for environmental protection against the waste of wasted electrical
components, such as the Restriction of Hazardous Substances (RoHS), Waste from
Electrical and Electronic Equipment (WEEE)[10-11] and End of Live Vehicles (ELV),
legislation introduced to the UK in 2003.[12-13] Due to these health claims and EU
directives, the amount of research in lead-free piezoelectric ceramics has grown
exponentially since 1997, as shown by Figure 1.1.
Figure 1.1. Number of publications cited in refereed journals based on lead-free

piezoceramics (between 1050 and November 2008) (from Rdel et al).[3]

The subject of lead-free piezoelectrics is one of high interest, and was even reported on by
L.E. Cross in Nature.[14] In this report he mentioned the high usage of PZT, and how Saito
et al. had successfully produced a lead-free NKN-based material with properties similar to
PZT (and a d33 piezoelectric coefficient value that was higher) in the same publication.[15]
Additionally, this research group, based at Toyota (Japan) oriented the NKN-based
material which resulted in properties comparable to doped and optimised PZT (this is
further discussed later).[15-16] These publications have caused much interest in NKN-
based piezoelectric ceramics and so is a relevant and currently topical material under
investigation. The characteristic properties of lead-free properties compared to those of
PZT are shown in Figure 1.2. The European LEAF project program (2001 - 2004), involved
the investigation of piezoelectric alternatives for PZT, mainly focussing on Sodium
Potassium Niobate, Na0.5K0.5NbO3 hereafter named NKN, and its dopants.[17]
Figure 1.2. Piezoelectric coefficient Curie temperature comparison of PZT materials to

BaTiO3 (BT), BNT and NKN based materials in the literature (from Shrout and Zhang).[18]
Other lead-free piezoelectric material systems include BNT (Bi0.5Na0.5TiO3) and BKT
(Bi0.5K0.5TiO3). These were also investigated in the LEAF program.[17] BNT is a
ferroelectric perovskite with rhombohedral structure at room temperature with a high
Curie temperature of 320C and large remnant polarisation of 38 C/cm 2.[19-22] It is,
however, known for its poor resistivity, high coercive field (EC = 73 kV/cm) and difficulty
to pole (saturation is difficult to achieve).[3, 19] Highly dense samples need a
conventional sintering temperature of over 1200 C or superior processing methods such
as hot pressing.[3]
BKT has a slightly higher Curie temperature of 380C with tetragonal structure at
room temperature,[22] though like BNT, it is difficult to sinter without using hot pressing
methods.[23] By combining the two systems (BKNT) superior properties have been

found,[24-25] When BKNT has been combined into a tertiary system with BaTiO 3 (BT)
enhanced properties have also been found, and this is a material under high interest
also.[26-28]
NKN is a highly researched material as a lead-free piezoelectric ceramic. It is a mixture

between ferroelectric KNbO3 and antiferroelectric NaNbO3 where there is a morphotropic
phase boundary (MPB) for the (Na0.52K0.48)NbO3 formulation;[29-30] most research,
however, is conducted at an equal ratio of sodium to potassium. Like BNT, NKN is known
for its sintering difficulties, and suffers from deliquescence (degradation in contact with
moisture). Typical properties of NKN include Pr and EC of 15 C/cm2 and 13 kV/cm.[31]
Doping NKN significantly improves the density, microstructure and piezoelectric
properties. Many variations have been reported, however the most significant and
effective finding has been the addition of lithium to the system. By substituting lithium
into the A site of the perovskite structure, the properties are significantly enhanced.
Typical lithium doped NKN properties include Pr and EC of 22-23 C/cm2.[32-34]
1.2 Aims and Objectives of this Investigation

This investigation is aimed at reporting novel and innovative research that has been
undertaken in order to further the field of research in NKN-based materials. A major
objective for this investigation is to examine how NKN behaves under doping. In this
investigation, perovskite NKN is doped with copper, lithium and tantalum additions, as
well as with strontium barium niobate (Sr0.5Ba0.5)Nb2O6 (a piezoelectric material with
tungsten bronze structure) which has not been previously attempted in the literature.
High resolution X-ray diffraction methods have been utilised in order to obtain structural
information for the doping effects. This involves utilising this technique in-situ with
doped NKN as a function of temperature.
Another objective of this investigation is to develop NKN-based thick films in order to

investigate the effect of orientation to the formulations. Template particles are produced
in order to orient the thick films as an RTGG (reactive templated grain growth) process. A
method of thick film processing is developed in order to utilise small amounts of powder,
to produce tapes 25-200 m thick. The sintering conditions are investigated in order to
find the optimal processing conditions for the optimal formulation of NKN-based oriented
thick films.

2 LITERATURE REVIEW
This chapter is devoted to the processing and properties of piezoelectric materials being
investigated in this study. Based upon information in literature, this review is intended to
show a foundation for the novel, original research carried out in this study.
2.1 Electroceramic Properties

Throughout the twentieth century, the use of ceramics in electronics has evolved. In the
early 1900s, the use of ceramics was for the properties of high resistivity and chemical
stability. However throughout the last century, the widespread properties of
electroceramics have been exploited for a wide range of applications.[35] Many different
properties of electroceramics can be observed and manipulated for various applications.
2.1.1 Dielectric Properties

Dielectric materials are good electrical insulators, meaning that they have high electrical
resistivities, however they are affected by an applied electric field, E. An applied field
causes the positive and negative charges in the material to slightly rearrange or displace
and form electric dipoles, each having a moment, p. The dipole moment per unit volume is
the polarisation, P.[36] There are four types of polarisation mechanism, and which are
present depend upon the material. These mechanisms are illustrated in Figure 2.1.
1. In all dielectric materials, atomic, or electronic, polarisation can occur where the
negatively charged electrons in an atom will displace slightly to align themselves with
the positive electrode of the applied field. The positively charged nucleus shifts
slightly towards the negative electrode. The electrons and nuclei return to their
original positions once the field is removed. The overall polarisation effect is relatively
small compared to the other types; however it occurs in all dielectric materials. It is
not affected by the temperature of the material.
2. Where the material has an ionic lattice, the anions and cations will adjust themselves
so as to align with the field. There are many different combinations of polarisation
effect, depending upon factors such as the crystal structure. This creates a higher
amount of charge carriers and ion mobility, thus is a prevalent mechanism and is
affected significantly by the temperature of the material. It is this polarisation
mechanism that creates ferroelectric and piezoelectric effects.
3. In dipolar materials, such as polymers, the applied field will orientate the molecules to
align with the field. This is also known as orientation polarisation, and its net effect
is larger than atomic polarisation because molecular dipoles are larger than atomic

dipoles. This effect causes the dielectric constant to be inversely proportional to the
applied temperature.
4. Space charge polarisation is slightly different, in that electrons will travel across the
grain until they hit a defect such as a grain boundary. As the defect presents a
potential barrier, space charge is created across the grain. These charges can occur
due to the manufacturing process (charges become trapped) though only occur in low
frequencies (up to 1000 Hz).[2, 35-36]
Figure 2.1. Schematic diagram showing different polarisation mechanisms in a material

(from Moulson and Herbert).[35]
Polarisation or charge storage, allows for the miniaturisation of technology in the modern
world. A higher degree of polarisability of a material allows miniaturisation. An example
is capacitors. When an electric field, E, is applied across two parallel capacitor plates of
area A and distance h from each other (as illustrated in Figure 2.2a), one plate becomes
positive and the other negative. This means that a surface charge density, p, is stored on
each plate. The permittivity of a vacuum is a constant of 0 = 8.854 X 10-12 F/m[37] and so
the total capacitance, C0, of the plates in vacuum is given by Equation 2:1.[38]

Equation 2:1
When a dielectric material is placed in between the parallel plates, the applied field causes
the material to become polarised. This is illustrated in Figure 2.2b. The susceptibility of
the material, e, results in the capacitance of the plates to increase by a factor of (1+ e)
and thus the permittivity, , of the material is defined by Equation 2:2. This creates the
concept of the relative permittivity of the material, r, otherwise known as the dielectric
constant, which is an intrinsic property. This is defined in Equation 2:3.
The amount of charge that can be stored in a capacitor, Q, is dependent upon the voltage
applied and the capacitance, C. This relationship is shown in Equation 2:4. The
capacitance itself is dependent upon the permittivity, r, the area of the parallel plates, A,
and the thickness of the dielectric material, t. The capacitance is defined by Equation 2:5.
Equation 2:2
Equation 2:3
Equation 2:4
Equation 2:5
Figure 2.2. Schematic diagrams showing how charge can store on capacitor plates in vacuum
(a) and how a dielectric material (grey) in between them can play a role (b) (from Moulson
and Herbert).[35]
The relative permittivity, r, is a dimensionless property found in materials and is defined

as the ratio between the permittivity of the material and the permittivity of free space.
There are two components that make up the relative permittivity of a material real, ,

and imaginary, , parts. Their relation to the dielectric constant is given as Equation 2:6.
is the permittivity, already explained. In electronic physics, the out of phase voltage of
an ac electric field is always 90 out of phase behind the in-phase current. In reality, this
difference is not exactly 90 as the current lags behind slightly in dielectric materials. If
the angle of lag is defined as , then the amount of lag is defined as tan , otherwise known
as the loss tangent.[2] This is defined by Equation 2:7. It is the amount of capacitive
current that is lost, or dissipated, as heat.[35] Jaffe also explains this as loss from resistive
leakage or dielectric absorption.[39]
Equation 2:6
Equation 2:7
The permittivity, or dielectric constant, is affected by heat and applied frequency; these
alter the dipoles within the material and also increase the mobility of charge carriers.[2,
35, 40] The four polarisation mechanisms that were previously described are shown in
Figure 2.3 as a function of frequency.
Figure 2.3. Polarisability of dielectric constant (r) and loss (r) as a function of frequency
(after Moulson and Herbert).[35]

2.1.2 Piezoelectric Properties
Piezoelectricity was discovered by Jacques and Pierre Curie in 1880.[41] It translates as
pressure electricity.[2] Piezoelectric ceramics are ferroelectric by definition. They must
have a Curie temperature, TC, below which the structure of the material cannot be
symmetrical from the centre, due to the formation of dipoles within the material (as
explained in Section 2.1.3). Of the 32 crystal classes that characterise the symmetry of a
unit cell, 21 do not have a centre of symmetry. Those which are centrosymmetric are
unable to polarise, as the symmetry of the atoms compensate for any small changes in the
ions under an applied field. Of the 21 non-centric classes, twenty exhibit the piezoelectric
effect. The one that does not exhibit this effect is the cubic class 432, which have elements
of symmetry, though not through the centre.[42]
The piezoelectric phenomenon has two interchangeable stimuli, depending upon the
application of the ceramic. Under an applied stress, forcing compression of the material, it
undergoes a strain whereby it induces electric polarisation. The relationship between the
two is proportional, and so conversely, under an applied electric field, it will also exhibit
induced strain. This strain causes a slight shrinkage of the piezoelectric. This only occurs
when the material is below TC, when the unit cell structure is non-centrosymmetric (ie not
cubic).
Figure 2.4. Structure of PZT cubic perovskite (left) and how it is affected in its tetragonal
form to create a dipole under applied electric field (right) (from Callister).[43]
Figure 2.4 shows schematically how an electric field can influence the material to shrink
and expand by creating dipoles in the unit cell structure. As explained, the application of
an electric field, or a mechanical stress, induces a dipole to be created in the unit cell,
which in turn creates a mechanical stress or electric field respectively. This causes a shape
change in the material, where usually it is known for piezoelectric ceramics to shrink.
How much the material shrinks by is known as the piezoelectric coefficient of the material,
and each is unique to a particular composition as an intrinsic property.

The direct piezoelectric effect is when an electric charge, Q, is produced from a material
with the application of a stress, T. This allows the dielectric displacement, D, to be defined
in Equation 2:8, where d is a constant. When an applied field, E, is subjected to a
piezoelectric material, it generates a strain, S, which is defined as Equation 2:9. Again,
there is a constant showing the proportionality of the two parameters, also d. d is the
same for both instances, and so is known as the piezoelectric constant, which is defined in
Equation 2:10. Due to two differences in measurement parameters, d has two units of
measurement that of Coulombs per Newton (C/N a small number, so usually shown in
pC/N) for the direct piezoelectric effect, and meters per Volt (m/V) for the converse
effect.[39]
Equation 2:8
Equation 2:9
Equation 2:10
Piezoelectric materials need to undergo a poling process in order to allow the materials to
exhibit their piezoelectric characteristics, allowing the direction of polarisation to change
within the material. This is done by subjecting the material to a static electric field with
varying temperature with respect to time.
The amount of polarisation with respect to a polar axis depends upon the structure
of the material. Although a single crystal can completely polarise, polycrystalline ceramics
cannot due to the pinning of domains by grain boundaries and defects. Tetragonal
structures can reach up to 83% polarisation, whereas orthorhombic structures can
polarise significantly better to 91% due to the difference in the packing of atoms in the
structure.[35] However in tetragonal Barium Titanate, the polarisation can only reach
approximately 50% of a single crystal due to the internal strains preventing 90 domain
switching.[35]
There are many different piezoelectric constants that can be measured in a ceramic
material. They are generically denoted as dij, where i denotes the electric field or
displacement, and j denotes the direction of the mechanical stress or strain. For example,
the transverse piezoelectric coefficient is denoted as d31.[44] This relates to the field
along the polar axis and the strain perpendicular to it. However the most common
piezoelectric coefficient used in publications and comparisons is that of d33, where the
strain and the applied field are measured along the polar axis.[35] It can be defined by

Equation 2:11, where Q is charge applied, C is capacitance, V is voltage applied and F is
force applied.[45]
Equation 2:11
Figure 2.5. Schematic of k parameter (after van Randeraat and Setterington).[41]
Another piezoelectric parameter that must be discussed is the electromechanical coupling

coefficient, k. k2 measures the conversion ratio of electrical and mechanical energies,
depending upon whether the converse or direct piezoelectric methods are applied for
measurement. Like the relative permittivity, it is also a dimensionless parameter, as it is a
proportion being calculated. It is defined by Equation 2:12 (for direct piezoelectric
effect) and Equation 2:13 (for converse piezoelectric effect).[4, 39] It must be noted that
k2, and thus k, are both < 1 due to the energy conversions never being fully complete.[39]
Equation 2:12
Equation 2:13
There are many types of k factor, however the most important are kp and kt. In a thin
piezoelectric disc, the coupling between the electric field in the z-axis (or 3-direction ie
through the thickness of the disc) and the simultaneous mechanical actions in the x- and y-
axis directions is known as the radial coupling or radial vibration, known as the planar
coupling coefficient, kp. A schematic presentation of this is shown in Figure 2.5. The
formula defining kp is given in Equation 2:14,[46] where fr is the resonant frequency and fa
is the anti-resonant frequency.
The coupling between the electric field in the z- (or 3-) direction and the
mechanical vibration in the same direction is known as the thickness coupling coefficient,
kt.[41, 47]
Equation 2:14

2.1.3 Ferroelectric Properties
A ferroelectric material is one which exhibits spontaneous polarisation, where the
direction of electric moments within can be changed by applying a field, and the
relationship between field and polarisation which takes the form of a hysteresis loop.[35,
39, 42] This phenomenon was first discovered by Valasek in 1921 with Rochelle salt.[48]
This is the reason why ferroelectricity is sometimes termed Rochelle-electricity in
France and Germany.[49] This behaviour is only observed until its Curie temperature, TC,
where the material is no longer ferroelectric. Although given the prefix of ferro, a
ferroelectric is not observed in iron-based materials, but was given the name due to the
similarities to ferromagnetism.[49] Ferroelectric materials are a subset of piezoelectric
materials, where some exhibit ferroelectric properties and some do not.[50]
There are three main structures that exhibit ferroelectric properties, that of Perovskites,
Tungsten Bronze Type (TBT) and Bismuth Layered-Structured Ferroelectrics (BLSFs).
Perovskite materials are known to have properties most useful for actuator and high
power applications, whereas BLSFs have better characteristics for resonator and ceramic
filter applications.[13] In this report, Perovskite materials are predominant, being the
structure of the lead-free material NKN, and the traditional PZT material.
Figure 2.6. Variation of r of BaTiO3 as a function of temperature. Corresponding phase

structures are also provided (after Richerson).[2]
A ferroelectric material undergoes the polarisation described in section 2.1.1, however

this significantly varies according to the applied temperature, as a material can undergo
phase transformations in order to keep the crystal structure at its most energetically
favourable. As the polarisation reaches the upper limit of its stable structure, the relative
dielectric constant, or permittivity, r, increases significantly. This is evident in the
example of Barium Titanate in Figure 2.6. Eventually, a certain temperature is reached

where the permittivity reaches a considerable maximum at the Curie point, TC, and then
experiences a considerable loss. This limiting point is where a ferroelectric materials
properties behave as a paralectric material (a standard dielectric, and no longer
ferroelectric). By how much the permittivity decreases after this point is defined by the
Curie-Weiss law, defined in Equation 2:15, where A is a material constant and T is a given
temperature above TC (it must be noted, that Equation 2:15 is given in different forms in
different sources, though the general principle is the same the one provided here is that
provided by Jaffe et al[39]). There is a difference between C and TC, which is that TC is
the temperature at which the structure changes and constant drops, as described, whereas
C is a point near TC but is an extrapolation of the experimental data in order to follow the
formula.[35, 39, 48]
Although the Curie-Weiss law is well-renowned, Uchino and Nomura modified the
equation in 1980 to allow a better fit to observed behaviour shown as
Equation 2:16,[51] and it is this that is employed in current literature.[52-

53] [m denotes the property at the transition. C and are constants, 1 2 where = 1
is for a normal ferroelectric material and = 2 is for a ferroelectric relaxor]
Equation 2:15
Equation 2:16
Figure 2.7. The displacements of ions in BaTiO3 that occur in the cubic-tetragonal transition
(from Moulson and Herbert).[35]
An example of how r changes with respect to temperature is illustrated in Figure 2.6, with
the example of BaTiO3 (BT). As illustrated, the increase of applied temperature transforms
BT through three different phases of ferroelectric behaviour (that of rhombohedral,
orthorhombic and tetragonal), before reaching a maximum permittivity at TC ~ 120C.
These three structures are non-centro-symmetric, meaning that the central ion (titanium

in this case) is not exactly central, and conversely the barium ions also shift slightly in
order to compensate for this, and thus a dipole is created in the unit cell. The central atom
in perovskites is usually highly polarisable (for example, Ti ions have a charge of 4+)
which helps the dipole to form easily. How much the ions distort in BT is illustrated in
Figure 2.7. At TC, however, the unit cell becomes cubic, thus symmetrical, no longer
allowing spontaneous polarisation to occur in the material. This means that the material
is then paraelectric and so the permittivity significantly drops, as described earlier.
When a ferroelectric material undergoes spontaneous polarisation, PS, a surface charge is

created from the dipoles in the material. A depolarising field, ED, is then also created in the
material (Figure 2.8); to minimise the large opposing energies, the material undergoes
twinning. This means that the material divides into regions of opposing polarity, called
domains. In this case, they are called 180 domains as they are directly opposing
direction, as illustrated in Figure 2.8. The boundaries between the domains are called
domain walls, and these are displaced when the domains alter their direction in order to
align with the applied electric field.[49] The size of the domains is determined by energy
and grain size conservation when transforming between the paraelectric cubic to the
ferroelectric state.[54]
Figure 2.8. The initial surface charges in a material when spontaneously polarised (right)
and how energy is preserved through 180 domains (left) (from Moulson and Herbert).[35]
(a) (b)
Figure 2.9. Schematic diagrams showing (a) how a polycrystalline ferroelectric material
splits into 90 and 180 domains (from Moulson and Herbert).[35] and (b) domain walls in
tetragonal BT (A-A are 90 walls, B-B are 180 walls) (from Jona and Shirane).[42]

In polycrystalline materials, each grain will have a different direction of domains, so an
unpoled ceramic will have no overall polarity as the domains will cancel each other out.
However, as the material is taken below its paraelectric phase at TC, the grains need to
adjust their structure to remain stable and remain in an energetically favourable state. In
order to minimise the strain within the structure, 90 domains can also be formed, as
these are more energetically favourable.[38] Both these types of domain are found in
tetragonal structures,[48] and are schematically depicted in Figure 2.9. Arlt reported in
1987 that there are two main configurations of domain, with the example of tetragonal
BT.[54] In grains smaller than 10m, lamellar structures are visible where 90 domains
are formed across the grain. If the grain size is larger than 10 m, a herringbone structure
is observed, where 90 domains (Figure 2.9b) are separated by one direction and then
split by 180 domains, illustrated in Figure 2.9a. This, however, is the case for BT, whose
visible domains were reported by Matthias and Von Hippel in 1948.[55-56]
In 1990, Arlt published a more generic theorem for all ferroelectric materials.[57]
This is where there needs to be a critical grain size in order to see any lamellar domains
form in a grain, which sees the stress energy in the grain decrease, as shown in Figure
2.10. As the stress energy decreases further, the grain size reaches a larger critical grain
size needed to produce more complex herringbone-type domains within it. Eriksson et al.
confirmed the theory that as the grain size increases, so does the domain size (in nano-
sized grains).[58]
Figure 2.10. The stress energy in grains in terms of grain size, accompanied by the domain
structure visible in the corresponding grains (from Arlt).[57]
How domains move within their boundaries depends upon vacancies present in the
material. Vacancies on the A-site in perovskites allow for easy domain wall motion as they
reduce local stresses in the domain, thus allowing domain switching to occur easily. This
results in a soft material. O-site vacancies, however, act as pinning points along with the

grain boundaries, reducing the wall mobility (especially where grain size is relatively
small). This is hardening of a ceramic, and leads to a reduced tan . [35, 59]
Figure 2.11. Schematic of typical ferroelectric P-E hysteresis loop, including diagrams
showing the domain orientation at various points (from Damjanovic).[60]
A ferroelectric material is where dielectric materials under an external electric field can
change the spontaneous polarisation direction.[40] The grains in a ceramic will all have
random orientation of domains in a polycrystalline ceramic, thus creating a net
polarisation of zero, shown by point A on Figure 2.11. With the addition of an applied dc
field to the material, as long as the material temperature remains below the Curie point,
TC, the domains are forced to align with the direction of the electric field. This increases
with applied field until a saturation point, D, where all domains that are not pinned or
under internal stresses have aligned with the field. When point D is extrapolated back to
zero applied field, this is the saturation point of domains, or saturation polarisation,
shown as Ps in Figure 2.11. The material has now undergone poling. This means that
when the applied field is taken away, there will still be a net alignment of domains, known
as the remnant polarisation, Pr.
Once the field is reversed, the domains change direction, taking slightly longer to
switch to align in the opposite direction, again to a point of saturation, known as PS
shown at Point G. As the field is alternating between negative and positive field, the
pattern exhibited is shown as a hysteresis loop. This means that as the field is increasing
in a positive direction, the loop goes through point EC, the coercive field (the field at which
the polarization is zero); conversely when the field is decreasing to the negative, the loop
goes through EC. This is the strength of the field applied where the net polarisation of the
material is zero. As these points are not where the field is zero, it is here where domain
switching occurs. The hysteresis loop is most pronounced when it is for a single crystal,

and thus polycrystalline materials show a smaller loop due to the defects in the grains,
such as grain boundary pinning, vacancies and impurities. The shape of the hysteresis
loop is dependent upon factors such as the temperature, test sample dimensions, humidity
of the sample before testing (it can be detrimental to some materials), the texturing of the
specimen, grain size and the thermal and electrical testing the sample was previously
subjected to.
Above TC, the loop no longer exhibits hysteresis and the behaviour resembles a
diagonal straight line, as now it is no longer ferroelectric.[2] The highest and most desired
piezoelectric properties of ferroelectric materials are exhibited when there is a high
degree of hysteresis.[61]
2.1.4 Impedance Spectroscopy

Impedance Spectroscopy is a relatively new non-destructive method of electrical
characterisation of materials.
When impedance points are plotted on a complex plane (that is a Z-Z Nyquist plot) with
respect to the applied angular frequency, the resulting plot should show in the form of a
semicircle. These semicircular arcs change with increasing temperature.[62-63]
Figure 2.12. Exemplar impedance plot for yttria-stablised zirconia, showing the three
possible contributions for polarisation processes (from Moulson and Herbert).[35]
There are three electrical phenomena that can be represented in impedance spectra, those
due to the bulk material, grain boundary effects and interfacial polarisation. This is shown
by Figure 2.12. These three interface contributions, along with their equivalent circuit, is
illustrated in Figure 2.15. When there is a single arc seen on the Nyquist plot, starting very
close to the origin, for dielectric materials (such as NKN), the electrical contribution is
thought to be from the bulk or grain. If there is a smaller second semicircular arc
interfering on the right hand side (that is, from lower applied frequencies, usually seen at
lower temperatures), this is the beginning of grain boundary effects.[63]

Figure 2.13. Illustration showing the electrode-ceramic interface cross-section, with
respective equivalent circuits (from Waser).[64] [el is the electrode-ceramic interface, b is
the bulk and gb is the grain boundary contribution]
It is from these contributions that an equivalent circuit of the material can be derived,
using electrical components for each of the phenomena for an accurate model of the how
the material behaves. An exemplar diagram is shown in Figure 2.13 and Figure 2.14. It is
necessary for an appropriate equivalent circuit to be modelled on a material in order to
understand it and its electrical properties.
Figure 2.14. An example of (a) a series-parallel circuit which could produce the impedance
plot in part (b) (after Moulson and Herbert.).[35]
Impedance spectroscopy can determine the type of conduction the sample uses can be
found, such as ionic or electronic conduction. Computational simulations of ionic
transport in ABO3 perovskites have been modelled by Saiful Islam in 2000 and show the
activation energy for the migration of oxygen vacancies is ~ 1 eV, for A-site cation
transport is ~ 4 eV and B-site cation migration is ~ 14 eV.[65]

2.2 Piezoelectric Materials and their Properties
The majority of piezoelectric materials considered in this investigation are perovskite,
ABO3, which in its most basic cubic form is illustrated in Figure 2.17. In the case of barium
titanate [BT], the Ba2+ ions are situated in the A-site corners of the standard unit cell, each
surrounded by 12 oxygen ions, creating a face-centred cubic (FCC) lattice. The Ti4+ ions sit
on the B-site central octahedral interstice.
Figure 2.15. The cubic unit cell of perovskite BaTiO3 (after Richerson).[2]
Perovskites are known for their high degrees of porosity and thus are difficult to achieve a
high density. They are also known to have low Curie temperatures and can be difficult to
pole.[13] Despite this, there is much interest in perovskites to replace PZT.
There are two types of ferroelectric material soft ferroelectrics are based upon
hydrogen-bonding where under TC, the ferroelectric ordered structure that forms
provides specific positions for the hydrogen atoms to pair up and these form the
reversible dipoles. Such materials include Rochelle salt, sulphates, sulphites, nitrides and
nitrites. Hard ferroelectrics are typically oxides that exhibit similar properties to BT;
they are not water-soluble and are mechanically hard and polarise due to a single central
cation of high charge within an octahedron of oxygen anions.[2] It is these hard
ferroelectrics that are addressed in this investigation.
It must also be noted that the soft and hard terms are applied to oxide
ferroelectrics to describe donor and acceptor doped materials, respectively.
In many of the solid solutions discussed in this section, there is an optimum composition
at which enhanced electrical properties are exhibited. At this composition two structural
phases coexist in the solution, and there is a structural transformation. It is called the
morphotropic phase boundary (MPB).[35] This region is further discussed in each
section.

2.2.1 Lead Zirconium Titanate (PZT)
Although the first piezoelectric ceramic was BaTiO3 (BT), the PbTiO3-PbZrO3 (PZT) system
is now the most popular ferroelectric and piezoelectric material in industrial applications.
It has been developed and optimised for a wide range of uses, and is now recognised as a
smart material.[66]
The Pb(Zr1-xTix)O3 phase diagram is shown in Figure 2.16. It is a solid solution of

ferroelectric PbTiO3, which has TC = 495C, which is tetragonal at room temperature, with
antiferroelectric PbZrO3 which is orthorhombic at room temperature and has TC =
234C.[35]
Figure 2.16. Phase diagram for PZT, showing various properties of PZT at different
compositions and the PZT MPB (in green) (after Lee and Bell).[67]
The morphotropic phase boundary (MPB) indicated on Figure 2.16 is of major interest as
superior piezo- and dielectric properties are found there. Jaffe, Roth and Marzullo
discovered this MPB effect in PZT in 1954.[1] For PZT, it is the state of structural change
from rhombohedral to tetragonal where the two structures coexist. This in the range of
0.455 x 0.48 for PbTiO3 and seems to be temperature independent.[35]
As with other ceramics, the doping of other ions into the PZT structure can also increase
its properties. For example, the MPB can shift with doping; isovalent Hf 4+ replacing Zr4+ in
the B-site increases the MPB to 52 mol% PbTiO3, though conversely adding Sn4+ to the B-
site reduces the MPB to 42 mol% PbTiO3 (and lowers TC from 370 to 250 C).[35]

In terms of electrical properties, undoped PZT has a Pr of 50-75 C/cm2.[68] With
increasing density, the piezoelectric and dielectric constants rise from 60 pC/N and 330 to
240 pC/N and 680 respectively.[69] The reason for the poor initial electrical properties in
undoped PZT is due to the difficulty in orienting domains in the tetragonal region, and
domain clamping by oxygen vacancies.[69] Barium titanate, like PZT, is also tetragonal
and exhibits high dielectric and piezoelectric properties without doping. Domain clamping
is synonymous with the higher density and electrical properties, as with higher densities
there are fewer oxygen vacancies in the system.
Berlincourt discussed the differences between acceptor and donor doping in PZT.[68]
Acceptor doping is where a substitution occurs in the lattice and there is a free electron
present, such as adding Fe3+ to a Pb4+ B-site. Acceptor doping leads to a lower permittivity
and piezoelectric coupling, and a higher mechanical Q value. Conversely, donor doping is
the site substitution where an electron hole is left over, such as doping Bi 3+ onto the Pb2+
A-site in PZT. Donor doping leads to higher permittivity, piezoelectric coupling and
resitivity (can be 1000 times higher) whilst losing mechanical Q value properties.[68]
PZT is used for transducer applications and load-bearing applications, for example in
actuators used in applications below 400C.[34, 69] The fact that PZT contains a
significant fraction of PbO, which is deemed toxic by the US Health Department, and EU
legislation has limited the manufacture of new components containing Pb means that
there is a growing interest in Pb-free piezoelectric materials. These alternatives include
BaTiO3, Bi1/2Na1/2TiO3 and NKN-based ceramics.[3, 70-71]
2.2.2 Barium Titanate (BT)

Barium Titanate, BaTiO3, is the classic ferroelectric perovskite material. Its cubic unit cell
is illustrated in Figure 2.15, showing barium (2+) cations in the corner A-site positions,
with the oxygen (2-) anions in the centre of the cell faces, creating a face-centred-cubic
(FCC) structure. The octahedral interstice, the B-site in the centre, is filled with a titanium
(4+) cation, which due to its high polarisability (4+ charge) can easily form a permanent
dipole below 130C, its Curie temperature, TC.[39] At room temperature, however, the
tetragonal phase of BT is stable. This is where one of the cubic edges has elongated, whilst
the other two have decreased in length slightly, though staying at the same ratio to each
other.[42] This is depicted in Figure 2.17.

There is also another structure barium titanate [BT] can be metastable at room
temperature in, which is the hexagonal unit cell, however this is non-ferroelectric and is
less common, so is not discussed here.[39]
Figure 2.17. The phase structures, polarisation temperatures and transition temperatures
of Barium Titanate (after Moulson and Herbert).[35]
a and c are parameter lengths of the unit cell, and P is the polarisation direction
Barium titanate is an intermediate compoud found at a 1:1 ratio in the BaO-TiO2 phase
diagram, thus defining BaTiO3 as the optimal stoichiometric material that exhibits
superior dielectric and piezoelectric properties. This structure is indicated by a green
dashed line in Figure 2.18.
In 1953, Merz reported that above 107C, the ferroelectric P-E hysteresis loops become
pinched in the middle, creating two smaller hysteresis loops.[72] This antiferroelectric
behaviour is visible until 128C, where a straight line is exhibited in replacement of
hysteresis. This is where paraelectric behaviour begins, and so it is very close to the 130C
found by Jaffe, Cook and Jaffe.

Figure 2.18. The phase diagram of the BaO-TiO2 system, with BaTiO3 shown in green (after
Jaffe).[39]
As the temperature continues to decrease to below freezing, the edges between the two
sides of equal length distort their 90 edges to create an orthorhombic unit cell. Jona and
Shirane, however, report that this transition occurs at 5C and not zero, which is in
accordance with the report by Matthias and von Hippel in 1948.[42, 56]
The final phase transformation occurs at -90C, where the lengthened edge, c,
shortens to the same length as the other two parameters, a. However at this stage there
are no right angles in the unit cell as all sides are now under shear to create a
rhombohedral structure. The polarisation direction of the dipoles within each cell is
parallel to the direction of elongation in each transforming instance. This, in its simplest
form, is due to the central B-site Ti4+ cation shifts from the centre towards the oxygen
anions (towards one in tetragonal, two in orthorhombic and three and
rhombohedral).[39] This is also illustrated in Figure 2.17 as P, without ions being shown.
Although these are well-known properties for BT, the exact transition
temperatures can vary due to impurities, doping, grain size, rate of cooling, and stress
conditions of the sample.[39]
By doping BT with other perovskite materials, the TC characteristics will move from
120C. Whether TC goes higher or lower depends upon the dopant. SrTiO 3, for example,

causes the temperature to decrease from 130C to below zero with over 30% doping.[2]
Conversely, when the Ba2+ions are replaced by isovalent Pb2+ and Ca2+, the Curie
temperature increases with increasing doping additions. Figure 2.19 illustrates how TC
can be altered by the addition of Pb, Ca, Sr, Zr and Sn dopants on the Ba2+ A-site.
Figure 2.19. Graph depicting the change in Curie temperature of BT with x mol% of each
dopant on the Ba site (from Yanagida).[40]
In tetragonal BT, 90 and 180 domains are visible in the grains. 90 domains are usually
seen to be lamellar, herringbone or dagger-like, however 180 domains are significantly
different in that their boundaries are curved and seems to be like a watermark.[73]
2.2.3 Potassium Niobate, KNbO3 [KN]

KN is a perovskite material, whose TC is found at 425C.[48] Below this, the tetragonal
phase is most favourable until the temperature falls below 220C where it transforms to
an orthorhombic structure. The final phase transition, to rhombohedral, occurs at -140C.
All of these phase transformation temperatures are much higher than those of BT.[48]
However these transition temperatures are reported to be 435, 225 and -10C by Jona and
Shirane.[42]
Due to the relatively low melting point of KN (1050C), well sintered KN samples
are difficult to produce. This is unlike BT, whose phase symmetries and phase transition
sequences are identical to KNbO3 (unlike any other ferroelectric material).[42].
The ferroelectric behaviour of KN was first reported by Matthias and Remieka in

1951.[74] It exhibits spontaneous polarisation of 0.9 C/cm2 at room temperature, which
increases to 26C/cm2 near TC. Like with BT, there is hysteresis of the dielectric constant
of KN with respect to temperature, illustrated in Figure 2.20.[48]

Figure 2.20. The dielectric constant hysteresis behaviour of KN with respect to temperature
(after Megaw).[48]
There are problems processing KN as K2O is volatile and evaporates at high temperatures.
Potassium oxide is also known for deliquescence, and so must be carefully handled.[75]
2.2.4 NaNbO3 [NN]

Kakimoto reported a TC for NN at approximately 365C, which is similar to that of PZT.[75]
It is known to be antiferroelectric meaning it has a remnant polarisation of zero,[42] and
when subjected to an electric field produces two hysteresis loops, one each in the positive
and negative applied field directions (Figure 2.21).
The structure of NN is orthorhombic at room temperature up to 360C (15C),
where it undergoes a phase transition (it still remains orthorhombic, but in reality
becomes pseudo-tetragonal as the c/a ratio is 1.0023) at 375C. This ratio decreases until
the structure becomes paraelectric cubic from 640C. It must be noted, however, that
there are transitions at 450-470C and 518C as there are changes in electrical
properties.[48]
Figure 2.21. Typical antiferroelectric hysteresis behaviour (after Uchino).[4]

In 1951, the Curie temperature for NN was reported to be 480C by Matthias and
Remeika.[74] According to Kakimoto, NN undergoes seven phase transitions as
temperature increases,[75] showing it is highly sensitive to temperature. Jona and
Shirane classed the phase transitions into the major transitions.[42] NN has a cubic phase
until 640C, below which the phase becomes non-polar tetragonal (or pseudo-tetragonal)
until 562C. At this temperature, the structure becomes non-polar orthorhombic, or a
pseudo-tetragonal phase until it is cooled to below 354C, where it remains orthorhombic
but becomes anti-ferroelectric. The material finally becomes truly ferroelectric in its final
monoclinic phase, which occurs at -200C. It was found by Reisman that these phase
transitions are highly sensitive to internal strains, and so the exact transitions were only
found after much annealing of the sample.[42, 76] The lattice parameters for NN are
provided in Figure 2.22.
The large differences in between the rhohombohedral-orthorhombic phase
transitions reported by Megaw[48] (and by Reisman et al.[76]) are explained by Jona and
Shirane in terms of the hysteresis behaviour.[42] During cooling, the phase transition is at
-200; however when heating the material, it occurs at a much higher temperature of -
10C.
Figure 2.22. Diagram showing the lattice prarmeters of NN (after Jona and Shirane).[42]
Volume cube root indicated in green
Although NN was shown to be ferroelectric in 1951, with a spontaneous polarisation

value, Cross and Nicholson reported that a double hysteresis loop developed, similar to
that exhibited in the paraelectric phase of BT. Like in BT, if the field is large enough, then
the double loop behaviour is like that expected for a ferroelectric, thus the ferroelectric
characteristics are only slightly larger than those for an antiferroelectric. This has
resulted in the material being known as anti-ferroelectric.[48]

Dungan and Golding that showed that at 270C there is a significant drop in the
ferroelectric properties of NN, but not a structural change.[77] There is a significant loss
in polarisation at this temperature, which is irreversible, exhibiting a ferroelectric to
antiferroelectric transition. Once this temperature has been reached, no hysteresis loops
are observed in the material, even at room temperature. However, (Na0.98K0.02)NbO3 does
exhibit hysteresis once the antiferroelectric transition is reached.
2.2.5 Lithium Niobate, LiNbO3 [LN] and Lithium Tantalate [LT]

LN and LT have a rhombohedral unit cell at room temperature. It is not known whether it
is possible for the LN ions to sit in the correct perovskite positions, but the closest
comparison is to rhombohedral BT. The actual structure for these two piezoelectric
materials is trigonal ilmenite (similar to FeTiO3) at room temperature.[35, 75] The space
group for both LN and LT is R3c, where parameter a is 5.4920 and 5.4703 , and angle is
55 and 56, for LN and LT respectively.[48]
LN and LT are reported to be piezoelectric at room temperature, but only exhibit

ferroelectric properties in single crystals above 200C (Figure 2.23).[42, 48]
Due to poor densification during sintering, and high TC, both LN and LT tend to be
utilised in single crystal form.[78] Unlike the other ferroelectric materials reported here,
their coercive field strength and spontaneous polarisations rise with temperature, and
exhibit no Curie temperature.[42].
Figure 2.23. Dielectric Constant, , Saturation Polarisation, Ps, and Ec values for LN as a
function of temperature (from Jona and Shirane).[42]
2.2.6 Strontium Barium Niobate (SBN)

Strontium barium niobate (Sr1-xBax)Nb2O6 (0.25 x 0.75), SBN, has a tetragonal bronze-
type structure, composed of a network of NbO6 octahedra. Due to this network, the
structure is comparable to a Perovskite with different octahedra rotations, and a longer
unit cell.[79]

In 2009, Lili et al. produced SBN with a density of 79.4% of the theoretical, when sintered
at 1320C for 2h.[80] This exhibited a low dielectric constant of <600 at temperatures up
to 140C, along with losses below 0.012 at 10kHz. When adding 1.5wt% SiO 2 the material
properties significantly improved, the dielectric constant reaching a maximum of 4322 at
85C, and losses below 0.085. It is thought that an amorphous silica layer developed at the
grain boundaries, restraining abnormal grain growth, creating a more equiaxed
microstructure.[80-81]
2.3 Sodium Potassium Niobate (NKN)

2.3.1 Recent Pure NKN investigations
NKN was first reported as a potential piezoelectric material by Egerton and Dillon in
1959.[29] Feng et al. explained that as NaNbO3 is added to KNbO3 the stability of the
perovskite structure decreases.[82] Unless the KN-NN solution is very close to the NN
side (>98%), the entire solid solution is ferroelectric. However enhanced dielectric and
piezoelectric properties are observed along the MPB, which is indicated on the NKN phase
diagram (Figure 2.24). The labels F and P show which phases are ferroelectric (F) and
paraelectric (P) whilst the O, T, M and C subscripts for the phase structures indicate
whether they are orthorhombic, tetragonal, monoclinic or cubic, respectively.
The MPB is usually found in between two different phases, such as orthorhombic
and tetragonal, but in this case, the MPB is different as it separates two different
orthorhombic phases (at lower temperatures) and two tetragonal phases at higher
temperatures. The MPB materials are generally known to exhibit enhanced and superior
electrical properties,[1] and this case is no exception.
In order to form an ordered ferroelectric perovskite structure, it is more likely when the
two cations sharing the A or B sites have ionic radii that are significantly different in
size.[83] NKN follows this rule, as the ionic radii of Na+ and K+ are 0.97 and 1.33
respectively[83-84] (Chang et al. report these to be 1.39 and 1.64 [85]).

Figure 2.24. The phase diagram of the NN-KN solid solution system (after Jaffe et al).[39]
In 2009, Baker et al. published the phase diagram for NKN at temperatures up to 500C
(until the paraelectric cubic phase) (Figure 2.25).[86] The figure shows the polymorphic
phase transitions in the NKN system, as well as slight changes in oxygen tilting. Jaffe et al.
did not specify the actual phase structures. It must be noted that this phase diagram is a
function of KN addition to NN, whereas Figure 2.25 is a function of NN addition to KN (ie
reversed). The space groups are given, and underneath these there are the parameters in
terms of magnitude (for example, cubic structure is defined as aaa as all parameters are
the same size) and oxygen tilting (superscripts of 0, + and denote the direction of tilting
in the x, y and z axes), a notation defined by Glazer.[87] The subscripts define the B-site
cation displacement directions (also as 0, + and in the same way) a notation developed
by Stokes et al.[88]
It is noted that there are discrepancies in the reported structure theory. In 2010, Inagaki
et al.[89] reported NKN to have a Bmm2 structure after Katz defined the parameters of
KNbO3 (an NKN end member) as such.[90] However, Zhang et al in 2011 indicated NKN to
have pseudo-cubic Amm2 structure.[91] This Amm2 structure concurs with that of Baker
et al.[86] however both forms have been utilised in publications.

Figure 2.25. Revised phase diagram for NKN including phase structures (after Baker et
al).[86] Dotted lines indicate change in tilting.
The main focus of NKN in this investigation is (Na0.5K0.5)NbO3, a composition very close to
the MPB (Na0.48K0.52)NbO3. Its transition temperatures are TO-T 190-200C and TC =
420C.[17-18, 29] This material is well known for its deliquescence and difficulties in high
densification using the conventional mixed oxide processing route.
(a) (b)
Figure 2.26. NKN P-E hysteresis behaviour according to (a) Ichiki et al.[92] and (b) Zhang et
al.[31]
Typical piezoelectric properties for undoped NKN are d33 = 80 pC/N,[29] but this has been
found as high as 105 pC/N.[93-94]
Ichiki et al. in 2004 found hysteresis in NKN to have Pr = 8.9 C/cm2 and Ec = 9.0
kV/cm (shown in Figure 2.26a) though only in a field of 1.5 kV/cm (though the publication
says up to 4 kV was applied),[92] but higher remnant polarisations have been found.[31,

93, 95-97] Zhang et al., however, produced an NKN sample with significantly better
properties.[31] They showed that a sintering temperature of 1060C produced fully
saturated hysteresis loops with Pr and Ec being 15 C/cm2 and 13 kV/cm respectively in a
4 kV/mm field (Figure 2.26b), and d33 a significantly higher 122 pC/N. No other
publication finds such high piezoelectric constant results for pure NKN.
Chang et al. reported the highest hysteresis properties for undoped NKN.[95]
Whilst investigating the doping of alkaline earth titanates to NKN, the control sample for
pure NKN gave hysteresis values of Pr = 18.8 C/cm2 and Ec = 9.65 kV/cm. These are high
values compared to others in the literature. Table 21 shows a exemplar summary of
undoped NKN properties from the literature. These increases of NKN properties from the
original findings by Egerton and Dillion[29] are due to the further investigation and
understanding of the NKN system, and optimisation of processing procedures.
Table 21. Hysteresis Properties of pure NKN (in order of field threshold, E).
Reference Authors Year Pr (C/cm2) EC (kV/cm) E (kV/cm)

[92] Ichiki et al. 2004 8.9 9.0 1.5
[95] Y. Chang et al. 2006 18.8 9.65 3
[93] Zuo et al. 2008 13.6 9.9 3
[96] Zuo et al. 2006 15.4 11.5 4
[31] Zhang et al. 2007 15 13 4
[85] R-C. Chang et al. 2007 15 14.8 4
[97] Fukada et al. 2008 9.0 26 4
The processing conditions for NKN must be taken into consideration, as NKN is
notoriously difficult to sinter and densify. Zhang et al. investigated the hysteresis
behaviour as a function of sintering temperature.[31] They showed that a sintering
temperature of 1020C led to a density of 69.4% theoretical, and hysteresis behaviour was
not observed, which could be due to the insufficient densification. When the same
formulation was sintered at 1080C, densification reached a significantly higher 94.4%
theoretical, and produced fully saturated hysteresis loops. This shows how important the
sintering temperature is to the processing of NKN ceramics.

Figure 2.27. P-E Hysteresis for (Na0.5K0.5)(Nb0.995Mn0.005)O3 with different cooling rates (see
text) (from Inagaki et al).[89]
The cooling rate, as well as the sintering temperature must also be taken into
consideration. Inagaki, Kakimoto and Kagimiya tested two 0.5 mol% Mn-doped NKN
samples, sintered at 1050C, but upon cooling between 1050 and 950C (1.25 and 0.25
C/min).[89] The resulting hysteresis data for the two samples is significantly different;
the sample having a higher cooling rate, shows leaky hysteresis loop with Pr = 26
C/cm2 and EC = 20.4 kV/cm (which are normal results for NKN) shown as Sample A in
Figure 2.27. The sample cooled at the slower rate shows enhanced properties in terms of
hysteresis loops and significantly higher remnant polarisation of 52 C/cm2 and coercive
field of 13.0 kV/cm (Sample B in Figure 2.27). These properties are highly desirable for
NKN, and shows how sensitive NKN is to processing conditions.
2.3.2 NKN Doping for Enhanced Properties

There are five main effects that doping can have on a ceramic material:
1. Modifying the transition temperatures of a material in order to adjust the temperature
range of a material for a particular application.
2. Restrict domain wall motion so that the dissipation factor of the material can be
reduced.
3. Cause the formation of second phases and thus a heterogeneous composition which
can also change the Curie temperatures and widen the range of temperatures
exhibiting a large permittivity.
4. Control the size of crystallites by introducing vacancies and electron holes which will
inhibit crystal growth due to pinning and increase the dielectric constant below the
Curie temperature.
5. Control the valency and the oxygen content of the B-site ion so that the material can be
sintered in oxygen deprived atmospheres and yet still keep its dielectric properties of
high resistivity. This is due to lower valency substitutions of the B-sites which act as
acceptors.[35]

Figure 2.28. XRD diffractograms of (a) orthorhombic and (b) tetragonal NKN, with peak
identification (after Skidmore et al.).[98]
As sintering temperature increases, the A-site Na+ and K+ are lost due to volatilisation,
leading to increasing amounts of A-site vacancies in the lattice.[99] When NKN is doped,
its characteristic orthorhombic structure can change to tetragonal. This is where doping
NKN brings the polymorphic phase transition (in this case, orthorhombic to tetragonal)
down to room temperature (from ~200C).[99] Due to similarities of the XRD spectra for
these two phases (where orthorhombic and tetragonal peaks are located at the same 2
values, shown in Figure 2.29), there are two main ways of distinguishing the phases. The
first is that the orthorhombic phase has split peaks at 22 and 32 2 (the (100)/(010) and
(110)/(011)peaks respectively). The tetragonal phase shows a characteristic peak
splitting at 45 2 for the (002)/(200) peaks.[100] This, however, is not always the case.
(a) (b)
Figure 2.29. Diffraction profiles of <100> and <200> peaks for (1-x)NKN-xLi0.5Bi1.5TiO3
ceramics, at areas of interest (a) 20 2 25 and (b) 44 2 48 (from Jiang et al).[101]

The second method focuses on the intensity ratio of the double peaks. Upon closer
inspection of the (001) / (100) double peaks at 20-25 2 (Figure 2.29a) and the (002) /
(200) double peaks at 44-49 2 (Figure 2.29b), it can be seen how the orthorhombic and
tetragonal peaks are defined. In the case of Figure 2.29, NKN has been doped with x mol%
Li0.5Bi0.5TiO3 (LBT), and specifically shows how the orthorhombic structure of NKN can
transform into tetragonal with LBT addition. Pure NKN has the left peak (h00) higher than
the right (0k0), as expected for orthorhombic structures. At x = 3 and 5 mol% LBT, the
structure is tetragonal, which is shown by the left peaks (now (00l)) in tetragonal
structures) being significantly smaller than the right (now (h00) in tetragonal).[101] As
the ratios of the two peaks have significantly changed, this is a good indication of whether
the NKN structure is orthorhombic or tetragonal at first glance, and is commonly used as
the argument for the presence or transition of the two structures.[83, 100-102]
Skidmore and Milne suggested a peak intensity ratio () formulation in order to
investigate the presence of orthorhombic and tetragonal phases.[103] These are shown
as Equation 2:17 and Equation 2:18, where I is the intensity of the peak. They proposed
that = 1.85 for orthorhombic NKN and = 0.53 for tetragonal NKN.[98]
Equation 2:17
Equation 2:18
2.3.2.1 Excess K and Na Doping

Potassium and sodium are both A-site cations that sit in the NKN structure. Having an
excess or depletion of one of these changes the properties of NKN. It is useful to dope
NKN with excess sodium due to the well-known volatility of K and Na during sintering.
Kim et al. investigated the addition of Na2O to 95NKN-5LiTaO3 (5LT) and found that excess
sodium caused increased abnormal grain growth.[104] The addition of sodium also
resulted in a lowering of optimal sintering temperature. The optimal addition was 1 mol%
Na2O (sintered at 1050C) where the material exhibited properties of d33 = 230 pC/N, kp =
0.43, r = 470, Pr = 11.7 C/cm2 and EC = 11.8 kV/cm.

Figure 2.30. Density and relative density of (Na0.52+xK0.48)0.942Li0.058NbO3 with 0 x 0.035
(from Li et al).[99]
Li et al. doped (Na0.52K0.48)0.942Li0.058NbO3 with excess Na and the effect on density was
significant, increasing from 77.4% with no excess sodium up to 94.5% at x = 0.015 (Figure
2.30). [99] They showed that excess Na promoted liquid phase sintering; this is desired
as it promotes densification, accelerates grain growth and thus enhances the electrical
properties. The liquid phase is thought to be present due to the excess of A-site ions (as
lithium is also substituted into the A-site as it has a 1+ charge) and so creates a liquid
phase as the solid solution saturation limit has been reached. Electrical properties for this
formulation are given in Section 2.3.2.3 due to the discussion regarding Lithium doping in
NKN.
2.3.2.2 Alkaline Earth Doping

Malic et al. reported that the addition of 0.5 mol% AETiO 3 (AE = Sr, Ba) to NKN promoted
densification and decreased the NKN transition temperatures.[7] The addition of MgTiO3
is detrimental to the densification process, whereas Barium on the A-site causes minimal
changes, and generates a second phase. All of this was confirmed by Chang et al. in 2006
and 2007;[95, 105] density, kp and d33 values significantly decreased with MgTiO3 addition
(though the dielectric r value rose from 421 to 480). Ca and Sr additives to the A-site
increased the density from 96.4 to 97.8 and 97.1 g/cm 3 respectively, but the electrical
properties diminished slightly. [95]
The addition of 3 mol% strontium to NKN (not in the form of a titanate) promoted
superior piezoelectric properties, and increased the grain size and thus resistivity.[106]
As this is undesirable, MnO was also added to the system; the addition of over 0.5 mol%
MnO resulted in enhanced properties, although exact figures are not reported.

(a) (b)
Figure 2.31. (a) Piezoelectric d33 and Qm values, and (b) P-E hysteresis behaviour for
(1-x)NKN-xBT + 1 mol% CuO (from Lin, Kwok and Chan.[83]
Lin, Kwok and Chan doped NKN with BaTiO3.[107] Their optimal formulation is 94NKN-
6BT + 1 mol% CuO (copper oxide is added as a sintering aid) which exhibits enhanced
properties, such as a Curie temperature lowered from 421C for NKN down to 314C for 6
mol% BT doping (both with 1 mol% CuO added). The Pr = 14.0 C/cm2 is higher than that
found for undoped NKN, though the Ec of 11.6 kV/cm is higher, which is undesirable.[83,
93] Although the remnant polarisation value was not the largest (Figure 2.31a), other
values were optimal, such as the d33 value was 193 pC/N (Figure 2.31b), considerably
higher than for NKN.
Chang et al. investigated the addition of 0.5 mol% BT and found properties
including r = 95.8%, d33 = 85 pC/N, kp = 0.26 and r = 393.[95] Park et al. investigated a
much higher addition of 5 mol% BT to NKN, and as a function of sintering
temperature.[108] They reported that with an optimum sintering temperature of 1060C,
enhanced piezoelectric properties of d33 = 225 pC/N and = 1058 were exhibited; much
higher than those reported by Chang et al.[95] This shows that BT is a evidently
successful dopant to enhance the properties of NKN.
CuO doping is often added to perovskites as a sintering aid. It promotes a liquid phase
during sintering and promotes densification (which in turn promotes enhanced
piezoelectric properties).[46, 109] It yields NKN ceramics that are denser than those
without Cu-doping.[83, 109] As Cu2+ is introduced into the NKN lattice, it occupies the
Nb5+ B-site (similar ionic radii at 0.73 and 0.64, respectively) which causes the unit cell to
expand slightly.[46, 109] It also produces oxygen vacancies in the lattice, as the doping is
not charge balanced. This replacement is shown in Equation 2:19 in Kroger-Vink
notation.[46] If oxygen vacancies are introduced to an electroceramic, they become
harder.[35, 59] Yang et al. found the optimal addition of CuO to be 0.25 mol% where the
maximum relative density and kp values were ~93% and 41.7%, respectively.[46]

Equation 2:19
Park et al. also investigated the addition of CuO as a sintering aid to 95NKN-5BT.[109]
They found the optimal addition to be 1 mol% CuO. In this case, the optimal properties
included r = 94.5%, d33 = 230 pC/N, kp = 0.37 and r = 1150.[109]
Mn, like Cu, also sits on the B-site in NKN and so is also used as a sintering aid.[89] Again
in 95NKN-5BT, along with 2.0 mol% CuO and 0.5 mol% MnO (as sintering aids), enhanced
properties were reported by Ahn et al. including d33 = 248 pC/N, kp = 0.41 and r =
1258.[110] These are both higher than reported by Yang et al.[46] and Park et al.[109],
and also includes a higher copper oxide addition.
2.3.2.3 Li, Ta, Sb and Ag Doping

These four oxides are successful dopants for NKN, leading to enhanced electrical
properties. The addition of lithium to NKN brings about an MPB (morphotropic phase
boundary) where enhanced electrical properties are observed at the transition from
orthorhombic to the tetragonal phase. The addition of Li 2+ to the A-site of NKN brings
about an MPB with a wide transition, as literature reports suggest it to be between 0.3 -
0.7 mol% lithium additions. Lithium is added in various forms, such as LiNbO3, LiTaO3 and
LiSbO3.[103, 111-113]
Niu et al. studied the addition of lithium to NKN.[114] Figure 2.32 shows XRD profiles for
x mol% Li addition to NKN. For up to 4 mol% Li doping there is an orthorhombic structure
that is expected for NKN, but additions above 7 mol% lead to a tetragonal structure.
Hence the 5 and 6 mol% doping gives rise to a phase boundary (shown as PB on Figure
2.32a) where the two phases coexist. This is more so in the 5 mol% formulation, as 6%
shows both phases but has a higher degree of tetragonality. Similarly, Zhang et al reported
the addition of 5.2 mol% Li addition to NKN gave mixed orthorhombic and tetragonal
phases at room temperature.[115] Thus the 5-6 mol% Lithium addition to NKN is of
particular interest because of the enhanced electrical properties that are exhibited at the
MPB in the system. Song et al. reported the solubility limit for Lithium addition to be 7
mol%.[116]

(a) (b)
Figure 2.32. XRD profiles of (a) (Na0.5K0.5)1-xLixNbO3 (after Niu et al)[114] and (b)
Li0.058(Na0.521+xK0.48)0.942NbO3 (after Li et al).[99]
Li et al. showed that there must be an MPB (as opposed to just a polymorphic phase
transition) with lithium addition when investigating the addition of excess sodium to 5.8
mol% Li-doped NKN.[99] By the addition of excess Na, there is a significant discontinuity
in the peaks between 0.015 and 0.020 doping for Na (Figure 2.32b). As all the processing
conditions remain the same, the orthorhombic peaks should not have this anomaly; this is
seen to be a difference in orthorhombic parameters and so an MPB. This is confirmed as
the MPB is known to show enhanced electrical properties, which is clearly seen in this
doping region (0.015-0.020) in Figure 2.33. The optimal excess Na-doping addition for
this 94.2NKN-5.8LN formulation is x = 0.015, where properties include d33 = 279 pC/N, Pr
= 27.1 C/cm2, kp = 0.46 and TC = 465C (higher than for pure NKN).

Figure 2.33. Piezoelectric and dielectric properties for Li0.058(Na0.521+xK0.48)0.942NbO3 (from Li
et al).[99]
Shen et al. reported the lattice parameters for (Na0.535K0.485)1-xLix(Nb0.08Ta0.02)O3 for 0.02
x 0.07.[102] It is clearly shown the MPB region (indicated on Figure 2.34) is between the
two distinguishable orthorhombic and tetragonal phases. It should be noted that the
orthorhombic phase has relatively similar parameter lengths, and angle does not stray
far from 90 (Figure 2.34); this concurs with the concept of considering orthorhombic
NKN as pseudo-cubic.[89, 117-118] [ is the angle between a and b parameters in the
pseudo-cubic unit cell. This is further explained in Section 4.2.1.2 and Figure 4.6]
Figure 2.34. Lattice parameters and (angle) value for structures of (Na0.535K0.485)1-
xLix(Nb0.8Ta0.2)O3 (0.02 x 0.07) (from Shen et al).[102]
Shaded area indicates MPB region.

In terms of transition temperatures, 6 mol% lithium is the optimal addition for NKN. This
addition causes the Curie temperature to increase, from 420C[29] to 450C (although Niu
et al. reported a high value of 474C).[111, 114, 119]
The TO-T phase transition for NKN is at 200C,[70, 120] Niu et al. reported this to
be significantly lower by 67C.[114] Higashade et al. report this to be even lower, at
15C.[121] These findings show that the 94NKN-6LN (LiNbO3) composition subjects NKN
to a much larger temperature range in the tetragonal region (a range of up to 240C
larger), although this is still a formulation with mixed orthorhombic and tetragonal phase.
6 mol% Li doping compositions exhibit d33 = 175 pC/N, which is significantly higher than
for pure NKN (110 pC/N)[114] and Pr = 20 C/cm2 and Ec = 22 kV/cm.[121] In
comparison with undoped NKN, the Pr value is significantly higher than for NKN (13.6
C/cm2) but the Ec value is also significantly higher (undesirable) as it is 9.9 kV/cm for
NKN.[93]
These results are significant, and show lithium to be a successful sintering aid for NKN.
The Li+ sits in the A-site of the perovskite lattice, allowing the single phase to remain, and
the grain size to significantly increase (from 1.3 m for undoped NKN to 3.3 m for 6
mol% addition (and an even higher value of 4.2 m for 6.5 mol% addition).[114] This is
also reported by Song et al. where the addition of Li increases the average grain size as a
direct relationship to the amount of liquid phase found in the ceramic.[116] Similarly
Zhang et al. showed the addition of 5.2 mol% LiSbO 3 (another Perovskite in the form
ABO3) enhances the P-E hysteresis properties up to Pr = 25 C/cm2 and Ec = 18.5
kV/cm.[115]
The most promising material was reported by Saito et al. from the Toyota research group
in Japan.[15] They produced a material doped with Li, Ta and Sb in the formulation
(K0.44Na0.52Li0.04)(Nb0.86Ta0.10Sb0.04)O3 that had properties comparable to standard non-
doped PZT [Pb(Zr0.52Ti0.48)O3]. Although limited information is given, this ceramic has a TC
of approximately 260C and a d33 ~ 300 pC/N. This formulation was further enhanced
through texturing, which is discussed in Section 2.4.
The highest remnant polarisation of lithium doped NKN was published by Wu et al, where
5 mol% LiSbO3 addition to K0.4Na0.6NbO3 produced results of Pr = 30.8 C/cm2 and Ec =
14.0 kV/cm.[122] The d33 value is also significantly higher at 280 pC/N.

2.4 Texturing
2.4.1 Introduction to Texturing

Texturing is the alignment of grains in the microstructure. An oriented material exhibits
enhanced electrical properties as it behaves more like a single crystal. The orientation of a
material is measured by the Lotgering factor, f, using Equations 2:20-22 from the sum of
the main {h00} peaks and the sum all of the peak intensities for the oriented material
against the same in the randomly-oriented material (P and P0, respectively).[123-124]
Equation 2:20
Equation 2:21
Equation 2:22
2.4.1.1 Tape Casting

The tape casting process has been developed for electronics requiring thin sheets of
dielectrics to be produced at low cost and high quantity. There are three main tape casting
processes:
1. The doctor blade process. This involves the ceramic powder to be converted to a
slurry using binders and solvents, and then casting it onto a moving surface. A
blade is positioned at a particular height in order to achieve a specific thickness. A
flexible tape is produced, which can then be utilised differently depending upon
the application. The general process is illustrated in Figure 2.35. This is the most
utilised process for tape casting.
2. The waterfall technique. The slurry is dropped into a trough at a rate at which
there is a perpetual curtain falling into a trough underneath (which then
recirculates around up to the top again) and a substrate is slid across this slurry
curtain to obtain a film of uniform thickness and is quickly dried once on the
other side. This is illustrated in Figure 2.36.
3. The paper-casting process. Low-ash paper (the type results in different thicknesses
of film) is used as a substrate and is rolled through a slurry, to which it gets wet
and the slurry adheres to it, and is then passed through a heater to dry and is
rolled up. The paper is later removed through firing.[2]

Figure 2.35. Schematic of the general doctor blade tape casting process (from Richerson).[2]
Figure 2.36. Schematic Diagram for the waterfall casting process (from Richerson).[2]
The slurries created are usually created by adding binder, solvent and plasticiser to the
ceramic powder. The binder is usually a long chain polymer to provide the film with
internal flexibility and holds the ceramic slip together once dried; the solvent is added for
the slip, so that it can be cast easily onto the tape, and the plasticiser is to provide
flexibility of the tape (for easier handling).[125-126] The amounts added are dependent
upon the desired thickness, the fabrication process and the nature of the ceramic powder.
Deflocculants and homogenisers may also be introduced to the slurry, if needed for the
slurry properties. All the additives must be able to be burnt out easily during sintering.
Resulting tapes are usually divided up, electroded (if necessary), stacked on top of each
other, laminated through pressing, fired to burn out the binder and other additives, and
finally electroded to attach to the relevant circuit.

2.4.2 Texturing of Polycrystalline Ceramics
There has been much interest in the texturing of electroceramics, due to the possibility of
achieving enhanced electrical properties as the material approaches the characteristics of
a single crystal.
A popular method of texturing ceramics is to incorporate oriented seed particles, which

can promote the growth of grains in a particular orientation.[127-128] There are two
common forms of oriented template particles: (i) needle-shaped acicular particles and (ii)
plate-like particles (Figure 2.37).
Figure 2.37. SEM micrographs of (a) TiO2 acicular particles, and (b) plate-like BiT particles
(after Jing et al.).[129]
In order to incorporate these particles into the ceramic, they are often mixed with the
calcined ceramic powder to produce a slurry that can be tape cast (discussed in section
2.4.1.1) and sintered. Examples of texturing ceramics are outlined below.
2.4.2.1 Using BiT Particles for RTGG

Plate-like BiT (Bi4Ti3O12) particles are utilised in RTGG texturing of Bi 0.5Na0.5TiO3 (BNT)
and Bi0.5(Na,K)0.5TiO3 (BKNT)-based formulations.[129-135]
An example of BiT particle morphology is shown in Figure 2.37b. Hong et al. report BiT
plate-like particles 3-20m in diameter and 0.5 m thick.[131] Very similar sizes (5-20 m
diameter and 0.5-0.7 m thick) were reported by Motohashi and Kimura.[132] Jing et al.
reported slightly smaller BiT particles of approx. 5 m diameter and a thickness of less
than 0.5 m.[129] Fuse and Kimura, by contrast, produced three different sizes of BiT
particles by sintering at temperatures of 950, 1050 and 1150C, yielding particle sizes in
the ranges of 1-3, 5-15 and 20-30 m, (and thickness 0.14, 0.3 and 0.6 m), respectively.

Fuse and Kimura do not specify the concentration of BiT particles added to
Bi0.5(Na0.5K0.5)TiO3 but kept the addition within the stoichiometric ratio of the
product.[130] They reported that TiO2 was added as a sintering aid. Samples with BiT
particle sizes of 5-15 m and 70 nm sized TiO2 particles resulted in the highest Lotgering
orientation factor, F, of approximately 90%. (The Lotgering factor is fully explained and
defined using Equations 7:1 7:3 in Section 7.8.1.1). Additionally, the Lotgering factor
increased with the sintering temperature, though using larger TiO2 particles of 150 nm did
not achieve higher F factor than 60%. This shows that powder particle size is also an
important factor in RTGG processing. This is agreed by Hong et al, who report that a fine
particle size promotes densification, and at lower temperatures.[131]
Figure 2.38. SEM micrographs of BiT particles (a) and the resulting BNKT microstructure
(after Jing et al,).[129]
Seni and Tani reported the successful orientation of using Bi 4Ti3O12 (BiT) plate-like
particles.[136] They report a 92% Lotgering factor using the RTGG method, however do
not provide any evidence (such as XRD patterns) to prove this. A previous report by Tani
does, however, include the XRD spectra demonstrating the orientation.[137]
In terms of electrical properties, the texturing of BNKT using BiT particles is

advantageous. In terms of P-E hysteresis behaviour, Hong et al. reported a significant
increase in the remnant polarisation of textured Bi 4Ti2.996Nb0.004O12 (ie Nb-doped BNKT)
tape in comparison to one produced using no template particles (and thus randomly
oriented), where Pr = 24.5 and 12.4 C/cm2, respectively.[131] The result is shown in
Figure 2.39. Here, only 5% BiT particles were introduced to the matrix powder, and
produced a Lotgering factor of over 96%.
Although this is evident from Figure 2.39, Yilmaz et al. (the same research group)
give contrasting statements in a publication three years afterwards.[138] Here they claim
that randomly oriented ceramics are expected to give a higher Pr and lower EC value than
TGG textured ceramics (near to the MPB composition). Although this was for a different

material (NBT-5.5BT), this is the opposite of what they reported for BNKT. Furthermore,
in the same investigation, they report that BiT particles cannot orientate NBT-5.5BT
(94.5% (Na0.5Bi0.5)TiO3 - 5.5% BaTiO3) successfully.[131]
Figure 2.39. Hysteresis behaviour of Nb-doped BNKT thick films, showing results for
randomly oriented and textured (using BiT particles) (after Hong et al.).[131]
2.4.2.2 Using SrTiO3 Particles

Yilmaz et al. report that the Lotgering factor of BNT-BT materials increases with sintering
time.[139] Having added 5 vol% SrTiO3 (ST) platelets to BNT-5.5BT, a Lotgering factor of
70% was seen after 1 hour, which significantly increased to 94% after 12 hours sintering
at the same temperature (illustrated in Figure 2.40a). This shows that the sintering time
enhances good texturing when the main driving force is the small matrix grains reacting
with the oriented template particles in the initial stages. This rapid rate from the first
hour decelerates significantly as the sintering time increases, although the orientation
continues to steadily increase to 96% after 12 hours. The rate is slower due to grain
coarsening and grain impingement.
(a) (b)
Figure 2.40. (a) The orientation of NBTBT as a function of sintering time, and (b) The
diffraction patterns for randomly oriented (blue) and 5% added SrTiO3 template particles
(pink)in NBTBT (after Yilmaz et al).[139]

After 12 hours, the texture in the NBTBT sample is clearly evident (Figure 2.40). The XRD
spectra are significantly different for randomly orientated and for the textured samples.
The two are shown in Figure 2.40b. The significant rise in the {200} peak and decrease of
the {100} peak is a clear indication of successful orientation in the sample. This is a
desired result, and so shows that ST template particles are viable for orienting NBTBT.
2.4.2.3 Using TiO2 Particles

TiO2 particles are different to the BiT and SrTiO 3 particles described previously. In
contrast to their plate-like morphology and orientation, TiO2 particles are acicular
(needle-shaped) and fibrous; their morphology is shown in Figure 2.41a. Jing et al.
reported these to be 2-15 m long with a diameter of 0.2-2 m.[129] These are similar
dimensions to those reported by Sato, Yoshida and Kimura who reported length and
diameter to be 10 and 0.3 m, respectively.[140]
Sato et al. utilised acicular TiO2 particles which are aligned in the <001> directions.[140]
A sintering temperature of 1200C was needed in order to produce equiaxed grains (as
opposed to needle shaped grains) in RTGG of BaTiO3. However these grains are very small
(1-2 m) and did not lead to high density. Cold Isostatic Pressing (CIP) was required in
order to reach 96% theoretical density and a desireable microstructure with grains of size
over 50 m. This was due to the disintegration of the whisker particles into equiaxed
grains at sintering temperatures above 1200C. The process of CIP, however is
undesirable as it increases the time and cost of production, especially when other methods
have been proven to be successful without this extra step. The resulting electrical
properties of this material are not reported, so cannot be compared to other RTGG
processes.
Figure 2.41. TiO2 template particles, and the resulting BNKT microstructure (after Jing et
al).[129]

Jing et al. utilised TiO2 particles for the RTGG production of BNKT.[129] In this case, they
reported the whiskers to produce very low orientation, of maximum 26.4% with a 40%
template addition (up to 80% template particles were added in this investigation). The
optimal resulting microstructure using TiO2 particles is shown in Figure 2.41b. In
comparison with the microstructure for the identical BNKT material utilising BiT particles
(Figure 2.38b), it is clear that utilising TiO2 particles was not successful for BNKT
production. This is due to the diffusion of TiO 2 into the matrix grains, whose stability is
questioned in the work of Sato et al.[140]
By investigating this in parallel with the same methodology using BiT particles
(previously discussed in section 2.4.2.1), Jing et al. came to the conclusion that the
utilisation of template particles in RTGG must meet the following three criteria:
Anisotropy there must be a large amount of anisotropy in the particle, and
especially in comparison to the raw powders
Low reactivity there must be a low reactivity of the particles in order to avoid
dissolution of the particles into the matrix grain (and thus forming undesired
secondary and/or intermediate phases)
Crystallographic similarity the particles must have some order of similar crystal
structure with the final ceramic product to ensure a homogenous and complete
transformation during sintering.[129]
2.4.3 Texturing of NKN
2.4.3.1 Using BNN and NN particles

The orientation of NKN is a relatively new approach, and few research groups have
investigated this method. The first research group to publish any data regarding textured
NKN was Toyota in Japan in 2006.[16] Takao et al. reported a textured NKN sample with a
Lotgering factor, F, of 96% (though the graphic shows 93%) with 1mol% CuO doping.
This was done by using 5 at% NaNbO3 template particles in the tape casting slurry. It is
reported that during sintering at temperatures above 1000C, the template particles react
with the formed NKN matrix powder at the oriented particles surface, and so orientation
of the tape occurs, as the temperature continues to increase. They found that between
1050 and 1075C orientation increases from 22 to 75%. The optimal results were found
using a sintering temperature of 1100C for one hour in an oxygen atmosphere, giving a
density and orientation of over 95%.
The production of NN particles is a two-stage process, and all research groups employing
NN particles as a template for NKN orientation all report this process (with slightly

different conditions). First, oriented Bi2.5Na3.5Nb5O18, BNN, particles are produced using
the molten salt synthesis (MSS) approach (where powders react and sinter in a molten
saline environment). This is done using Bi 2O3, Na2CO3 and Nb2O5 raw powders, in the
stoichiometric ratios as shown in Equation 2:20[141] and synthesised at temperatures
above 850C in a salt flux. The synthesised BNN particles are, after multiple hot washing,
then reacted with Na2CO3 in order to produce a topochemical conversion process, as
shown in Equation 2:21[141] which results in {100} oriented NN particles to be produced,
again using the MSS approach.
5 Bi2O3 + 7 Na2CO3 + 10 Nb2O5 4 Bi2.5Na3.5Nb5O18 + 7 CO2 Equation 2:23
4 Bi2.5Na3.5Nb5O18 + 3 Na2CO3 10 NaNbO3 + 5 Bi2O3 + 3 CO2 Equation 2:24
Bi2O3 + 6 HCl 2 BiCl3 + 3 H2O Equation 2:25
The topochemical reaction involves a weak covalent network of [Bi2O2]2+ in between large
layers of Perovskite [(Bi0.5Na3.5)Nb5O16] which are based around Nb2O6 octohedra. As the
[Bi2O2]2+ layers are broken down, and converted to Bi2O3, the Bi3+ A site vacancies are
replaced by Na+ ions from the Na2CO3. This results in a strong homogenous NaNbO3
morphology to be formed.[118] This conversion reaction is illustrated in Figure 2.42.
Figure 2.42. Schematic diagram of the BNN topochemical conversion reaction to NN (from
Yan et al).[118]

In 2007, a group led by Yan et al. in China reported the production of NN template
particles.[118] This publication is significant, as it is the first one to report a full
experimental procedure of the two-stage process; however some minor details are
omitted. The BNN and following NN particles were produced in a similar method to the
Toyota group, though there are more details of the process. They also explain that the
final hot washing procedure is done by hot washing with alternative hot de-ionised water
and HCl. This not only washes away the salt from the MSS procedure but also the Bismuth
Bi2O3 bi-product by washing with HCl (shown in Equation 2:22).
Yan et al.[118] also reported that there are other BNN compounds that can be produced,
and so the production of the desired BNN depends upon the synthesis conditions and must
be monitored. Other possible formulations that have been detected include
Bi2O2[(Bi0.5Na0.5)Nb2O7] and Bi2O2[(Bi0.5Na2.5)Nb4O13]. It is further reported, however, that
the presence of small amounts of these two compounds is not detrimental to the second
stage of NN particle production process, as these both also easily transform into NN.
Another group from China led by Feng looked at BNN and NN particle production for the
orientation of BT and NBT (Na0.5Bi0.5TiO3).[127] Their production of BNN used the same
conditions, although the NN conversion conditions are not reported. The resulting
template particles were significantly different than those reported by Takao and Saito;[16]
they produced particles 20m wide (slightly larger) however with ten times the thickness
of 5m. This is possibly due to using an alumina crucible as opposed to the platinum
crucible used by the other two groups, however full production conditions were not
specified.
Feng et al also reported an optimum of 30 wt% addition of template particles in order to

orient BT).[127] They found 10 wt% addition led to an orientation of 0.32; this increased
to 0.62 with 30 wt% particles. Although these figures cannot be directly compared to
behaviour in NKN due to the possible differences in orientation process in the two
Perovskite materials, it can be assumed that the difference are affected in some way by the
different morphology of the template particles.
Table 22 shows a summary of the optimal processing conditions and results for BNN
particle formation. This amalgamates all the above research for a quick reference.

Table 22. Summary of properties and processing of BNN particles (optimal results) with
references.
Particle size / Tsint (C) / Salt Salt : oxide

Ref. Authors Year
thickness (m) time (h) medium ratio
[16] Takao et al. 10-15 / 0.5 1100 / - NaCl - 2006
[142] 2008
Chang et al. - 1125 / 6 NaCl 3:2
[123] 2009
[141] Zhang et al. 15-30 / 0.6-1.0 1130 / 4 NaCl 1:1 2009
NaCl +
[127] Feng et al. 20 / 5 1100 / 2 1:1 2008
KCl
[124, NaCl + 2008
Gao et al. 5/1 1100 / 2 1:1
143] KCl 2010
850 / 1,
[118] Yan et al. 15 / 0.5 NaCl 1:2 2006
1100 / 2
2.4.3.2 Using KN Particles

KNbO3 (KN) is one of the end members of NKN, and so is a very good candidate for a
precursor for oriented NKN. Saito and Takao first published this new processing route in
2007, reporting the synthesis of KN particles by forming K 4Nb6O17 initially, and
subsequently forcing a topochemical microcrystal conversion with K 2CO3 to form KNbO3
(in a similar process to the formation of NN from BNN particles).[144]
Figure 2.43. XRD diffraction profiles for 1 mol% CuO doped NKN (a) randomly oriented (Tsint
= 1050C) and (b) with 10% KN particles added (Tsint = 1175C) (from Saito and Takao).[144]

Having added 10% KN in a stoichometric ratio, Figure 2.43 shows how the orientation in
the ceramic changes the ratio of the {110} and {111} peaks. This change brings about a
Lotgering factor of 39.7% orientation along the {001} direction. The 1 mol% CuO-doped
NKN containing the precursor particles requires a higher sintering temperature (1175C
as opposed to 1050C) though does significantly modify the electrical properties.
Texturing increases the dielectric constant from 220 to 306, even though the density
decreases from 99.2 to 90.5% theoretical.
2.4.4 Summary of Texturing Piezoelectric Ceramics

In order to promote orientation of a ceramic, tape casting should involve template
particles, where the templates are already oriented in a particular direction. These are
then used as seeds to promote growth in a particular crystallographic direction of the
matrix grain. The following points must be considered in determining a suitable template
and method in order to achieve advantageous results:
1. Template particle material. Kimura et al. report that it is vital that the precursor is
anisotropic and contains elements that are in the final product composition.[133]
Without this, diffusion between the matrix and templates during sintering will not
take place easily, thus destroying effective sintering and texturing. Also, the
particle material must have low reactivity, as Jing et al. and Sato et al. reported the
diffusion of TiO2 into the matrix lattice, thus destroying the morphology of the
template particles.[129, 140]
2. Template morphology. The shape of the template particle will affect the growth of
the matrix grain; hence necessary to make a choice between acicular (needle-
shaped) and plate-like particles. Jing et al. showed that the production of oriented
BNKT was significantly more successful using plate-like BiT particles than using
acicular TiO2 whiskers.[129]
3. Template particle size. There is a correlation between the powder particle size and
the template particle size for successful texturing. Fuse and Kimura investigated
three different sizes of BiT particles and two sizes of TiO2 powder particle
size.[130] They reported that the optimal orientation and microstructure
depended upon the template grain surface area and matrix grain size; these are the
factors controlling adhesion between the two, and thus determine the growth rate
of the template grains.
4. Sintering Temperature. Fuse and Kimura reported that the Lotgering factor
increases with increasing sintering temperature.[130]
5. Sintering Time. Yilmaz et al. report that in order to reach a Lotgering factor of over
90%, a sintering time of 12 hours is needed for ST templated NBTBT. However

after only one hour, a factor of 70% can be achieved.[139] After this initial
accelerated orientation, further texture enhancement slows due to grain
impingement and coarsening. This is in concurrence with Zhao, Zhou and Yan in
their investigation with BiT particles in BNKT.[134] This, then, is a factor that is
time and resource dependent.
6. Amount of Particle Addition. The amount of particles to be added has been highly
investigated. Hong et al. report excellent results for BNKT using only 5% BiT
particles (and a resulting Lotgering factor of >96%).[131] In the case of NBTBT,
the optimal addition of BNN particles is 30 wt%, though this only produces a
Lotgering factor of 62%.[127]
7. Slurry dispersion. Kimura et al. report that the powder particles must be well
dispersed within the slurry; this can be ensured through the use of a
dispersant.[133] If there is not sufficient homogeneity in the mixing of the slurry,
heterocoagulation (agglomeration of particles) can occur.

3 EXPERIMENTAL PROCEDURES
3.1 Raw Powders

The starting powders, including the manufacturers and the purity, are presented in Table
3.1 below. EC (Enzyme Comission) and CAS (Chemical Abstracts Service) registry
numbers are also provided as these are a commonly accepted standard used for chemicals.
The sodium and potassium carbonate powders were stored in covered glass beakers in an
oven at 100C at all times, due to their susceptibility to deliquescence in moisture. All
other starting powders were stored in the manufacturers plastic bottles in a cool, dry
cupboard until use.
Table 31. Details of raw starting powders
Compound EC No. CAS No. Manufacturer Purity

Na2CO3 207-838-8 497-19-8 Sigma Aldrich (Fluka) 99.8 %
K2CO3 209-529-3 584-08-7 Sigma Aldrich (Fluka) 99.0 %
SrCO3 216-643-7 1633-05-2 Sigma Aldrich 99.9+ %
BaCO3 208-167-3 513-77-9 Sigma Aldrich 99.98 %
Nb2O5 215-213-6 1313-96-8 Sigma Aldrich 99.9 %
Fe2O3 215-168-2 1309-37-1 Alfa Aesar 99.945 %
Bi2O3 215-134-7 1304-76-3 Sigma Aldrich (Fluka) 98.0 %
NaCl 231-598-3 7647-14-5 Sigma Aldrich 99.5%
3.2 Sample Preparation
3.2.1 Mixed Oxide Processing Route

The starting powders of Na2CO3, K2CO3 and Nb2O5 were used to produce (Na0.5K0.5)NbO3,
which will from here be called by its acronym of pure NKN. They were mixed with SrCO 3
and BaCO3 in order to make (100-x)NKN-xSBN compositions, where SBN is an acronym for
the composition (Sr0.5Ba0.5)Nb2O6.
The amounts of the oxides of Na2O, K20, SrO, BaO and Nb2O5 required to produce
stoichiometric NKN and (100-x)NKN-xSBN composition were calculated on the basis of
their molecular weights to produce 50g and 100g batches.
These amounts were weighed using a Ohaus Adventurer Pro AV213 electronic
balance (0.0005g), before being put into a plastic bottles. For milling, each batch of
powder had an equal ratio of powder mass to weight of zirconia balls (of diameter 6mm)
and the same amount in cubic centilitres of propan-2-ol as a reagent. These batches were
vibratory milled for 20-24 hours, then dried in an oven at 90C for 12 hours and the
zirconia milling balls subsequently removed.

The resulting powder was then transferred into an alumina crucible, covered with an
alumina tile, and calcined in a Carbolite Chamber Furnace at 850-1000C for 4 hours, with
a heating and cooling rate of 180C per hour. The calcined powder was subsequently
mixed with 0.0-0.6wt% additive, such as Fe2O3 powder, as a sintering aid, and re-milled in
a plastic bottle, again with the 1:1:1 ratio of powder to zirconia balls to propan-2-ol. After
drying, the resulting powder was stored in a glass bottle in an oven at 100C until
required.
A flow chart of the processing route is illustrated in Figure 3.1. Table 3.2 shows the
formulations that were prepared in this study.
Figure 3.1. Flow chart illustrating the processing route and characterisation techniques
used for this mixed oxide route study

Table 32. Samples prepared in this study.
% NKN in composition % SBN in composition wt% addition of additive
100 0 0 -
100 0 0.2 Fe2O3
100 0 0.3 Fe2O3
100 0 0.45 Fe2O3
99 1 0.3 Fe2O3
99 1 0.45 Fe2O3
98 2 0.45 Fe2O3
97 3 0.45 Fe2O3
96 4 0.45 Fe2O3
96 4 0.3 ZnO
96 4 0.3 NiO
90 10 0 -
An Ohaus Adventurer Pro AV213 electronic balance was used to weigh out 5g batches of
the composition powders. They were then transferred into a steel die and pressed
uniaxially into compacts 20mm in diameter and approximately 16mm in height, using a
load of 0.8-0.9MPa. The compacts were placed on platinum foil (to ensure there were no
reactions between the ceramic powder and the furnace substrate), covered by an
aluminium crucible, and sintered in air using a Vecstar Chamber Furnace at 1050-1160C
for 4-72 hours (with a heating and cooling rate of 180C/hr).
The (100-x)NKN-xSBN compositions are denoted as xSBN; for example 98NKN-2SBN will
be denoted as 2SBN. The 0.45wt% iron-doped samples will be denoted as xSBNF, such as
97NKN-3SBN + 0.45wt% Fe2O3 will be denoted as 3SBNF.
3.2.2 Orientation Casting

Tape casting is a processing technique used to produce ceramics with a preferred
orientation with respect to one particular direction. In order to achieve oriented grains in
the NKN material, pre-oriented template particles needed to be produced. The
experimental procedure is based upon a patent by Toyota in Japan[145] that has already
been used by other research groups in Asia.[15, 118, 123, 127, 141-143] This is a two-
stage process. First Bi2.5Na3.5Nb5O18 particles are produced, from which NaNbO3 particles
can be formed by a topochemical reaction. The experimental procedure has been altered
from those in other publications in order to achieve the optimum template particle results.
A flow chart of the following procedure is given as Figure 3.2.

Figure 3.2. Flow Chart illustrating the processing and characterisation techniques used for
this tape casting study
3.2.2.1 BNN Particle Production

Bi2.5Na3.5Nb5O18 (hereafter named BNN) particles are produced by mixing Bi 2O3, Na2CO3
and Nb2O5 to their stoichiometric BNN formula; the chemical equation is below as
Equation 3:1.[141]
5 Bi2O3 + 7 Na2CO3 + 10 Nb2O5 4 Bi2.5Na3.5Nb5O18 + 7 CO2 Equation 3:1

The powders were mixed together with a 1:1 ratio of powder mass to zirconia balls (of
diameter 6mm) and an equal amount in cubic centilitres of propan-2-ol as a reagent, and
vibratory milled for 18-20 hours. Once the mixture was left overnight to dry in an oven set
at 90C, a weight for weight ratio of NaCl was added to the resulting powder and further
vibratory milled for 1 hour, again in propan-2-ol. This mixture was then left in the oven
set at 90C to dry overnight. Once dry, the resulting powder was taken in 2g batches and
put into a platinum crucible sealed with an alumina lid and heat treated in a Vecstar
Chamber Furnace for 1050-1100C for 2 hours (heating rate 300C/hour, cooling rate
180C/hour).
3.2.2.2 Hot Washing

Once complete, the platinum crucible was placed into a beaker of deionised water, and
sonicated for 30 minutes at approximately 65C. Light stirring was applied from a glass
rod to ensure complete dissolution of the resultant powder.
The resulting hot solution was then used for hot washing. The set up for this is
shown in Figure 3.3.
Figure 3.3. Schematic showing set-up of Hot Washing Procedure.
The hot solution was poured into a Buchner funnel with a 24mm filter base, which has a
Whatman 25mm diameter GF/C glass microfibre circular filter (thickness 1.2m) placed
on it. The conical flask under the Buchner funnel was under vacuum so that the filtration
is accelerated. The water of the solution , along with the NaCl salt that was dissolved in it
was filtered through, leaving the BNN particles behind. These were lightly scraped off the
filter paper using a microspatula and placed into a beaker. These again were dissolved in
deionised water, lightly stirred with a glass rod and again filtered using a new filter if
necessary. Filters were usually changed every 1-2 filtrations. After the 8th filtration, the
resulting filtered water product was tested for salt using diluted silver nitrate (AgNO 3). If
Cl- ions are present, then the water turns cloudy.[143] Eight hot washes were sufficient to
show all the NaCl had been filtered away.
The resultant particles were placed in a small glass vial and placed in the oven set
at 100C in order to dry for further use.

3.2.2.3 NN Particle Production
The BNN particles were taken from their storage oven and mixed with the formulaic ratios
of Na2CO3 and NaCl as a flux according to the formula in Equation 3.2.2.[141] The powders
were lightly mixed together in a platinum crucible using a glass rod, in order to minimise
aggravation of the BNN particles. The crucible was covered with alumina and put in a
Vecstar Chamber Furnace at 950C with a soaking time of 4-8 hours (heating rate
300C/hour, cooling rate 180C/hour).
4 Bi2.5Na3.5Nb5O18 + 3 Na2CO3 10 NaNbO3 + 5 Bi2O3 + 3 CO2 Equation 3:2
The resultant mixture then underwent alternate hot washing, which is described in
section 3.2.2.2, and washing in HNO3 (1N) in order to remove the BiCl 3 bi-product of the
topchemical conversion, as per Equation 3.3.[141] After successful subsequent hot
washing, the resultant NN particles were left in a glass beaker in an oven set at 100C in
order for the water to evaporate and the NN particles remained.
Bi2O3 + 6 HCl 2 BiCl3 + 3 H2O Equation 3:3
In order to avoid particle agglomeration in samples (discussed in Chapter 7) NN particles

were mixed with dispersant Dispex A40 by Siba. The particles were held in a beaker,
having been dried in an oven, and added 2 drops along with approximately 50ml de-
ionised water. They were then sonicated for 20 minutes and then left in the same oven set
at 100C in order for the water and solvent to dry.
3.2.2.4 Oriented NKN Production

The flow chart for the process is shown as Figure 3.4.
Powders of composition 95NKN-5LN and 94NKN-6LN, with varying additives of 0, 0.4 and
0.8wt% CuO added as a sintering aid, were prepared using the mixed oxide route
described in Section 3.2.1. This is to fulfil the formulation (100-x)NKN-xLN + y wt% CuO,
which will now be denoted as xLN + y wt% CuO (x = 5, 6 and y = 0, 0.4, 0.8).
Small batches of powder were utilised as the techniques and volumes of binder, plasticiser
and solvent were being refined throughout the investigation, which is discussed in
Chapter 7. The optimal route is described here.

Figure 3.4. Flow chart for the production of templated NKN-based oriented tapes
In order to produce a successful tape for casting, a binder, solvent and plasticizer is
required. The manufacturers data are presented below in Table 33. The binder is
Polyvinyl Butyral (PVB) and the solvent is a combination of 45% Ethanol and 55%
Toluene in solution. The plasticizer is Dibutyl Phthalate, which is used to prevent
brittleness in the tape for easy removal from the substrate.

Table 33. Manufacturers data for slurry additives
Compound EC No. CAS No. Manufacturer Purity

PVB (Butvar B-98) - 63148-65-2 Sigma Aldrich (Fluka) -
Toluene 203-629-5 108-88-3 Fisher Scientific -
Ethanol 200-578-6 64-17-5 Fisher Scientific -
Dibutyl Phthalate 201-557-4 84-74-2 Sigma Aldrich 99%
A batch of 0.6g pre-calcined copper-doped xLN powder was placed into a MAX 100 plastic
jar (made for the Hauschild SpeedMixer DAC 150FVZ-K). When necessary 10 or 15 wt%
NN particles were added to the powder and mixed gently with a glass rod in order to
prevent damage to the particles. The slurry additives were then added to this powder
mixture, in order to be mixed.
The optimal ratio of powder to slurry additives was 60% powder to 40% slurry
additives. This led to the addition of 0.03g binder, 0.35ml solvent and 0.056g plasticiser to
every 0.6g pre-calcined powder. The mixture was mixed with a glass rod for 10 seconds
and then the jar was sealed with a lid and placed in the SpeedMixer at 2200 rpm for 30
seconds. The resulting slurry was then ready to be cast.
3.2.2.5 Tape Casting Techniques

Thick film tapes (50-300m thickness) were cast using two methods. The first method
was using a steel die. The die measured 100 x 50 x 15mm, with a removable 20 x 55 x
14.9mm steel block that sits inside. This created a 100m track within the steel block. In
the same way as the glass slide casting method, the slurry was poured onto one side of the
track, and a slide was used to drag the slurry across and create a 100m tape. This is
illustrated in Figure 3.6. As the block being cast onto was removable, the tape was easy to
remove using a razor blade to slide under the tape.
Figure 3.5. Schematic illustrating the Mechanism of Metal Die Casting.

The second method of casting was using a glass slide with masking tape attached to either
side (lengthwise) in order to create a track approximately 100m thick for casting the
slurry. The slurry was poured onto one side of the track, and using another glass slide,
pushed along the track to form a tape. This method is illustrated in Figure 3.5. The tape
was easily removed by removing the masking tape from the glass slide, and then running a
razor blade under the tape to remove it from the glass slide.
Figure 3.6. Schematic Diagram of Glass Slide Casting.
In order to investigate thicker films, once one tape was cast and had dried, another layer of
masking tape was added on top of that already present, and then another drop of slurry
was added on top of the dried cast tape, and cast again. This tape measured approximately
200m thickness and was also investigated.
Once the tapes were dry on the glass and metal slides, each tape was sliced into
approximately 1cm2 sections and peeled off using a stainless steel razor blade. These
sections were placed onto platinum foil ready to put into the furnace.
As the investigation continued, the cut tapes were placed on top of each other using
tweezers, then placed in between two highly ground, polished and surface ground (using a
Jones & Shipman 1400X Surface Grinder) 50 x 50 mm stainless steel plates that were made
specially for this procedure. The tapes were pressed at 10kg/cm 2, peeled off the bottom
plate carefully using a razor blade, and then placed onto platinum foil ready for sintering.
The sintering was undertaken in the same way as in the mixed oxide route,
explained in Section 3.2.1, at temperatures 1030-1150C (180C/hour) on a platinum
foil substrate, and covered with an alumina crucible.
3.3 Characterisation Techniques

The starting powders were characterised in terms of structure and grain size.
3.3.1 Density Measurement

The diameter, and thus radius, r, and height, h, dimensions of the centre of each sample
were measured using a micrometer screw gauge (0.0005mm). These dimensions are

used to find the volume, V, of each sample. The sample mass, m, was measured using an
Ohaus Adventurer Pro AV213 electronic balance (0.0005g).
The density of the sample was calculated using Equation 3:4.[2]
m m

V r 2 h Equation 3:4
In order to find the theoretical density, T, of each material, Equation 3:5 was used, using
the number of formula units per cell, Z, the molecular mass, M, the unit cell volume, V, and
Avogadros constant, NA = 6.023 x 1023 molecules/mol).
Z .M
T Equation 3:5
N AV
The relative density, r, is defined as the ratio of calculated density to the theoretical
density in order to give a percentage of sample densification, given in Equation 3:6.
c
r Equation 3:6
T
_________________________________________________________
For the following characterisation techniques, the sample was cut into discs of 1-2mm
thickness using a circular diamond wheel. This created sample discs ready for analysis.
3.3.2 X-Ray Diffraction (XRD) Procedures

X-ray diffraction techniques are used to identify the phases present in powders and
sintered ceramics, and to determine lattice parameters. X-rays have high energy and short
wavelengths, , on the scale of the atomic spacing. The operational principle of XRD is that
a beam of X-rays are directed at the surface of a sample. In the case of a simple crystalline
solid, the beam can be considered impacting on a series of atomic lattice planes (Figure
3.7). Here the parallel X-rays that are in phase with each other (1 and 2) are directed from
a beam at an angle, , onto a material with regular crystalline atomic spacings and lattice
plane spacing depth, dhkl, as illustrated in Figure 3.7. The X-rays are both diffracted and
absorbed, however it is the diffracted ones that are considered in this instance. Atoms P
and Q (on Figure 3.7) diffract the X-rays, both at angle to the atomic plane. The path
length of incident beam 2 is longer than that of beam 1 due to the depth of the second
layer of atoms (row B). This means that the beam has a longer path length through S-Q-T
on the diagram. If S-Q and Q-T both have a distance dsin, the extra path length of beam 2
is defined as 2dsin.

n 2d sin Equation 3:7
If this extra path length is the same length as one, or a complete amount of wavelengths,
n, then the diffracted beams will be in phase with each other and thus constructively
interfere creating superposition of the peaks, given in Equation 3:7, known as Braggs
Law.[146] This means that there is a high intensity of diffracted beams at the detector at
that point. A detector is positioned on the opposite side of the sample, in order to record
the intensity of the diffracted beams. The angle between the X-ray source producing the
incident beams and the plane of the sample surface is (as illustrated in Figure 3.7) and
this is the same angle on the other side between the surface of the sample and the
detector. This results in the detector recording all data in terms of 2. As 2 increases,
the constructive and destructive interference of the diffracted beams, depending upon the
atomic structure of the sample, will record a particular intensity at the detector for each
2 step, resulting in a peak profile. It is through this peak profile that the atomic structure
of a material can be calculated.
Figure 3.7. Theoretical Illustration of X-Ray Diffraction (from Callister).[43]
During this research study, all XRD undertaken was in the form of powder diffraction. All
samples were examined this way in order to determine the composition without internal
strains in the sample. Raw oxide and calcined powders were used in their original state,
slightly ground to ensure an even fine powder distribution. For sintered samples, a
section of the sample bulk was crushed to a fine powder using a pestle and mortar. A thin
layer of silica paste was applied to an amorphous silicon disc for adhesion, onto which the
powder was applied to achieve a thin even layer of powder for XRD characterisation. Any
excess powder was removed from the disc.
A Philips XPert-MPD - Diffractometer was used for phase determination, using a
Cu-K X-ray radiation tube. It had a beam of wavelength = 1.54060, a current of 40 mA
and a 45kV voltage. The diffraction scanned in 0.050 steps between scanning angles of
10 and 80 2. The beam and detector were held for 15 seconds at each step in order to
achieve a high resolution.

The resulting XRD data was analysed using several methods. Peak profiles were matched
on the PANalytical XPert HighScore Plus software using existing stick pattern data from
the International Centre for Diffraction Data (ICDD) database. This confirms a single
material phase, or can identify the possible various phases present in a sample. This is
done by inputting the possible elements in the sample, and searching for all inorganic
compounds with these elements with similar peak profiles. These are then scrutinised by
eye, in order to match the most suitable and realistic published stick patterns to the
observed data.
Another method of XRD analysis was using the TOPAS program to undergo
Rietveld refinement. This procedure is explained in Section 3.3.5.
3.3.3 Synchrotron Energy Dispersive Powder Diffraction

Synchrotron data was collected at two different Synchrotron radiation sources. The
technique involved in analysing synchrotron data works on the same principle as XRD.
However, as a synchrotron source generates a much higher intensity of X-rays, this higher
intensity allows a better resolution and thus makes Rietveld Refinement (see Section
3.3.5) more accurate.
An electron gun in high vacuum and electric field emits a beam of electrons through a
linear accelerator, shown as section 1 in Figure 3.8. The beam then enters a booster ring
(section 2), where the beam is accelerated by a radio frequency voltage source.
Electromagnets provide the necessary forces to allow the accelerating beam to orbit
around the ring repeatedly until the beam is at a high enough speed (near to that of the
speed of light) and is subsequently released into the main synchrotron storage ring
(section 3). Here the beam orbits in a circle, again its path bent by high field
electromagnets. As the direction of the beam changes, the beam is accelerated and thus
emits high energy photons, emitted as X-ray beams released at a tangent to the direction
of travel. This allows many beamline stations (section 4), each with a high energy X-ray
beam, to be used simultaneously for experimentation. The high intensity of the X-ray
beam can be filtered down to a very small wavelength (at Diamond this is done in the
Optics Hutch (section 7)). This small wavelength allows for a larger penetration depth in a
sample, in comparison with laboratory XRD (as explained in Section 3.3.3).

Figure 3.8. Schematic Diagram of Diamond Synchrotron (Oxford, UK), with its main
components highlighted.[12] (1)Electron gun and linear accelerator; (2) Booster
Synchrotron; (3) Storage Ring; (4) Beamlines; (5) Front End; (6) Optics Hutch; (7)
Experimental Hutch; (8) Control Cabin; (9) Radiofrequency (RF) Cabin; (10) Diamond House
3.3.3.1 Daresbury Synchrotron Data Collection

Initial data collection was collected at Station 6.2 at Daresbury Synchrotron Radiation
Source (SRS), UK. This was a Powder Diffractometry Station, which for this study was
especially set up for in situ data collection. The sample was placed in an alumina crucible
on a stage inside an enclosed MRI (Materials Research Instruments) TC-Basic
furnace,[147] shown in Figure 3.9. The furnace was tilted to 11 2 and sample height
adjusted (using a integrated micrometer underneath the stage) to ensure the beam
reached the sample surface exactly. The sample was then heated via a filament
underneath the stage whilst simultaneously recording diffraction profiles for the material.

sample
filament
thermocouple
Figure 3.9. Diagram of inside MRI TC-Basic furnace utilized for experiment at Daresbury
SRS, station 6.2 (after MRI).[147]
Each sample was run with the radiation beam at wavelength = 1.40000 , with the
furnace set to increase temperature at a rate of 2C/minute between 20 and 550C, with
38 sample scans per minute, for the first sample, 99.5NKN-0.5CuO + 0.6wt% Nb2O5 and
subsequently 3C/minute for the remainder of samples. The samples investigated are
given in Table 34.
Table 34. Samples under Investigation at Daresbury SRS, Station 6.2.
Sample Formulation Sample State

99.5NKN-0.5CuO + 0.6wt% Nb2O5 Solid Pellet
99.5NKN-0.5CuO + 0.6wt% Nb2O5 Powder
96NKN-6LT Powder
Data was extracted and normalized to find the d-spacing for each channel on the detector,
the capillary scan was subsequently subtracted. The beam intensity slowly decreased
throughout the day at Daresbury SRS, and thus this had to be normalized as well. This was
done by determining the base ion reading for each scan, finding the average intensity and
dividing the base ion reading by the average intensity. This yields a correction for the
change in background intensity. The corrected data was then analysed using Microsoft
Excel (2003) and TOPAS (v.4.2) for refinement (see Section 3.3.4).

In order to directly compare the results, data for every four scans (that is, covering every
12C for Section 4.2.1 and 8C for the subsequent investigations) were collated and the
intensity values had a multiple of 2,000 added; they were then plotted against 2 (in order
to view the profiles one above another). By taking the initial values of every four scans,
and creating a .xy file of 2 and intensity, the file could be opened in TOPAS (v4.2) ready
for refinement.
As the calculated 2 values were in error by a small amount, an hkl phase was
obtained using the double peak at 22C. This hkl phase was determined to have an
orthorhombic structure, which was expected. By running an initial refinement, the
calculated model gave a very good fit with the observed data. By applying this hkl phase
to other refinements with similar peak shape, an accurate and close fit was obtained.
When the peak shape changed significantly, a new hkl phase was determined in
the same way, until a close fit was again found, and refinements were obtained as before.
3.3.3.2 Diamond Synchrotron Data Collection

The second Synchrotron source was Diamond Light Source in Oxford, UK. Here Beamline
I11 (BL-I11) was used for powder diffraction. A schematic representation of this beamline
is illustrated in Figure 3.10.
Figure 3.10. Schematic Representation of Beamline I11, showing approximate distances of

main components from source (from Thompson et al.).[13]
The finely crushed powder samples were fed into a borosilicate glass capillary and
mounted onto a brass holder provided by BL-I11 set up to be rotating in the path of the
beam in the diffractometer. The wavelength of the beam was 0.826988 ; it was set to
scan for one hour at room temperature, between the angles of 5 and 70 two-theta in 0.01
millidegree 2 steps.
Resulting data was converted to .xls and .xye files, opened in Microsoft Excel
(2003) for initial peak comparison and then TOPAS (v4.2) for refinement, respectively.
The samples that were investigated at this station are shown in Table 3.4. All
samples were in powder form, where a section taken from the bulk of the sample was
finely crushed using a pestle and mortar.

Table 3.4 Samples investigated at Diamond Light Source, BL-I11.
Sample Formulation of (100-x)NKN-xSBN + 0.45wt% Fe2O3

x Sintering Temperature
0 1100C
0.5 1100C
1 1100C
2 1140C
3 1140C
4 1140C
3.3.4 Rietveld Refinement

The program used for Rietveld refining XRD and Synchrotron profiles in this investigation
was TOPAS, initially version 3.0 and subsequently version 4.2. It can be used alongside the
ICSD (Inorganic Crystal Structure Database) and is widely used for structure analysis and
refinement.
The initial structure file for NKN was created using the structural information for KNbO3
published by Kumada et al in 2007.[148] No Na0.5K0.5NbO3 structural data was available
until 2010. By creating this structure file and applying it to a synchrotron diffraction
profile of undoped NKN; the slightly adjusted parameters were saved as a new structure
file for NKN. This new .str file was applied to synchrotron and laboratory XRD data of all
other formulations in this investigation for refinement.
The theory of the refinement of crystallographic profiles was conceived and developed by
Rietveld in the 1960s. There was a difficulty in the refinement of overlapping reflections,
and so he employed a least mean squares refinement program, adapted to recognise and
obtain intensity values from overlapping peaks. Rietveld, after two less successful
publications,[149-150] published a paper in 1969 successfully describing the parameters
that are needed for successful refinement.[151] It is defined as the least mean squares
rule, given as Equation 3:8, where wi is the weight of each observation point, yi (obs) is the
observed intensity of each step, and yi (calc) is the calculated model intensity at each step.
Equation 3:8

Figure 3.11. An original Gaussian peak fitting of observed data (dotted) and calculated
profile (linear) by Rietvelds refinement method (material unknown) (from Rietveld).[151]
This method worked very well, as illustrated in Figure 3.10, and is still used in computer
programs used today. There are five areas that are important in peak refinement of
diffraction data:
1. Peak shape for neutron diffraction patterns, peak shapes are Gaussian (Figure
3.10) and can be fitted easily. For other diffraction methods, however, peaks can
rarely be fitted so easily in this way. The other possible peak shape is Lorentzian,
which is narrower and sharper, with a longer tail at the base. In synchrotron
radiation profiles, the peaks are more complex as they are a combination of the
two types. This is solved by using a pseudo-voigt function, where the addition of
the Lorentzian and Gaussian functions can be adjusted using the parameter.
2. Peak width particle size can affect the peak by broadening it. To take this into
consideration, a peaks width is measured at half the height of the maximum, a
term known as FWHM (Full Width at Half Maximum). It is a function of 2, and so
gives approximate starting values for each peak to initialise refinement.
3. Preferred orientation correction in polycrystalline materials, there can be a
tendency for a particular orientation to be favourable in grains. This affects the
peak profiles, which is considered in the refinement.
4. Method of calculation the minimal different in generic terms is given as Equation
3:8.
5. Background although not a major factor, it must be considered in refinements.
Some materials naturally have high backgrounds, and most sample holders or
substrates are amorphous. If the background is taken into consideration, the
refinement can lead to a better fit and a lower R-value.[151-152]

The R-value is an important indicator of a successful refinement. The lower the R-value
(most importantly, the weight profile, R wp), the lower the deviation between the observed
data and the calculated model. A difference plot is usually given, showing any maxima of
differences between the two data sets, and a successful refinement shows no significant
maxima. The Rexp value is the expected R-value for the refinement taking into
consideration the number of data points in the data and the number of parameters used
for refinement. The ratio of Rwp to Rexp is known as the Goodness of Fit (GOF) value. This
is a commonly used value to determine a good fit between the observed data and
calculated model; the lower the value the better the fit.[153]
3.3.5 Scanning Electron Microscopy (SEM) and EDAX

Electron microimaging was undertaken using a Zeiss EVO60 Scanning Electron
Microscope (SEM), equipped with EDAX for chemical analysis. It was used to examine
both powder and solid ceramic samples.
In SEM, an electron gun fires a beam of electrons down towards a sample, and is
accelerated and focussed though apertures and electromagnetic lenses, as Figure 3.11
illustrates. High resolutions can be obtained in SEM due to the small wavelength of
electrons. The limitations of using an electron beam include the level of vacuum (and
absorbtion by air molecules) and charging of the sample.
Figure 3.12. Schematic Illustration of how an SEM works (from University of South
Denmark).[14]

In order to avoid sample charging in SEM imaging, they are first carbon-coated. Sintered
solid samples from both the as-fired top and the bulk were analysed. The bulk sample was
ground using 400 to 1200-grade SiC, followed by polishing on 6 m then 1 m diamond
paste, followed by polishing with dilute OPS (Oxide Polishing Suspension) Colloidal Silica
solution for 20 minutes. The sample was washed with soap and ethanol in between each
stage. One half of the polished bulk sample was subsequently thermally etched in hot
dilute sulphuric acid for 10-30 seconds.
This sample, along with a as-sintered top sample, was then stuck onto an
aluminium SEM stub using a conductive carbon adhesive, and carbon-coated using an
Edwards Sputter Coater (E306A). Silver DAG was then applied between the sample and
the stub, in order to aid electrons dissipation from the sample during SEM imaging.
3.3.6 Electrical Property Measurements

Samples were cut into discs, as previously described, approximately 1 mm in thickness,
and lightly ground using 1200-grade SiC.
One cylindrical face of the sample was coated with 71% wt/wt silver paste
(C2000107P3 Gwent Electronic Materials), dried in an oven set at 100C for 15-20
minutes, the other face coated and dried in the same way. It was then placed diagonally
onto an alumina crucible and fired in a Carbolite ESF 12/10 Chamber Furnace for 2 hours
at 550C (with a ramping rate of 180C).
The sample was then ground around the edges using low grade SiC in order to
avoid short-circuiting and conductance of the sample disc. A new diameter was measured,
around various points of the sample, where the average diameter was taken when needed.
3.3.6.1 Field Response Measurements (P-E Hysteresis Loops)

High field measurements were conducted on silver-coated sample disc under silicone oil
at room temperature (22 2C) using a computer-controlled function generator (Hewlett
Packard 33120A) and a high voltage amplifier (Trek 609D-6). A specially constructed
current amplifier was used to measure the induced current, which was then integrated
numerically to yield the charge, Q, and then the polarisation P. The applied field and
induced current waveforms were downloaded to the PC using a 16-bit National
Instruments A/D card.[154] Field-Polarisation response loops were obtained whilst
exposed to fields up to 6kV/mm, or until breakdown was observed.

3.3.6.2 Dielectric Measurements
Another coated sample, with a surface area A and thickness t, was placed in between two
electrode wires, as illustrated in Figure 3.12. This set-up was clamped in between two
alumina plates, and placed into a glass tube in a Carbolite MTF 9/15/130 Tube Furnace.
Figure 3.13. Representation of Sample prepared to be clamped in between two alumina

plates, in preparation for dielectric and impedance analysis.
The furnace was set to rise between 25C (room temperature) to 555C, which is known to
be above the Curie temperature of NKN, TC = 418C for pure NKN,[97, 155] in 10C steps
with 20 minutes dwelling time at each temperature.
A Hewlett Packard 4192A Impedance Analyser was used to determine the
capacitance, C, and loss tangent, tan , for the material at each temperature, at frequencies
of 10 Hz to 10 MHz. The capacitance can then be converted to relative permittivity, r, by
use of Equation 3:9. [0 is the permittivity of free space, 0 = 8.854187 x 10-12 F/m] [37]
0 r A
C Equation 3:9
t
3.3.6.3 Impedance Spectroscopy

Two electrode wires were
placed on either side of the disc and with the same set up in the
glass tube as described in Section 3.3.8.2. Angular frequencies () of 5 Hz to 12.5 MHz
were applied to the sample at temperatures in the range of 25 to 645C, in steps of 20C
with 20 minutes at each temperature.
The resulting impedance data (Z and Z) readings for each frequency are then
Z * A Z * r 2 1
*
converted into resistivity ( and respectively) by using t t
Equation 3:10, and then plotted on a - graph to produce a Cole-Cole
semicircular plot. [Here 0 is the permittivity of free space, 0 = 8.854187 x 10-12 F/m,[37]
A is the surface area of the capacitor plates (the surface area of the disc top), and t is the
distance between them.]
Z * A Z * r 2 1
* Equation 3:10
t t

From a semicircular plot, the point at which the semicircle reaches the x-axis (real
resistivity component) on the right hand side defines max. As resistivity is inversely
1
'min
proportional to conductivity , the min was found for each temperature by
'max
Equation 3:11.
1
'min Equation 3:11
'max
Ea
0 e k BT
Equation 3:12
Ea
Using
0 e k BT
Equation 3:12, the Arrhenius relationship, where Ea
is the activation energy, kB is Boltzmanns constant (kB = 1.38065 1023 J/K) [37] and T
is an absolute temperature, a ln -1000/T graph was plotted. From this, a linear
relationship is normally observed, where the gradient of the line is -Ea/kB. From this, the
activation energy was obtained.

4 THE EFFECT OF TEMPERATURE ON NKN-BASED FORMULATIONS
4.1 Introduction
4.1.1 Background and Objectives

The aim of collecting synchrotron data was twofold. As well as collecting original data for
doped NKN, a synchrotron investigation of the structure of a powder as a function of
temperature had not been attempted before at the Daresbury SRS (Warrington, UK). The
station (Station 6.2) was set up to enable the experiment to be undertaken. Not only was
it a first for the station, but the experimental work aided the design of a new station for
Diamond in Oxfordshire, UK.
High resolution diffraction spectra could be collected on the station in
approximately 30 seconds, so the limiting factor of the experiment was the heating rate in
the furnace. Initially this was 3 C/minute but was subsequently adjusted to 2 C/minute).
A problem with the RAPID2 detector system,[156] on the SRS station only became
apparent after the data had been collected. Essentially due to incorrect adjustment, x-rays
falling in between two detectors were recorded by one or the other detector, not both.
This gave rise to irregular peak shapes in some of the data reported in this chapter. Had
the system been working correctly, the GOF values would have been significantly lower
and the final parameters more accurate.
The primary aim of the study was to investigate the change in structures of the NKN
materials as a function of temperature.
4.1.2 Methodology
A significant time after collection of the data, it was found that there was misalignment of
the detector in the synchrotron station. This caused the measured 2 values (and their
corresponding intensity counts) to be in the wrong positions, such that they were
stretched over a wider range of 2 than they should have been. This led to refinement
problems, as the standard NKN model could not be applied for refinement in the normal
way. In order to address this, the characteristic of one set of peaks was investigated as a
function of temperature.
In many XRD investigations of NKN, the 200 and 002 double peak is used in most
literature as the primary basis for phase determination.[119] Due to the overlap of
orthorhombic and tetragonal diffraction peaks for NKN, this double peak can reveal the
dominant phase by comparing the ratio of the two peak heights.[98, 113, 157] Therefore,
in the present study, this double peak was investigated and modelled at each temperature.
4.1.3 Materials Selection
Prior studies indicated the benefit of doping NKN with Cu, Li and Ta. Lithium and
Tantalum are also highly researched dopants to NKN, where there is a significant increase
in properties at the 5-6 mol%[5, 103-104, 112, 158-162] In the present study, samples of
99.5NKN-0.5CuO + 0.6wt% Nb2O5 and 94NKN-6LiTaO3 (6LT) were prepared using the
mixed oxide route.
4.2 Niobium and Copper Doped NKN

The 99.5NKN-0.5CuO + 0.6wt% Nb2O5 samples (density 95% theoretical) were
investigated in two forms: as a sintered pellet (of 8mm diameter and 1mm thickness) and
as a crushed powder. The ceramic sample was seen to deform under high temperatures,
most probably due to internal strain, and so there were problems with the resulting
diffraction data. For this reason, the same material was also investigated as a crushed
powder, over an identical temperature range.
4.2.1 Diffraction data for the sintered pellet

The collected diffraction spectra for the sintered pellet were converted into workable files
for Microsoft Excel (see Experimental section 3.3.3). Due to the large amount of data,
every fourth scan was normalised and plotted above one another for comparison (Figure
4.1).
Figure 4.1. Diffraction spectra of 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet sample
over 20 60 2 range, as a function of temperature (C).

The diffraction spectra for the sintered pellet show two significant phase transitions at
~300C and ~515C (Figure 4.2). The transition temperatures, TO-T and TC, for NKN are
known to occur at ~210C and 418C;[17, 29] therefore the observed transitions are up to
100C higher than expected. Furthermore, the higher temperature transition clearly
shows peak splitting, indicating that the final cubic phase is not yet fully developed. This
behaviour is not expected for NKN at such high temperatures.
Figure 4.2. Diffraction spectra of 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet sample in
the double peak area under investigation with respect to temperature (C).
By refining the diffraction data, the modelled peaks fitted very closely to the observed
profile, for example Figure 4.3. This is for data collected at 31C (one of the initial
refinements) and shows the close fit between the modelled (red) and the observed profile
(blue). The grey line beneath the data shows the differences between the experimental
data and the model, indicating a good fit.
Figure 4.3. Peak modelling for data collected at 31C for orthorhombic 202 and 020 peaks.
The blue line shows the observed data, and the red line shows the calculated model.

4.2.1.1 Lattice Parameters
The resulting lattice parameters are plotted in Figure 4.4. Below the transition at 300C,
NKN exhibits an orthorhombic structure and all three lattice parameters are clear and
distinct. There is however, no systematic relationship between the lattice parameters and
temperature (Figure 4.4). The correlation may be stronger if the whole diffraction data
were refined, rather than working with just two peaks in the spectra. It must also be
noted that refinement is different for every profile. The modelling of data for identical
parameters and conditions can produce significantly different results. This is shown by
the Goodness of Fit (GOF) function (indicating the similarity of the calculated and
observed profiles). The GOF value for the data points at 175C (which looks anomalous in
Figure 4.4) is actually the lowest (having a very low GOF of 2.5 in comparison to 6.9 - 9.8
for data collected at lower temperatures). Thus the 175 C data are not anomalous.
The data do, however, confirm an orthorhombic phase, which is expected for NKN,
but up to 300C, approximately 100C higher than expected.
6.5
6.0
a (ortho)
parameter length (A)
5.5
a (tet)
a (new tet)
5.0 c (ortho)
b (ortho)
b (tet)
4.5
b (new tet)
4.0
3.5
0 50 100 150 200 250 300 350 400 450 500 550
Temperature ( C)
Figure 4.4. Lattice parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet sample.
Symbols: Green for orthorhombic phase, red for tetragonal phase, and blue for new
tetragonal phase; circle for a, square for b and triangle for c parameters.
Above the phase transition of 300C, there was very good refinement in fitting the data to
a tetragonal structure. The fitting to an orthorhombic phase was impossible after 307C,
and so the transition is clear and defined. Figure 4.5 shows the refinement for data
collected at 307C where the majority of peaks are associated with the tetragonal phase.
There is, however, a small peak at 40.2 2, which is associated with the orthorhombic
phase, showing that the two phases coexist at this temperature. By the next temperature
scan (315C) this small peak has and disappeared. The coexistence of two structures at a
phase transition in NKN was reported by Tellier et al.[163] The b lattice parameter has
merged into the c parameter (tetragonal structure has b = c) and does not vary
significantly with incrasing temperature. Again, due to limitations of the data, a direct
relationship between the two lattice parameters and temperature cannot be drawn.
However, it is clear that a tetragonal phase is present after the transition.
Figure 4.5. Profile Refinement for data collected at 307C. Thick blue line denotes the
tetragonal phase component of the refinement.
At temperatures above 500C, a new phase starts to develop. Although this is also a
tetragonal phase, the a and c parameters are very close together, and by 520 C
increasingly becomes the dominant phase; for example the dominant split peak at 523C
in Figure 4.2. It is clear that the two lattice parameters are converging to represent the
cubic phase in NKN. The transition at 500C is much higher than the 418 C expected for
undoped NKN.[29] Whilst the doping may well have modified the transition temperatures
slightly, additional problems were caused by the uncalibrated furnace on the station, and
so the inferred transition temperatures must be treated with caution.
4.2.1.2 Pseudo-cubic Parameters

The parameters reported in much of the literature are given as pseudo-cubic cell
parameters, as there is a relationship between the orthorhombic parameters known for
NKN and a monoclinic phase, with similar parameters of (a b c 4, 90.3).[163]
This cell choice is becoming increasingly popular for NKN, although was initially reported
by Katz and Megaw in 1967.[90] A schematic diagram showing the relationship between
the structures is shown in Figure 4.6.

Figure 4.6. Relationship between orthorhombic Bmm2 unit cell (a0 b0 c0), tetragonal unit
cell (at bt ct) and pseudocubic unit cell (a1 a2 a3 ) with atomic positions (from Ishizawa et
al).[117]
In 2001, Singh et al.[164] reported the orthorhombic parameters of NKN, with no mention
of pseudo-cubic parameters. However in later papers by other workers,[117, 163, 165]
similar dimensions are reported as pseudo-cubic, and with higher precision. This is
shown in Table 41. It must be noted, however, that using these parameters or the
original parameters for Rietveld refinement will lead to the same conclusion, and so it is
understandable for Singh et al.[164] to report these parameters as orthorhombic.
Table 41. Summary of reported NKN pseudo-cubic parameters (at room temperature).
Author Year a () b () c () ()
Singh et al.[164] 2001 3.994 4.016 3.935 -
Wu et al. [165] 2008 4.000 3.940 4.000 90.34
Tellier et al.[163] 2009 4.0046(4) 3.94464(3) 4.00200(5) 90.3327(5)
Ishizawa et al.[166] 2010 4.0054(1) 3.9551(1) 4.0054(1) 89.854(3)
Figure 4.7 shows the pseudo-cubic parameters from this study for the copper-doped NKN,
along with corresponding schematics of the unit cell shape using these parameters. The
solid figures are provided to show an exaggerated (not to scale) example of the
dimensions of the unit cell for each phase. It is clear that as the temperature increases, the
parameters increase. The initially relatively small orthorhombic unit cell lengthens in the
a and c lengths at 300C before b also increases significantly to form a near-cubic unit
cell above 500C. Ishizawa et al. reported the cubic unit cell to have a length of 3.9924(1)
above the cubic transition (at 401C, which is lower than the transformation
temperature recorded in this investigation); the new tetragonal (near-cubic) phase has
dimensions a and b of 4.9393(4) and 4.96568(9) , respectively. Even though these two
dimensions are very close to each other, they are not close to the cubic unit cell

dimensions found by Ishizawa et al.[117] and Tellier et al.[163] This shows that when
there is a major transition from tetragonal to cubic, the unit cell could significantly change
to a smaller volume. Such behaviour, however, can only be speculated in the present
investigation.
5.2
a' = c' (ortho)
5.0
a' = c' (tet)
a' = c' (new tet)
4.8
b' (ortho)
4.6 b' (tet)
b' (new tet)
4.4 b
c
a
4.2
4.0
3.8
0 50 100 150 200 250 300 350 400 450 500 550
Temperature ( C)
Figure 4.7. Pseudo-cubic parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet
sample. Symbols: Green for orthorhombic phase, red for tetragonal phase, blue for new
tetragonal phase; square for a (and c) and triangle for b parameters. The cubes show the
pseudo-cubic parameters for the phases for direct comparison.
Table 42 shows the average lattice parameters for each phase present (in the pseudo-
cubic monoclinic format). The orthorhombic phase has a slightly larger unit cell than
those reported in Table 41, although lattice parameters are similar. This shows that
copper does affect the unit cell by increasing lengths of the parameters slightly.
Table 42. Average pseudo-cubic lattice parameters of phases present in Cu doped NKN
(sintered pellet) (accurate to 0.008 )
Pseudo-cubic Phase a () b ()
Orthorhombic 4.062 3.976
Tetragonal 4.995 4.036
New Tetragonal 4.952 4.494

4.2.2 Powder diffraction analysis for Copper and Niobium Doped NKN
Similar to the data set for the sintered pellet, every four diffraction profiles (that is, every
12C) was normalised and plotted (Figure 4.8).
Figure 4.8. The diffraction profiles for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 (crushed powder)
(C), as a function of temperature, at 20-60 2.
Although there were problems with the analysis of the diffraction data for the sintered
pellet, the data was relatively simple to refine. In contrast, the powder diffraction data is
more complex, showing every phase present, not just those present at the surface of the
specimen. The detailed powder diffraction data is presented in Figure 4.9. Whilst the
structural transitions are not as clearly defined as those seen in the data for the sintered
pellet (Figure 4.2), the main transitions for powder sample data are seen at ~140C,
~308C and ~364C.

Figure 4.9. Diffraction profiles for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 (as a crushed powder)
as a function of temperature (C) at 38-43 2.
At temperatures below 140C, the refinement of the double peak is relatively simple; the
orthorhombic phase is dominant and easily refined. This is shown in Figure 4.10,
representing the refinement for data collected at 72C. This refinement had a Goodness of
Fit (GOF) value of 3.9, which is a very low value for synchrotron data. This shows that the
phase is purely orthorhombic. It is a good representation of refinements below 140C,
where all refinements had a GOF value between 3.2 and 5.5.
Figure 4.10. The Rietveld refinement of the double peak at in data collected at 72C (using
orthorhombic parameters)
At temperatures around 140C, the data in Figure 4.9 shows a significant transition to a
new phase. The data collected at 144C was particularly difficult to refine, although a good
fit was found using both orthorhombic and tetragonal structures (with a GOF value of 9.8).
Nevertheless, at 152C, the modelling also showed a mixed phase system, although the
data exhibited a much better fit with a GOF value of 5.7. Data for the two components are
shown in Figure 4.11 indicating that two phases coexist; this is well documented.[83, 167]

Due to the complexity of the orthorhombic and tetragonal peaks and their overlapping
peak profiles, Rietveld refinement tends to result in lower precision data. Nevertheless, in
this region a GOF value of less than 10 is highly desirable.
At temperatures above 152C, mixed phases were detected in all the refinements.
Although the orthorhombic phase is a rather small component it cannot be ignored in
refinements as its presence does significantly affect the final outcome. It must be noted,
then, that the orthorhombic data in the final summary shows that the phase is present but
it is not the major phase in the system. Detecting the two phases in this region reflects the
benefit of high resolution synchrotron diffraction of a powder sample, in comparison with
a solid sample.
(a)
(b)
Figure 4.11. Profile refinement for data collected at 152C. The top thin blue and red lines
denote the observed and calculated lines respectively. The thick blue line in (a) shows the
tetragonal model, and the black line (b) shows the orthorhombic phase.
The orthorhombic phase remains a small component with increasing temperature until
280C. At this temperature, the orthorhombic phase becomes more prominent as the
second peak becomes more distinct. This can be seen clearly in Figure 4.9 where the 40.4
2 peak increases with temperature up to 304C due to development of the orthorhombic
phase component (Figure 4.12). This is an interesting finding since the well-documented
analysis suggests that the second peak being higher than the first in this region indicates a

tetragonal structure.[100, 113, 119] From the present investigation, however, it is the
orthorhombic phase that causes the second peak to fit better so that the tetragonal phase
is identified. The GOF values for data in the 168-296C temperature range are reasonable
at 5.3-6.1.
(a)
(b)
After 304C, the sharp second peak reduces in size and from 344C the two peaks integrate
and become one large, broad peak. At 344C, only one peak is visible in the diffraction
profiles, but it is clear that there are two peaks superimposed on each other, as can be
seen in Figure 4.13. It shows how both orthorhombic and tetragonal phases are present in
the structure, which is not expected for NKN at this temperature. The quantities of each
component cannot be calculated, due to the nature of the peak refinements, where only a
small section of the diffraction profile is being investigated.
(a)

(b)
With increasing temperature from 344C the superimposed peak develops to form one
single peak at 360C, which is narrow and clearly distinct. As this occurs, the
orthorhombic phase is lost and the material is purely tetragonal, which is expected for
NKN.[163] The pure tetragonal phase is present with increasing temperature until 432C,
although the peak becomes increasingly broader and shallower.
At 432C, there is a reintroduction of the orthorhombic phase to the system. There
should be no orthorhombicity in NKN at this stage (nor tetragonal, as NKN is reported to
be cubic above 418C).[117, 163] However there is an extra peak that cannot be defined
as tetragonal and fits when an orthorhombic phase is introduced to the refinement model.
4.2.2.1 Lattice Parameters

The collected parameters are shown in Figure 4.14. It clearly shows an orthorhombic
phase below 144C, which does not change as temperature rises, until the tetragonal
phase begins to form after the transition. When reflecting upon Figure 4.9, there is clear
peak broadening in the orthorhombic phase before the transition. Broadening can be the
result of strain which is relieved at the transition, transferring the system to a lower
energy state and changes in the unit cell (in this case, to tetragonal). As the temperature
rises towards the transition, the peak broadening shows that there is strain in the sample,
and the tetragonal phase is detected at 144C. As the orthorhombic phase is still detected
throughout the temperature range, it shows that not all of the specimen transforms to
tetragonal phase. This is possibly due to the inhomogeneous sample heating, where the
edges of the sample will have been hotter than the middle.
However, it is clear that the orthorhombic phase that is still present in the sample
has a smaller unit cell, with all three of its parameters shrinking in size, in order to
accommodate a larger tetragonal unit cell (whose symbols are denoted by squares). This
remains so until 360C, where the tetragonal parameters reduce significantly. As

discussed previously, at this temperature, the double peak becomes a superimposed
double peak (Figure 4.9). Although this still represents tetragonal, it has a new set of
lattice parameters from this stage.
6.0
5.5
a (ortho)
5.0 b (ortho)
c (ortho)
a (tet)
4.5
b (tet)
4.0
3.5
0 100 200 300 400 500
Temperature ( C)
Figure 4.14. Phase parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 crushed powder
sample. Markers: Square for tetragonal phase and triangle for orthorhombic phase; red for
a parameter, green for b parameter and blue for c parameter.
There is an issue with the sample, where it does not fully transform into cubic, nor does it
exhibit lattice parameters suggesting that such a transition is likely to take place (as
observed in Section 4.2.1 with the solid pellet). Undoped NKN has a Curie temperature of
418C; doping should not affect the transition temperature significantly. In the present
case, the experimental set-up (the position of the thermocouple) could have resulted in a
discrepancy between the actual temperature of the sample and the temperature recorded
by the thermocouple. This does call into question data for the initial phase transition at
~140C, which is lower than that of the literature data for TO-T for NKN at approximately
200C.[17, 29]
4.2.2.2 Pseudocubic Parameters

Figure 4.15 shows the parameters calculated for the powder sample after pseudo-cubic
conversion. The schematic solids (not to scale) show how the orthorhombic unit cell
decreases in size once the tetragonal phase is introduced to the system at 140C. From
this temperature, the tetragonal unit cell has a smaller b parameter wheras the a and c
parameters are significantly larger. At 360C there is a change in this tetragonal unit cell,

where the b parameter increases in length and the a and c parameters decrease slightly.
At this time, the tetragonal phases unit cell is slowly growing in size up to 500C.
5.2
a' = c' (tet)

5.0
a' = c' (ortho)
4.8 b' (tet)
b' (ortho)
4.6
4.4 b
c
a
4.2
4.0
3.8
0 100 200 300 400 500
Temperature ( C)
Figure 4.15. Pseudo-cubic parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 crushed powder
sample. Markers: Red for tetragonal phase and blue for orthorhombic phase; square for a
(and c) and triangle for b parameters. The cubes show the pseudo-cubic parameters for the
phases for direct comparison.
The final pseudo-cubic parameters were divided into three stages: 0 to 140C, 140 to
360C and 360 to 500C as these were where the significant changes in parameters
occurred. The average lattice parameters are presented in Table 43.
Table 43. Average pseudo-cubic lattice parameters for phases present in Cu doped NKN
(powder sample) (accurate to 0.006 )
Temperature Orthorhombic Tetragonal

range (C) a () b () a () b ()
0 140 4.107 4.026 - -
140 360 4.059 3.939 5.027 4.007
360 - 500 4.103 3.974 4.928 4.068
When comparing the initial monoclinic (pseudo-cubic orthorhombic) phase parameters

with published data (Table 41) the results are similar to the ~4.005 and ~3.950 a and
b parameters, although here they are both slightly higher. This shows that the copper
doping increases the unit cell slightly for NKN below 140C and above 360C; however
they are very similar in the intermediate 140-360C stage.

4.2.3 Electrical Properties of Copper and Niobium Doped NKN
Figure 4.16 shows the hysteresis behaviour of for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 with
Pr = 19.9 C/cm2 and EC =13.5 kV/cm. In this investigation, undoped NKN saturated
hysteresis could not be achieved. The highest Pr value for NKN found in the literature is
from Chang et al. with values of Pr = 15 C/cm2 and EC =14.8 kV/cm.[95] The present
values for copper doped NKN, are desirable, indicating that doping has a positive effect on
the remnant polarisation (higher) and coercive field (lower).
30
20
10
p (uC/cm2)
0
-40 -20 0 20 40
-10
-20
-30
E (kV/cm)
Figure 4.16. P-E hysteresis behaviour for 99.5NKN-0.5CuO + 0.6wt% Nb2O5.
4.3 Synchrotron XRD Study of Lithium Tantalate Doped NKN

Figure 4.17 shows the full diffraction profiles of every four scans (every 12C) as a
function of the temperature.
Figure 4.17. Diffraction profiles for 94NKN-6LT as a function of temperature (C).

The NKN-LiTaO3 formulation has been studied extensively, exhibiting superior properties
to undoped NKN.[33, 103-104, 112, 160, 162] The objective of this study was to
understand how the structure of the material changes with temperature. The analysis of
the data in terms of the double peak was again undertaken, due to problems associated
with alignment of the synchrotron station (Section 4.1). The change in peak profile with
temperature can be seen in Figure 4.18. The addition of 6 mol% LT to the starting
formulation gives rise to a tetragonal structure, as opposed to orthorhombic for the
previous cases. This is instantly recognisable as the second peak (002) is higher than the
first (200), indicating a tetragonal structure (in contrast for orthorhombic structures, the
first peak (200) is higher than the second (002)).[103]
Figure 4.18. Diffraction profiles for 200 and 002 peaks for 94NKN-6LT as a function of
temperature (C).
As the temperature increases from room temperature (22C), there is a clear transition
from tetragonal, as the double peaks transform into a single peak at 390C in Figure 4.18.
(a)

(b)
Figure 4.19. The refinement of 94NKN-6LT for data collected at 30C. The top blue and red
lines denote the observed and calculated lines respectively. The thick blue line in (a) shows
the tetragonal model, and the black line (b) shows the orthorhombic phase.
The room temperature data initially showed a tetragonal phase, but the refinement
improved when an orthorhombic phase was introduced (Figure 4.19). The two phases
were identified in all refinements until 130C. In contrast published data for solid
samples[162, 168] do not report an orthorhombic phase.
As the temperature increased above 130C, the data could be refined on the basis of a
single tetragonal phase. As the temperature increased, the c parameter decreased whilst
the a parameter remained constant. Although the precision of the refinements is still
lower than desirable (due to the double peak refinement procedure), the lack of
orthorhombic-tetragonal overlap gives a clearer impression of how the structure changes
with temperature.
It must be noted, however, that the first peak (200) begins to show signs of
broadening at 270C (Figure 4.20). Although many different refinement parameters were
explored, the broadening could not be modelled satisfactorily. The Goodness of Fit (GOF)
value remained relatively low, between 5 and 6.6 due to the broadening, but remained low
due to the simplicity of the one phase model. In Figure 4.20, for example, the data for
270C has a GOF value of 6.6. The peak broadening, however, is a minor issue. The
refinement confirms a fully tetragonal phase.

Figure 4.20. The diffraction profile for data collected at 270C, with peak broadening on first
peak.
At temperatures above 334C, the orthorhombic phase had to be reintroduced to the

refinement, as the main 200 peak (on the right in Figure 4.21) was asymmetric. The
orthorhombic phase is a very small component (Figure 4.21), although it does increase in
volume at higher temperatures, as shown in Figure 4.23. It must be noted that due to the
broadening of the first peak (200) and the introduction of a second phase, the GOF value
increased to 10-12, reflecting the lower precision of the refinement (for example, the data
in Figure 4.21 has a GOF value of 11.2).
Figure 4.21. The Rietveld refinement of 94NKN-6LT for data collected at 334C, the thick
black line showing the orthorhombic phase component.
As mentioned above, with increasing temperature the orthorhombic phase becomes more
important for the refinement model. A good example is shown in Figure 4.22b, indicating
that the orthorhombic phase is present, and the model would not refine without it.
Although the phase would be defined as tetragonal from laboratory XRD, it is clear under
higher resolution investigation that this is not simply the case. The GOF value for the data
in Figure 4.22 is 6.3, quite respectable. There is a small undefined peak visible at 40.35
2; this is insignificant as the peak disappears with increasing temperature and did not
warrant further attention.

(a)
(b)
Figure 4.22. The refinement at 336C, the thick blue line in (a) showing the tetragonal phase
component, and the thick black line in (b) showing the orthorhombic phase component.
As the temperature increased from 336C, the two peaks in Figure 4.22 slowly converged
into one broad peak leading to a significant transition at 390C. At 390C, this peak can be
modelled using both tetragonal and cubic parameters. Both refinements are similar but
the GOF value for the cubic refinement is marginally lower (11.5) than for the tetragonal
refinement (12.0), indicating that the cubic region has been reached. With further
temperature increase, the tetragonal phase is no longer compatible with the refinement
and so transformation to the cubic phase is complete. The final parameters for the
refinements for 94NKN-6LT are shown in Figure 4.23.

4.3.1.1 Resulting Parameters
6.2
6.0
5.8
5.6
5.4
5.2
c (tet)
5.0 c (ortho)
4.8 b (ortho)
a (tet)
4.6
a (ortho)
4.4 a (cubic)
4.2
4.0
3.8
0 50 100 150 200 250 300 350 400 450 500
Temperature ( C)
Figure 4.23. Resulting lattice parameters for 94NKN-6LT powder as a function of

temperature. Markers: Green for orthorhombic phase, red for tetragonal phase and orange
for cubic phase; square for a parameters, triangle for b parameters and circle for c
parameters.
Figure 4.23 shows the four stages of the structural development. The most unambiguous
section is the second stage (200-330 C), where no orthorhombic phase was detected.
There is a clear reduction in the length of the c lattice parameter as the tetragonal
structure is adjusting towards the cubic transition at 390C.
Lin et al. reported the properties of (Na0.5K0.5)0.96Li0.06 (Nb0.8Ta0.2)O3 and indicated
the tetragonal cubic transition to be at 350C.[107] This is a little lower than the value
determined by the present study (390C), where there was slightly less Ta in the
formulation (Ta0.06) and the difference between the crushed powder and solid
sample[107] may have been relevant. As discussed previously, it is also possible that the
temperatures recorded for the experiment are not reliable.
The detection of an orthorhombic phase before the cubic transition is also of interest. This
is possibly due to stresses within the material as the unit cell is adjusting in size. This has
not been reported previously, although it is rare for samples to be studied in powder form
for diffraction investigation for this kind. Tellier et al. found that there can be a mixture of
phases at a transition,[163] although only between the two phases on either side of the
transition. For an orthorhombic structure to be present near the TC is a new finding.
4.3.1.2 Pseudocubic Parameters
The resulting pseudo-cubic parameters are plotted in Figure 4.24, along with
corresponding schematic diagrams of the unit cell dimensions. The lattice parameters of
the orthorhombic phase (green) decrease in size as temperature increases from 50 to 200
C, and it is this smaller unit cell size that is present when the orthorhombic phase
reappears at 340C.
The tetragonal pseudocubic cell has significantly larger a and c parameters,
showing a wider and deeper unit cell, whilst the b parameter is relatively unchanged.
5.2
a' = c' (ortho)
5.0 b' (ortho)
a' = c' (tet)
4.8
b' (tet)
a (cubic)
4.6
4.4
b
c
4.2 a
4.0
3.8
0 50 100 150 200 250 300 350 400 450 500
Temperature ( C)
Figure 4.24. Pseudocubic parameters for 94NKN-6LT. Symbols: Green for orthorhombic
phase, red for tetragonal phase, and orange for cubic phase; square for a and triangle for b
parameters. The cubes show the pseudo-cubic parameters for the phases for direct
comparison.
The average lattice parameters are given in Table 44. The orthorhombic parameters are
very similar to those found for the orthorhombic phase of the Cu-doped NKN (sintered
pellet) of a = 4.06245 and b = 3.97616 . The copper doped crushed powder, however,
has a larger orthorhombic phase (a = 4.40680 and b = 4.02620 ) than that found for the
6LT sample.
Table 44. Average parameters of phases present in 94NKN-6LT (accurate to 0.008 )
Pseudocubic Phase a () b ()
Orthorhombic 4.079 3.948
Tetragonal 4.98 4.0172
Cubic 4.058 -
Saito and Takao[112] reported lattice parameters for (Na0.5K0.5)0.94Li0.06(Nb0.8Ts0.2)O3
having a similar composition to 6LT (different tantalum addition), but a single tetragonal
phase (using laboratory XRD) with a and c parameters of 3.948 and 4.015 respectively.
They do not report whether they are pseudocubic parameters, though it is clear that the c
parameter found in this study is significantly larger than that found by Saito and
Takao.[112]
4.4 Chapter Summary

NKN was doped in two different ways: (i) with 0.5 mol% copper doping and (ii) with 6
mol% LiTaO3. The copper-doped NKN was investigated in two forms: as a solid pellet and
as a crushed powder. All samples were investigated by x-ray diffraction in situ as a
function of temperature. Detailed analysis of the data revealed calibration problems
associated with the synchrotron station.
The experiments did prove useful, however, as the HATSAXS (High Automated
Throughput Small Angle X-ray Scattering,) beamline B21 at Diamond Light Source was
developed on the basis of the findings from this experimental work.
4.4.1 Copper and Niobium Doped NKN (Sintered Pellet)

For the sintered pellet, the x-ray spectra clearly showed two phase transitions at ~300C
and ~515C, somewhat higher than the expected values for TO-T and TC for NKN at ~190-
200C and 418C.[17, 29] Some of the difference may have been due to inadequate
furnace calibration and the set up of the thermocouple (between the sample and the
element, see Section 3.3.3.1).
Up to 500C the two phase transitions were observed for the sintered pellet
orthorhombic followed by a tetragonal phase. The orthorhombic phase exists to
temperatures up to 300C with average pseudo-cubic parameters of a ~ 4.06245 , and c
~ 3.97616 .
From 510-525C two tetragonal phases coexist in the material. The first is the
tetragonal phase that was observed throughout (pseudo-cubic parameters of a ~ 4.99557
and b ~ 4.0363 ); the second phase is initially detected and determined at 510C and
soom becomes the dominant phase as the temperature continues to increase above 525C.
This new tetragonal phase has near-cubic parameters (pseudo-cubic parameters where a
~ 4.9519 and b ~ 4.4941 ).
P-E hysteresis data was collected this formulation; critical properties were Pr = 19.9
C/cm2 and EC = 13.5 kV/cm, which is a significant improvement compared to the
properties for undoped NKN.[95]
4.4.2 The Copper and Niobium Doped NKN (Crushed Powder)

At temperatures < 140 C there is only orthorhombic phase present, with pseudo-cubic
parameters of a ~ 4.10680 and b ~ 4.02620 . Above 140C orthorhombic and
tetragonal phases coexist up to the limiting temperature of 500C. Up to 360C, the
orthorhombic cell parameters decrease in size (average pseudo-cubic parameters a =
4.05845 and b = 3.93863 ) in order to accommodate the tetragonal phase. The
tetragonal phase in this region has pseudo-cubic parameter sizes of a = 5.02694 and b
= 4.00747 .
From 360C up to 500C, in both the orthorhombic and tetragonal unit cells the b
parameter increases in size; the tetragonal a parameter also increases, but the
orthorhombic a parameter decreases in size. New average orthorhombic phase pseudo-
cubic cell parameters are a = 4.10285 and b = 3.97435 ; for the tetragonal unit cell
they are a = 4.92752 and b = 4.06810 .
Copper doping increased the unit cell size compared to that for published data for
undoped NKN.[117, 163]
4.4.3 Lithium and Tantalum Doped NKN (Crushed Powder)

There is a transformation to a cubic structure at 390C, where the unit cell parameter is
4.05795. Below this temperature, both orthorhombic and tetragonal phases coexist. The
tetragonal phase was detected at all temperatures below 390C, as is expected for 6 mol%
LiTiO3 doping,[162] with average pseudo-cubic parameters a = 4.98349 and b =
4.01715 . The a parameter found here is significantly larger than that reported by Saito
and Takao.[112]
An orthorhombic phase (with average parameters of a = 4.0916 and b = 4.0172
) was detected at low temperatures (20 - 200C). The orthorhombic phase was again
detected just before the tetragonal to cubic transition (340 390C), with a slightly
smaller unit cell volume. The existence of an orthorhombic phase just before the
transition to a cubic structure has not been detected previously in synchrotron studies of
NKN.
5 DOPING NKN WITH PIEZOELECTRIC SBN
5.1 Introduction
The focus of the study was to investigate the effect of doping piezoelectric NKN with
piezoelectric strontium barium niobate, (Sr0.5Ba0.5)Nb2O6, hereafter written as SBN. NKN
is an intensively researched material with much potential (after optimisation) as a
replacement for lead-based piezoelectrics. NKN can be doped by many different elements
and compounds,[95, 101, 169-172] however always in a perovskite (ABO3) form. Here the
perovskite (Na0.5K0.5)NbO3 (NKN) was doped with Sr0.5Ba0.5Nb2O6 (SBN), which is a
tetragonal tungsten bronze (TTB) type material, having a different crystal structure to
perovskite. This investigation is novel and innovative as there has been no evidence of
such research in the literature.
5.2 Characterisation of Starting Powders

The starting powders were characterised in terms of morphology, structure and chemistry
prior to use. The International Centre for Diffraction Database (ICDD) version PDF4+ was
utilised to determine raw powder phases.
5.2.1 Sodium Carbonate
(b)
(a)
Figure 5.1. (a) SEM micrograph of Na2CO3 particle and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns.
Sodium carbonate, Na2CO3, particles are elongated, typically 2mm x 0.5mm in size. An
exemplar particle from the powder is shown in Figure 5.1a. It is white in colour and the
purity is reported by the manufacturer to be 99.8%. EDAX examination showed the Na:O
ratio to be 45:55, which is expected for this powder (carbon content could not be
determined due to the use of carbon coating process for SEM analysis).
X-ray diffraction spectra for sodium carbonate were matched to two different forms of
Na2CO3 (ICDD 00-019-1130 [green lines] and 00-037-0451 [blue lines]) as shown in
Figure 5.1b. No extra phases were detected.
As sodium carbonate is known to be deliquescent, that is it reacts with moisture,
the powder was stored at all times (in a covered beaker) in an oven held at 200C at all
times.
5.2.2 Potassium Carbonate

Potassium Carbonate, K2CO3 (KC), was in the form of white particles approximately 10m
in diameter. An SEM micrograph of the powder is shown in Figure 5.2.
Figure 5.2. SEM micrograph of Potassium Carbonate powder.
When examining KC powder by X-ray diffraction, using identical conditions to those for
other powders in this section, it was clear that the diffraction pattern changed by the end
of the scan. It is thought that this was due to the potassium reacting with moisture in the
air causing its structure to change. For this reason, it was not possible to fit the data to a
reference stick pattern from the ICDD database, and so the data is not presented here.
This highlights the problem of the deliquescence of KC. In order to combat this reaction
with air moisture, the powder was kept in a covered glass beaker in an oven held at 200C
at all times.
5.2.3 Niobium Oxide
Niobium pentoxide, Nb2O5, is a much finer powder than the two discussed above. Nb2O5 is
white in colour with a particle diameter of approximately 200nm (Figure 5.3a). The X-ray
diffraction data for niobium oxide is shown in Figure 5.3b, where there was one phase
detected. This was a match to ICDD 04-008-0301 for niobium pentoxide.
(a) (b)
Figure 5.3. SEM micrograph of Niobium Oxide powder and (b) X-ray diffraction spectrum for
Nb2O5 with fitting to reference data shown by stick patterns.
5.2.4 Strontium Carbonate

SrCO3 is a white powder of acicular shape and has a particle size approximately 3m; a
typical SEM micrograph is shown in Figure 5.4a.
(a) (b)
Figure 5.4. (a) SEM micrograph of SrCO3 particles and (b) X-ray diffraction spectrum for
SrCO3 with fitting to reference data shown by stick patterns..
An X-ray diffraction spectrum of SrCO3 is shown in Figure 5.4b. The data showed two
phases were present in the sample (represented by green and blue lines in Figure 5.4b).
These were strontium carbonate (ICDD 00-005-0418) which is represented by the blue
lines, and so is the main phase present; also strontium oxide was also found (ICDD 00-001-
1113) denoted by the green lines on the stick pattern. As the second phase was only a
small percentage of the total, it will not affect the resulting formulations, as only small
amounts of strontium carbonate are included.
5.2.5 Barium Carbonate
Barium carbonate is a white powder with an elongated particle form, as shown in Figure
5.5a. The average particle length is 1.5m. EDAX analysis showed an exact ratio of 25:75
Ba:O which is expected for this composition (again, carbon could not be detected due to
the carbon coating of samples in preparation for SEM analysis).
The stick pattern fitting from XRD analysis resulted in one phase being detected,
that of BaCO3 (ICDD 01-074-2663).
(b)
(a)
Figure 5.5. (a) SEM micrograph of BaCO3 particles and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns.
5.2.6 Iron Oxide

Iron Oxide (Fe2O3) is a fine dark red powder. Figure 5.6a shows an SEM micrograph of the
powder morphology. The average particle size was found to be 200 nm, which at the same
scale as for niobium pentoxide.
(a) (b)
Figure 5.6. (a) SEM micrograph of Fe2O3 powder and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns..
The X-ray diffraction spectrum for Fe2O3 (Figure 5.6b) closely matches the reference data
(ICDD 00-033-0664). This shows that there are no other phases present.
5.3 Densification of Ceramics in the NKN-SBN System
In order to investigate the effect of SBN addition, 10 mol% SBN was initially mixed with 90
mol% NKN using the conventional mixed oxide route. After sintering for 4 hours at
1100C, the material had a very low density and was visibly unchanged. XRD analysis
showed that there was significant second (non-perovskite) phase in the material; it was
clear that the amount of SBN needed to be reduced. In general, NKN exhibits superior
properties when it is a single phase product.
Subsequently samples were prepared with 8, 6 and 4 mol% SBN; they were mixed,
calcined and sintered, under the same conditions; it was clear that the 4 mol% doping was
the limit for this system. There was no second phase present in the XRD spectra for the 4
mol% SBN samples, although the density was still low (~50% theoretical); the sample
remained white in colour and had the texture of chalk. The single phase that resulted for
96NKN-4SBN, however, showed potential and so this formulation was initially
investigated in some detail. It was clear that a sintering aid would be needed in order to
increase the density.
From this point, the x mol% SBN addition to NKN will be denoted as xSBN, such as the
96NKN-4SBN composition will be denoted as 4SBN.
It was first necessary to increase the sintering temperature of the 96NKN-4SBN from the
optimal 1100C for pure NKN up to 1140C in order to achieve significant densification.
Although the samples were of higher density, they still needed a sintering aid to achieve a
density of over 90% theoretical (this is 4.51 g/cm3 for NKN[173] and 4.50 g/cm3 for 4SBN.
As the difference between the two is so minimal, the theoretical density for NKN was used
throughout for all xSBN compositions (0 x 4).
There are many successful sintering aids for NKN in the literature,[32, 93-94, 174-175]
and so various available powders, such as nickel, manganese, zinc, calcium, cobalt oxides,
were added to the 4SBN system, all at 0.2 wt% levels, in order to investigate which had the
most potential. The most successful was CaO yielding over 4.3 g/cm 3, which is over 95%
of the theoretical. The density of 4SBN processed in the same way without additive was
2.37 g/cm3, showing doping is needed to achieve higher densities and good microstructure
development.
In a preliminary study of pure NKN the effect of iron doping on densification was
investigated.[176] All samples were sintered at 1090C for 4 hours. It was found that 0.3
wt% Fe2O3 addition was the optimal amount increasing the relative density from 90.7%
up to over 94%, as shown in Figure 5.7. Such an increase in density is highly desirable in
view of the correlation between high density and the resulting electrical properties of
NKN.[92, 177] This is consistent with the findings of Zuo et al. who reported that the
sintering of NKN ceramics can be significantly improved by the addition of a small amount
of iron oxide.[70] Zuo et al. also found that the addition of iron oxide creates oxygen
vacancies in the system, which could lead to a slight decrease in the size of the lattice.
However the material remained single phase and the diffraction peaks were
unchanged.[178] This proposal of Zuo et al. was tested for all compositions investigated in
this study. The data are entirely consistent with the theory and findings of Zuo et al.[70]
96%
95%
94%
Relative Density (%)
93%
92%
91%
90%
89%
88%
0 0.1 0.2 0.3 0.4
x% Added Fe2O3
Figure 5.7. Relative density of NKN as a function of x% Fe2O3 additions (after

Wegrzyn).[176]
In view of the previous work on iron oxide doping of NKN, a range of Fe 2O3 doping levels
were employed on the 4SBN composition. The use of ZnO additions was also investigated.
The results are shown in Figure 5.8. It is clear that high levels of ZnO do not enhance the
density, but the higher levels of Fe 2O3 significantly increased the density to 96.7%, which
is the highest density achieved. The addition of 0.6 wt% iron proved to be too excessive,
density fell to 85%. From this preliminary investigation, 0.45 wt% Fe2O3 was identified as
the optimum additions for the SBN system.
100%
90%

80%
70%
Fe2O3
60% ZnO
50%
0.00 0.10 0.20 0.30 0.40 0.50 0.60
x% Dopant Addition
Figure 5.8. Densities of 96NKN-4SBN (Tsint = 1140C) as a function of x wt% Fe2O3 and ZnO
addition.
From this point, 0.45 wt% Fe2O3-doped samples in the (100-x)NKN-xNKN system will be
given an F suffix, and so will be denoted as xSBNF, in the same way as the xSBN notation.
For example, 96NKN-4SBN + 0.45 wt% Fe2O3 will be referred to as 4SBNF. In the same
way, the NKN + 0.45 wt% Fe2O3 formulation will be denoted as NKNF.
100%
98%
96%
94%
92%
90%
88%
86%
84%
0 1 2 3 4
x wt% SBN
Figure 5.9. Relative densities of (1-x)NKN xSBN + 0.45 wt% Fe2O3 (0 x 4), all sintered at
1140C.
As 0.45 wt% Fe2O3 was found to be the optimum doping level found for 4 mol% SBN-
doped NKN, the same addition was used with 0, 1, 2 and 3 mol% SBN samples. The results
are plotted in Figure 5.9. In order to keep the results comparable, all samples were
sintered at 1140C. This is in part the reason for the low densities; for other compositions
(other than 4 wt% SBN) it is believed that lower additions and sintering temperatures are
nearer the optimum. There is, though, a clear and distinct area for investigation from these
results, which show a high relative density of over 96% to the theoretical in the iron-
doped formulations of 2, 3 and 4 mol% SBN doping of NKN. Consequently, these three
compositions were chosen for more detailed investigation.
5.4 X-ray Diffraction Analysis
5.4.1 Undoped xSBN

The (1-x)NKN xSBN (0 x 4) formulations were analysed with laboratory XRD in order
to assess how the structure changed with SBN addition. Figure 5.10 shows the diffraction
profiles for the formulations under investigation. The pure NKN sample shows a clear
orthorhombic phase, as expected.[96, 179] This was also the case, for all formulations up
to 3SBN. This is shown by the ratio of the first peak to the second at approximately 45 2
(ratio of (202) to (020) peaks); the first peak is higher than the second in all cases. This is
an accepted method of differentiating between orthorhombic / tetragonal Perovskite
structures in diffraction data. [101, 109, 180-181] The 4SBNF composition, however,
shows this doublet of peaks having approximately the same magnitude. This shows a
transition between orthorhombic and tetragonal in the system, where the two phases are
coexisting (with the possibility of a morphotropic phase boundary, MPB). For this reason,
the investigation concentrated on SBN addition up to 4 mol%. For compositions above
4SBNF, there was a clear second phase in the XRD data with additional peaks from SBN.
002
200
101
010
022 , 220
311 , 113
202
020
103
212
121
111
4 SBN
intensity (a.u.)
3 SBN
2 SBN
1 SBN
0.5 SBN
pure NKN
10 15 20 25 30 35 40 45 50 55 60
two theta
Figure 5.10. Diffraction spectra for (1-x)NKN xSBN (0 x 4). Indexing of orthorhombic
peaks based on the work of Wu et al.[165]
It must be noted that these SBN compositions (except pure NKN) did not sinter fully.
Their texture remained chalk-like and the samples were easily broken, even when the
sintering temperature was raised from 1090 to 1140C. This is undesirable and so iron
oxide was employed as a sintering aid.
It must be noted that the 101/010 peaks of 0.5SBNF and 1SBNF samples are significantly
smaller than for the other samples. It is unclear whether this is related to texture of the
material. If a material has orientation, some peaks in the diffraction profile disappear
whilst others grow (favouring the direction of orientation).[182-183] In this case,
however, all the other peaks are present, and so texture in the material is unlikely. It is
also difficult to achieve orientation using the mixed oxide route. As the reason for the
peak to disappear is not likely to be orientation, it is unclear for the reason behind this. As
the predominant materials being investigated are 2-4 SBNF formulations, further
attention to this anomaly was not given.
5.4.2 xSBNF Samples

The addition of Iron Oxide significantly enhanced the sintering process, as described in
section 5.3. As the optimal doping level was 0.45wt% Fe2O3, this amount was added to all
formulations for direct comparison.
The resulting XRD spectra for xSBNF are shown in Figure 5.11. All the samples in Figure
5.11 were fully dense, however they were still crushed to a powder prior to XRD
examination to ensure direct comparability with the data for undoped samples (Figure
5.10). It is clear from the diffractograms that all samples (Figure 5.11) are orthorhombic
with no evidence of a second phase, although the 4SBNF sample is the solubility limit for
SBN addition; larger amounts result in a second phase of SBN (as discussed earlier). This
resulted in 4SBNF being the compositional limit of the investigation.
4 SBNF
3 SBNF
intensity (a.u.)
2 SBNF
1 SBNF
0.5 SBNF
NKNF
20 25 30 35 40 45 50 55 60 65 70 75 80
two theta
Figure 5.11. Diffraction spectra for (1-x)NKN xSBN + 0.45 wt% Fe2O3 (0 x 4).
5.5 SEM Investigation
In much of the published literature for NKN-based systems, micrographs are presented for
as-fired surfaces. This is an unreliable method for comparing specimen microstructures.
The interiors of the samples tend to yield more representative microstructures, when
grain growth has not been enhanced by free surfaces and liquid phases or evaporating
components. Micrographs in this chapter are therefore based on polished internal sample
sections, not as-fired surfaces.
NKNF samples had a grain size of 3 m, which is the same as reported by Zuo et al. for
99NKN-1Fe2O3.[70] Samples prepared with 2-4 mol% SBN addition had a very similar
density of over 96% theoretical. However the grain morphologies varied. The micrograph
of 2SBNF (Figure 5.12) shows a relatively uniform grain size of average 3 m with lamellar
domains. However, as the amount of SBN is increased to 3 and 4 mol% (Figure 5.13) the
distribution of grain sizes is more uneven, with small grains for 3SBNF approximately 2
m in diameter and large grains up to 15 m in size (Figure 5.13); 4SBNF grains had the
same microstructure, though the larger grains were up to 20 m in size. The large grains
reveal more complex domain formations, including herringbone domain structures
(indicated by arrows in Figure 5.13). These complex herringbone domains are only
visible in the larger sized grains.[54, 184] Abnormal grain growth stems from the
presence of a liquid phase during sintering, and the driving force is from the surface
energy of the small fine grains.[106, 109] Abnormally large grains are commonly found in
NKN, where a bimodal grain size is expected in samples with optimal electrical
properties.[185-186] Jenko et al. reported NKN had larger grains measured 20 m
surrounded by a matrix of smaller grain size of 2 m.[185]
Figure 5.12. SEM micrograph of chemically etched 2SBNF.
Figure 5.13. SEM micrograph of chemically etched 3SBNF. Arrows indicate herringbone
domain structures.
(a) (b)
Figure 5.14. SEM backscattered imaging micrographs of second phases found in polished (a)
2SBNF and (b) 3SBNF. Yellow arrows indicate light grey second phase.
Figure 5.15. SEM backscattered imaging micrograph of second phases found in polished
4SBNF. Yellow arrow indicates light grey second phase, and red arrow indicates white
second phase.
In 2008, Jenko et al. reported that a second phase was present in NKN when sintered at
1100C.[185] This phase is found to be sodium deficient, however was not determined.
Such a second phase is also visible in the 2, 3, and 4 SBNF samples. In the 2SBNF and
3SBNF samples, a light grey second phase is visible (Figure 5.14); it is sparse in 2SBNF and
slightly more prominent in 3SBNF. EDAX analysis confirms that the second phase is
potassium rich, though contains all elements included in the formulation (Na, K, Sr, Ba, Nb,
Fe).
In 4SBNF, however, there are two second phases detected in backscattered mode.
The SEM micrograph for a polished sample (Figure 5.15) shows the matrix grains in dark
grey, and the second phases are shown as light grey and white (both indicated by yellow
and red arrows, respectively). This white second phase was not visible in the other
samples, suggesting that 3SBNF is the solubility limit for SBN addition. EDAX analysis
shows that this phase, in comparison to the one found in other SBNF-doped formulations,
is potassium deficient and barium rich. Laboratory XRD, however, shows no evidence of a
second phase in the system. Consequently, higher resolution XRD was undertaken by
synchrotron XRD. This is reported in Chapter 6).
5.6 Electrical Properties
5.6.1 Dielectric Properties

There were two threads of investigation. The first was investigating the relative
permittivities and transition temperatures of xSBNF (x = 2, 3, 4) in comparison with NKNF.
The second focussed on one formulation (2SBNF) and examined how the permittivities
and transition temperatures varied with sintering time.
5.6.1.1 Relative Permittivity as a Function of SBN Doping

By converting the capacitance for each sample into relative permittivity (for experimental
procedure, see section 3.3.6.2), which takes the sample dimensions into account, the
relative permittivity of each formulation can be directly compared to those for other
samples. As the formulations of interest are 2-4 SBNF, only these are being discussed in
this section. The NKNF sample was also analysed, in order to directly compare the effect
of SBN addition to NKN.
7000
1400
NKNF
1200
6000 2SBN
1000 3 SBN
800 4 SBN
5000
600
4000 400
Permittivity
200
3000
0
20 60 100 140 180 220 260
2000
1000
0
0 50 100
250 300 150
350 200
400 450 500 550
Temperature (C)
Figure 5.16. Permittivities of (100-x)NKN-xSBN + 0.45wt% Fe2O3 (4h) (at 100 kHz), with
lower temperatures magnified, inset.
It is clear in Figure 5.16 that as SBN is added to NKN, the transition temperatures, both TO-
T and TC decrease. The NKNF sample has a Curie transition temperature of 457C and TO-T
of 234C. This sample was sintered at 1100C, giving the optimal density and thus
sintering temperature for NKN. The SBN-doped samples were sintered at the higher
temperature of 1140C to yield optimal electrical results. When plotted together (Figure
5.17) the transition temperatures significantly reduce with increasing SBN. However
there is an interesting effect at the Curie transition. The 2SBNF sample has a significantly
lower relative permittivity value of 4500 at TC (427C), which is relatively small in
comparison to NKNF which was 6500 at 457C. So the 2SBNF sample has a smaller
relative permittivity value at the transition temperature than NKN (where TC is 30C
lower).
500
450
400
Temperature (C)
350
Tc
300
To-t
250
200
150
0 1 2 3 4
x SBN (%)
Figure 5.17. The transition temperatures of (100-x)NKN-xSBN + 0.45wt% Fe2O3 (4h)
As the SBN addition increases, the transition temperatures continue to decrease, but the
relative permittivity at TC increases again, to 6000 (at 416C) for 3SBNF. Similarly for the
4SBNF formulation there is a decrease again to 3800 (at a lower transition temperature of
397C). Although there is no direct relationship between the relative permittivity value
and SBN doping at TC, there is the significant decrease in the transition temperature, as
shown in Figure 5.17. This is the same for the orthorhombic to tetragonal transitions, TO-T,
where SBN addition to iron-doped NKN decreases from 234 to 196C. Again, there is no
direct relationship between the values of permittivity, as shown in the inset of Figure 5.16,
although there is a significantly higher permittivity in the 3SBNF sample.
Tashiro, Ishii and Wada reported that the Curie temperature of NKN decreases as the
addition of strontium to the A-site increases.[106] This is also the case for the doping of
NKN by barium titanate (BT); Lin, Kwok and Chan reported a linear decrease of
approximately 22C per 1 mol% addition of BT.[83] In the present study, the addition of
SBN decreased the Curie temperature by 14.7C per 1 mol% addition, which is at a lower
rate than with the addition of BT.
The decrease in the orthorhombic to tetragonal phase transition temperature is at
a rate of 9.0C per 1 mol% SBN addition, whereas the BT rate of decrease was by 25C per
1 mol%. The rates for SBN doping are significantly lower for both transition
temperatures, although significantly lower than the BT rate for TO-T. This significant
difference could be due to the Ti4+ atomic substitution into the Nb5+ B-site in BT (where
Nb5+ is in the B-site in both NKN and SBN).
5.6.1.2 Relative Permittivity as a Function of Sintering Time

To continue the investigation of SBN doping of NKN, one formulation was chosen (2SBNF)
and samples were sintered at various sintering times. These were 4, 8, 16, 24 and 72
hours. All samples were over 94% dense. The resulting relative permittivities and
transition temperatures were determined (Figure 5.18). The data shows that the sintering
time is not a significant factor. The 4 hour sintered sample has a TC of 427C, whereas the
72 hour sintered sample has 436C. There was even less difference for the orthorhombic-
tetragonal phase transition temperatures. These results show that it is not necessary to
examine (in any subsequent studies) the effect of sintering time in SBN doped NKN
samples.
500
450
400
Temperature (C)
350
Tc
300
To-t
250
200
150
0 10 20 30 40 50 60 70
sintering time (hours)
Figure 5.18. The effect of sintering time on the transition temperatures of 2SBNF.
5.6.2 Field Response Hysteresis Loops
5.6.2.1 Effect of SBN doping

The hysteresis behaviour of xSBNF (2 x 4) formulations were also investigated. Field
response measurements take into account the size of the sample, and so the results are
directly comparable to each other. In 2006, Chang et al reported the P-E hysteresis
behaviour of NKN along with 0.5 mol% AETiO3 (AE = Mg, Ca, Sr, Ba) alkaline earth
dopants.[95] They showed that the addition of these dopants was detrimental to the
remnant polarisation, Pr, of NKN as the undoped material had the highest Pr of 18.8
C/cm2 and a coercive field of Ec = 9.65 kV/cm. Such high properties have not been seen
for undoped NKN elsewhere.[155]
From the present work it is clear that when 0.3wt% Fe2O3 is added to NKN, the hysteresis
behaviour changes. It exhibits a slightly higher Pr of 22 C/cm2, which is desired, although
a larger coercive field of 16.5 kV/cm, which is undesirable. This can be seen through the
effect of a lossy hysteresis loop, which is shown in blue in Figure 5.19.
The preferred type of hysteresis loop is considerably more saturated with a much
lower coercive field and a higher Pr value, like the one shown in red in Figure 5.19; this is
for the 2SBNF formulation. This loop shows that the addition of SBN to NKN is highly
advantageous for hysteresis behaviour.
Both samples broke down in fields above 40 kV/cm, which is in agreement with
other NKN publications.[70, 106, 187]
NKN + 0.3 wt% Fe2O3 (Ts = 1090C) 30
2 SBNF (Ts = 1140C)

20
P (C/cm2) 10
0
-40 -30 -20 -10 0 10 20 30 40
-10
-20
-30
E (kV/cm)
Figure 5.19. Hysteresis behaviour of NKN + 0.3wt% Fe2O3 (Tsint = 1090C) and 2SBNF
(Tsint = 1140C)
30
2 SBNF 20
3 SBNF
4 SBNF 10
P (C/cm2)
0
-40 -30 -20 -10 0 10 20 30 40
-10
-20
-30
E (kV/cm)
Figure 5.20. P-E hysteresis behaviour for (100-x)NKN-xSBNF (2 x 4).
When comparing the hysteresis loop of 2SBNF to 3 and 4 SBNF samples (Figure 5.20), the
4SBNF sample is clearly the poorest formulation in terms of domain switching and Pr and
EC values. The 2SBNF sample has the highest Pr with 25 C/cm2, although 3SBNF has a Pr
of 24 C/cm2 and they both have identical coercive fields of EC = 8.8 kV/cm. In
comparison with pure NKN, which has a Pr of 18.8 C/mm2 and a Ec of 9.65 kV/cm,[95]
these are both significantly improved properties.
The 4SBNF sample shows a lower Psat (19 C/cm2), which could be related to the
second phases visible in the microstructure (Section 5.5). These could cause a larger
disruption in the microstructure and domain configuration, thus restricting domain wall
movement in larger grains.
Interestingly, the 3SBNF sample, although it has very similar properties to 2SBNF, when
under a negative field it does not reach full saturation of aligned domains to the direction
of the field. This occurs in a positive field, as shown by the sharp end on the hysteresis
loop, although in the negative field end of the loop is visibly more blunt and rounded,
indicating full saturation has not been achieved. When the field was increased, however,
the sample broke down and a fully complete saturated loop could not be acquired. The
rounding of loops at the extreme edges can be caused by conduction in the sample,[115]
which for such samples is undesirable.
Figure 5.21 shows the switching of 4SBNF as the applied electric field increases, to give a
fully saturated loop. A fully saturated loop is preferred as it shows that the domains are
fully switched and aligned with the direction of the applied field in both directions. The
sample exhibits a Pr and EC of 19 C/cm2 and 10 kV/cm respectively. These results,
however, are marginally enhanced from NKN, which exhibits maximal values of Pr = 18.8
C/cm2 and EC = 9.65 kV/cm.[95]
25
40 kV/cm
35 kV/cm 20
30 kV/cm
25 kV/cm 15
20 kV/cm
10
15 kV/cm
10 kV/cm 5
5 kV/cm
P(C/cm2)
0
-40 -30 -20 -10 0 10 20 30 40
-5
-10
-15
-20
-25
E (kV/cm)
Figure 5.21. Hysteresis behaviour of 4SBNF at varying field strengths.
It is difficult to directly compare these results with published data due to the lack of
tetragonal tungsten bronze type (TBT) materials doping perovskite NKN. Similar dopants
for the purpose of discussion are the alkaline earth doping of NKN (AE = Mg, Ca, Sr and Ba)
of which SBN (Sr0.5Ba0.5)Nb2O6 contains two of these(also on the A-site). Chang et al.
reported the effect of adding 0.5 mol% AETiO3 to NKN.[95] The resulting P-E hysteresis
behaviour showed a lower EC and higher Pr for undoped NKN than for any of the dopants,
as discussed earlier. The Pr value they reported for NKN is 18.8C/cm2 whereas the
2SBNF sample exhibits 25 C/cm2 (Figure 5.19), showing a significant rise in the remnant
polarisation; the coercive field values are nearly identical. This soft effect of a relatively
high Pr and low EC is a good result for SBN doping of NKN. Similar changes in properties
are often found near orthorhombic to tetragonal MPB regions due to the increased
number of directions in which the spontaneous polarisation can occur, along with an
increased number of domains in the microstructure.[188]
In spite of this enhanced result, similar Pr values have been reported, such as Pr =
25 C/cm2 and EC =18.5 kV/cm in 94.8NKN-5.2LiSbO3.[115] Although the remnant
polarisation value is identical to that of the 2SBNF sample investigated here, the reported
coercive field value is more than double that of the 8.8 kV/cm for 2SBNF.
The combined iron addition and SBN doping could have a significant effect on this
composition. When 0.5mol% Fe2O3 was added to NKN, Zuo et al reported the Pr value
increased from 15.1 to 21.5C/cm2.[70] This is a significant increase, attributed to the
addition of Fe3+ ions to the B-site Nb5+, creating oxygen vacancies. However, it is well
documented that acceptor doping (such as in this investigation) creates hard
piezoelectric materials with oxygen vacancies, which should decrease Pr and increase
EC.[18] This is due to the vacancies causing domain wall pinning, and this in turn causes
the coercive field to increase. The relatively small addition of iron in this case may counter
this hardening effect and optimise NKN. This effect may be seen with larger amounts of
iron doping.
In 2011, Li et al. reported that Li0.06(Na0.535K0.48)0.94NbO3 (NKLN) doped with 0.7mol% ZnO
as a sintering aid exhibited an optimal Pr value reaching 21 C/cm2 and EC =7.5
kV/cm.[99] This shows that 2SBNF and 3SBNF formulations exhibit properties
comparable to leading NKN dopants.
5.6.2.2 Effect of Sintering Temperature and Time

In a subsequent investigation of 2SBNF, the sintering temperature was increased from
1140C to 1160C. The resulting hysteresis behaviour was practically identical (shown as
blue in Figure 5.22), and so is not advantageous for the material, and yet would cost more -
in time and money.
A sample sintered at 1140C for 24 hours (as opposed to the standard 4 hours
used for all samples discussed in this chapter) was also investigated. As mentioned in
Section 5.6.1.2, the dielectric data did not vary greatly for the 4 hour sample, however it
exhibits significantly different hysteresis behaviour. As can be seen by the green line in
Figure 5.22, both Pr and EC are weakened, down to 23 C/cm2 and 21 kV/cm respectively.
The increased EC means that the material has become harder with the longer sintering
time. This is due to more oxygen vacancies being generated in the material.[155] These
vacancies must form during the sintering process, where there is more time available at
the elevated sintering temperature (in this case, 1140C) to allow oxygen to escape from
the material.
Although hardening is not necessarily a desirable property for doped NKN (as soft
piezoelectrics are used for ultrasound transducers, sensors and actuators[18]) it does
offer a beneficial reason for the longer sintering time. The sample can withstand higher
electric fields than other NKN materials, either here in this investigation or reported in the
literature.[70, 106, 187] This 2SBNF sample sintered at 1140C for 24 hours sustained a
field of 60 kV/cm, which is higher than any other value reported. The result is shown by
the orange line in Figure 5.22.
35
1160C, 4h 30
25
1140C, 4h
20
1140C, 24h 15
1140C, 24h 10
(higher E) 5
P(C/cm2)
0
-60 -50 -40 -30 -20 -10 -5 0 10 20 30 40 50 60
-10
-15
-20
-25
-30
-35
E (kV/cm)
Figure 5.22. P-E behaviour for 2SBNF sintered at 1140 and 1160C (4h) (navy and red
respectively), and at 1140C (24h) at 40 and 60 kV/cm (green and orange respectively)
When looking at the effect of fields applied to the 24 hour sintered sample (Figure 5.23), it
is clear that the saturation of domains does not occur as quickly as in 4 hour sintered
samples (see Figure 5.21). The S-shaped saturation curve is only initially visible at a
field of 35 kV/cm, which is nearly the breakdown field of the 4 hour samples. As Figure
5.21 shows for 4SBNF, the saturated S-shaped curve is already forming at a field of 15
kV/cm. This shows that there is faster switching in the 4 hour samples than in the 24 hour
sample.
5 kV/cm 30
10 kV/cm
15 kV/cm 25
20 kV/cm
25 kV/cm
20
30 kV/cm 15
35 kV/cm
40 kV/cm 10
45 kV/cm
50 kV/cm 5
55 kV/cm
0
P(C/cm2)
60 kV/cm
-60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60
-5
-10
-15
-20
-25
-30
E (kV/cm)
Figure 5.23. P-E behaviour for 98NKN-2SBN + 0.45wt% Fe2O3 (Tsint = 1140C, 24h)
5.6.3 Impedance Spectroscopy

Impedance Spectroscopy was used to investigate the resistivity, conduction processes and
activation energies of NKN and the NKN-SBN systems. The data is presented as -
plots, as opposed to the Z- Z plots that are usually shown in the literature. This is due to
the fact of the samples dimensions being included in the data, as defined in Equation 5:1,
(A is the surface area of the sample disc, t is its thickness and is the conductivity) and so
is more easily comparable to other data that is published elsewhere.
Z*A 1
* Equation 5:1
t
5.6.3.1 Varying SBN Content

The - plot for NKNF is shown in Figure 5.24, for varying temperatures. It is clear that
there is only one major impedance arc present, which is due to the bulk contribution to
polarisation and conduction in the material. There is a small second arc at low frequencies
(at the right end of the arc) from the grain boundary contribution, however this is not
taken into account in this case. The major contribution is from the grain, which is the main
arc, and so the data is extrapolated down to find max.
As the applied temperature increases, max and max both decrease (not only for this
composition, but for all of those investigated in this section). This loss in resistivity
behaviour is due to the presence of space charge polarisation in the ceramic
materials.[189]
As the temperature of the sample increases, it is clear that resistivity will decrease
(as more thermal energy is available), as shown in Figure 5.24. However the conduction
process needs to be identified.
0.14
465C
0.12 485C
505C
525C
0.10
545C
565C
0.08 585C
605C
"(km)
0.06 625C
645C
0.04
0.02
0.00
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 0.24
'(km)
Figure 5.24. - plot for NKN + 0.45wt% Fe2O3, with varying temperatures (465-645C)
Investigating the (100-x)NKN-xSBN + 0.45wt% Fe2O3 ceramics (all sintered for 4 hours)
shows how the resistivity of the system can change with SBN content. This is represented
graphically in Figure 5.25, at 545-550C (in the cubic region of the system). As NKN is an
insulator, it should have as high a resistivity as possible, or conversely the lowest
conductivity possible.
The iron-doped NKN composition (x = 0) was found to have a very low resistivity
of 0.08 km, however with the addition of 2 and 3 mol% SBN, this significantly increased
to 4.7 and 5.0 km respectively (at temperatures 545-550C). This shows that the
addition of TBT Sr0.5Ba0.5Nb2O6 to NKN is advantageous for the electrical insulative
properties of NKN. It must be noted, however, that 4 mol% addition was not so beneficial
to the system, as it had a lower resistivity of 0.27 km (but still higher than that of iron-
doped pure NKN).
3.0
0 SBN
2.5 2 SBN
3 SBN
2.0
4 SBN
"(km)
1.5
1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
'(km)
Figure 5.25. Resistivity spectra for (1-x)SBN + 0.45wt% Fe2O3 (4h) at 545-550C.
An Arrhenius plot (ln 1000/T) of resistivity data (Equation 5:2) is shown in Figure
5.26. The gradient of the linear relationship yields Ea/kB. These data are included in
Figure 5.26. By multiplying the gradient by Boltzmanns constant (kB = 1.38065 1023
J/K),[37] the activation energy is obtained (discussed later).
Ea
0 e k BT
Equation 5:2
1000/T
0
0.9 1.0 1.1 1.2 1.3 1.4
0 SBN
-2
2 SBN
y = -6.92x + 3.99
-4 3 SBN
4 SBN
y = -11.45x + 8.36
ln
-6
-8
y = -13.49x + 8.02
-10 y = -13.46x + 7.88
-12
Figure 5.26. Conductivity-temperature plots for (100-x)NKN-xSBNF + 0.45wt% Fe2O3, with
x = 0, 2, 3 and 4 mol% (navy, red, green, and blue respectively).
The relationship between activation energies with respect to SBN addition is depicted
graphically in Figure 5.27. It is observed that pure NKN has Ea = 0.60 eV ( 0.03 eV)
showing that the main contribution to polarisation is electronic conduction, and comes
from the bulk of the material. This is in agreement with Matsudo et al. who reported an
activation energy of 0.65 eV for NKN at temperatures above 390C.[190]
The activation energy increased significantly to above 1 eV with addition of SBN
(until 4 mol%), showing a change in conduction process within the material. Although this
is higher than that for pure NKN, all of these activation energies for this system show that
the conduction process stays the same in the material, in that the process is via oxygen
vacancy migration. It is well documented that an activation energy value of 1eV shows
ionic conductivity attributed to doubly-ionized oxygen vacancies VO (as shown in
Equation 5:6).[64, 191-192] This suggests that there are oxygen vacancies in the system,
even though iron doping helps improve the system density, there are still vacancies
present which allow conduction.
1.4
1.2
1.0
0.8
Q (eV)
0.6
0.4
0.2
0.0
0 1 2 3 4
x% SBN
Figure 5.27. Activation energies for (100-x)NKN-xSBN + 0.45wt% Fe2O3, with 4 hours
sintering time.
Zuo et al. studied the effect of Fe2O3 in NKN and reported Fe3+ ions replacing B-site
Nb5+.[70] The similar ionic radii of 0.64 for Nb5+ and 0.65 for Fe3+ allow relatively easy
substitution without distorting the crystal lattice. This replacement causes oxygen
vacancies, and further vacancies can result from SBN doping, aiding the sintering process.
Hence there are two sources of oxygen vacancies. As NKN suffers sodium and potassium
evaporation during sintering, a non-stoichiometric structure is results. Defect equations
showing the changes (written in Kroger-Vink notation) are given as Equations 5:3-5:7.
Equation 5:7 shows the defect equation for
the evaporation of sodium in the system, following Equations 5:3-5:6.
Equation 5:3
Equation 5:4
Equation 5:5
Equation 5:6
Equation 5:7
As the SBN and iron-doped NKN have higher activation energies, it suggests that there is a
decrease in the concentration of oxygen vacancies in the material in comparison with pure
NKN. This is in accordance to the density changes, showing that iron doping creates less
vacancies in the system, and so is another way of concluding that SBN and iron doping is
beneficial to the NKN ceramic system.[47, 65]
Perovskites such as NKN are known to contain intrinsic defects, which are
primarily vacancies on the A (in this case, Na and K) sites and the O sites. An increase in
the number of A-site vacancies increases the resistivity of perovskites, or conversely
decreases the conductivity, which is desirable. As the highest resistivity is observed in the
iron-doped 2 and 3 SBN samples, this could be a link to the number of vacancies in the
material. This means that free electrons in the material are captured by the electron holes
produced by the A-site vacancies, and thus less are available to freely conduct, thus giving
insulative properties.
Table 51 summarises the data for the (100-x)NKN-xSBN + 0.45wt% Fe2O3 system at
545C (paraelectric region). It may be concluded that the optimum addition for this
system is 2-3 mol% SBN addition, as it has the highest resistivity for the bulk (and thus
also the lowest conductivity values) for conduction.
Table 51. Summary of electrical data for (100-x)NKN-xSBN + 0.45wt% Fe2O3 system, at
545C.
X mol% SBN max (m) min (S/m) error (S/m) Q (eV)

0 80 0.0125 781.25 x 10-6 0.60
2 4700 0.00021 4.47 x 10-6 1.16
3 5000 0.0002 4.00 x 10-6 1.16
4 270 0.0037 137.04 x 10-6 0.99
5.6.3.2 Effect of Sintering Time
Figure 5.28 shows a - plot for 2SBN + 0.45 wt% Fe2O3 as a function of sintering time
for data collected at 645C (in the cubic region of the material), with sintering times of 4, 8,
16, 24 and 72 hours (all at 1140C). It is clear that as the sintering time rises from 4 hours
to 16 hours, the resistivity of the material increases from 0.75 km for 4 hours to 0.95
km for 16 hours (taking the main arc representing the bulk contribution). It then drops
dramatically as the sintering time increases to 24 and 72 hours (light blue and purple
markers respectively), where the resistivity significantly decreases to 0.12 km (for the
72 hour sample).
0.60
0.55 4h
8h
0.50
16h
0.45
24h
0.40 72h
0.35
0.30
"(km)
0.25
0.20
0.15
0.10
0.05
0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
'(km)
Figure 5.28. - plot for 98NKN-2SBN + 0.45wt% Fe2O3, with sintering times of 4, 8, 16, 24
and 72 hours at 1120C (navy, red, green, blue and purple respectively).
The Arrhenius plot of the data (Figure 5.29) shows that activation energies did not vary
greatly, around 1.15 eV (0.15 eV). With consistent values around 1.0 eV for all samples,
the conduction process as expected does not change with sintering time. Hence this
suggests the same conduction process as found in the previous section, indicating oxygen
vacancy migration.
1.4
1.2
1.0
0.8
Q (eV)
0.6
0.4
0.2
0.0
0 10 20 30 40 50 60 70 80
Sintering Time (hrs)
Figure 5.29. Activation energies of 98NKN-2SBN + 0.45wt% Fe2O3, as a function of sintering
time.
In order to produce an equivalent circuit for this composition, further work will need to be
undertaken. However, under closer inspection, the Cole-Cole plots do not pass directly
through the origin (typically less than 50 away from it), meaning that an extra
impedance element would need to be included in the circuit.[62]
The 4 hour sintered 2SBNF sample has a higher resistivity (both max and max) than the
24 hour sample (shown in Figure 5.28), even though the activation energies are similar.
From the P-E hysteresis behaviour, it is clear the 4 hour sample has a more desirable
hysteresis loop (ie a higher Pr and lower EC) than that of the 24 hour sample (Figure 5.22).
This clearly shows that a longer sintering time is detrimental to the electrical properties of
such samples.
5.7 Chapter Summary

The novel work on the addition of SBN to NKN yielded beneficial results in terms of
sample properties.
Fe2O3 is an effective sintering aid for NKN. The addition of 0.3 wt% Fe2O3 increased the
density from 90 to 94% theoretical. For the NKN-SBN system, a slightly higher addition of
0.45 wt% was required, resulting in densities over 96% theoretical in formulations
containing 2-4 mol% SBN. These formulations were investigated in this study. These
samples required a higher sintering temperature of 1140C, 40C higher than that needed
for NKN and NKNF. Laboratory XRD showed 4SBNF was the solubility limit for single
phase orthorhombic NKN.
In terms of grain morphology, 2SBNF showed equiaxed grain structures with 3 m size,
exhibiting lamellar 180 domains. The 3 and 4 SBNF samples showed bimodal grain size
distributions, where grains up to 15 m in size were found within a predominantly 2 m
grain sized matrix. The larger grains exhibited herringbone domain structures.
The electrical properties of samples prepared with 2-4 mol% SBN additions were very
encouraging. NKNF exhibited TC = 457C, TO-T = 234C, r = 336, Pr = 22 C/cm2 , EC = 16.5
kV/cm, Q = 0.60 eV and = 0.08 km. Typical values for NKN are TC = 420C, TO-T =
200C, r = 460, Pr = 18.8 C/cm2 , EC = 9.65 kV/cm, Q = 0.65 eV.[29, 95, 111, 165, 190]
The addition of SBN caused TC to decrease by 14.7C per 1 mol% SBN addition; the rate of
TO-T decrease was 9.0C per 1 mol% SBN addition. As SBN levels increased, the value of
permittitivity at the TC also decreased (the value for 4SBNF was approximately half that of
NKNF, 3750 and 6470, respectively).
In terms of hysteresis behaviour, the optimal formulation was 2SBNF, with fully
saturated loop resulting in Pr = 25 C/cm2 and EC = 8.8 kV/cm (though 3SBNF had very
similar properties). For higher level of additions, 4SBNF properties deteriorated
exhibiting Pr = 19 C/cm2 , EC = 10.0 kV/cm a smaller remnant polarisation than that of
NKNF.
Samples with 2SBNF and 3BNF additions exhibit the highest resistivity of 4.7 and 5.0
km, respectively. The 4SBNF formulation has significantly lower resistivity of = 0.27
km, although this is still higher than that for NKNF. The resulting activation energies for
2-4 mol% SBN additions are larger than 1 eV which suggests that the conduction process
is through an ion transport process, possibly oxygen vacancy migration.
The transition temperatures of 2SBNF did not change significantly with sintering time,
although longer sintering time yielded materials that can withstand higher electrical fields
(up to 60 kV/cm) producing fully saturated hysteresis loops. Longer sintering times also
resulted in a decreased activation energy, showing that conduction is slightly easier.
6 SYNCHROTRON ANALYSIS OF XSBNF FORMULATIONS
6.1 Introduction
As reported in Chapter 5, the laboratory XRD spectra (Figure 6.1) reveal a predominantly
orthorhombic structure, as expected for NKN compositions, with 4SBNF showing a
transition to tetragonal (indicated by peaks at 45-47 2 having identical height). The aim
of the synchrotron experiment was to investigate the phase content of orthorhombic and
possible tetragonal phases present in the NKN matrix using high resolution XRD. By doing
so, the changes in microstructure and unit cell lattice parameters as a function of SBN
addition could also be studied. Small amounts of second phase were detected in SEM
images, however, which were not revealed by laboratory X-ray diffraction. Figure 6.2
shows the visible second phases in 4SBNF, as light grey and white patches. The dark grey
matrix phase is NKN, though orthorhombic and tetragonal phases cannot be distinguished
in SEM.
The Diamond Light Source was therefore used to investigate the NKN matrix
structure and second phases in (100-x)NKN xSBN + 0.45wt% Fe2O3 ceramics. All
samples were investigated as crushed powder, to eliminate sample strain and grain
orientation.
Figure 6.1. Laboratory XRD profiles of (100-x)NKN xSBN + 0.45wt% Fe2O3 formulations (0
x 4)
Figure 6.2. SEM micrograph of 4SBNF polished sample, showing light grey and white second
phases in a dark grey NKN matrix phase. Yellow arrow indicates light grey second phase, and
red arrow indicates white second phase.
6.2 Synchrotron Data Analysis

The synchrotron diffraction profiles are shown in Figure 6.3. When compared with
laboratory XRD (Figure 6.1) the difference in resolution (including the presence of second
phases) is clear. The difference in the 2 peak positions is due to the use of radiation of
different wavelengths (laboratory XRD = 1.54060 and synchrotron XRD = 1.40000 ).
20000
4 SBN
18000
3 SBN
2 SBN
16000
1 SBN
0.5 SBN
14000 0 SBN
12000
10000
8000
6000
4000
2000
0
10 12 14 16 18 20 22 24 26 28 30
Two Theta (synchrotron)
Figure 6.3. Synchrotron XRD profiles of xSBNF formulations (0 x 4)
It is also clear in Figure 6.3 that there is a second phase detected in the 4SBNF sample (the
major peaks of this second phase are indicated), and is starting to form at lower SBN
additions. Though this is relatively low content in comparison to the 4SBNF peak
intensities, it is endeavoured to determine this phase (discussed in section 6.2.4).
6.2.1 NKNF Refinement
Data refinement shows that 0.45 wt% Fe2O3 addition to NKN does not significantly affect
the structure. The room temperature synchrotron data indicated that NKN was
orthorhombic, as expected. In Figure 6.4, the refined data is very close to the experimental
data, where an orthorhombic model was applied. The difference between the two is shown
by the grey line at the bottom of each diffractogram. This is confirmed by the small
Goodness of Fit (GOF) value of 3.61. This is an extremely close fit considering the large
number of data points in the refinement and the large range of 2. This shows that low
level iron doping does not affect the NKN structure. It is also a good starting point for the
refinements of SBN-doped formulations.
(a)
(b)
Figure 6.4. The refinement of NKNF as (a) the full refinement (square root y axis) and (b)
peak profiles of 10-50 degrees 2 (logarithmic y axis). The blue line shows the observed
data, the red line shows the calculated model, and the grey line below shows the difference
between the two.
The unit cell parameters resulting from this refinement are a = 3.94433, b = 5.64356
and c = 5.67611. The pseudocubic monoclinic parameter lengths a and b for NKNF are
3.9443372 and 4.002125 . These are very close values reported by Tellier et al for NKN
(a = 4.0046 and b = 3.9446 ).[163] This is a good indication that the refinement is
successful and that the iron addition does not have an effect on the orthorhombic NKN
unit cell size. This is in agreement with the findings of Zuo et al. that Fe2O3 does not
change the crystal symmetry ( 4 mol%).[70]
6.2.2 0.5 and 1SBNF Refinement
Data for 0.5SBNF refined well to an orthorhombic structure with a low GOF of 3.86.
Introduction of a tetragonal phase into the refinement model reduced the GOF to 3.02.
The refinement suggested that the tetragonal component amounted to approximately
14%, which is significant.
In light of this finding, a tetragonal phase was included in the NKNF refinement,
but the tetragonal phase did not improve the refinement in any way. This shows that SBN
doping is the sole cause of tetragonal phase formation in NKN. This, however, is a valid
conclusion as SBN has a tetragonal TBT structure.
When 1 mol% SBN was added to NKNF, the tetragonal phase was more prominent in the
material, supporting the argument that the tetragonal phase is present as a result of SBN
addition. The proportion of tetragonal phase increased to 21%, and the GOF value was
4.36. There are a number of small undefined peaks between 17 and 20 2, and
sporadically along the baseline; this is one reason for the higher GOF value in this case.
Figure 6.5. The refinement of 1 SBNF.
6.2.3 2-3 SBNF Refinements

Similarly, refinements of 2SBNF and 3SBNF gave orthorhombic to tetragonal ratios of 91:9
and 92:8, respectively. The GOF values were much lower, at 2.66 and 2.99 for 2 and 3
mol% SBN addition, respectively. Figure 6.6 shows the refinement of 3SBNF. In spite of
the very good fit between the experimental data and the refined model (the difference is
shown by the grey line in Figure 6.6), there were some peaks between 13 and 20 2 that
were not refined, giving rise to the slightly higher GOF value. Inclusion of SBN as a
separate phase did not improve the model or the refinement.
Figure 6.6. The synchrotron XRD spectrum and refined data for 3SBNF (logarithmic y-axis)
6.2.4 4 SBNF Refinement

This refinement was significantly different to previous ones as the second phase was
considerably more prominent (Figure 6.7a). By refining the whole diffraction spectrum
(5-145 2) with the orthorhombic and tetragonal phases, as previously, the ratio of
orthorhombic to tetragonal phase is 83:17, giving a GOF value of 3.37. In order to take
into account the second phase, SBN was included in the refinement model. Structural data
for SBN was taken from the work of Podlozhenov et al.[193] Inclusion of SBN in the
refinement model was successful (as is evident in Figure 6.7b) and the GOF value fell to
2.58, which is the lowest value recorded for all the refinements. The resulting model
showed 3% SBN phase in the material.
(a)
(b)
Figure 6.7. Synchrotron diffraction profile for 4SBNF (a) in the range 0-46 2, square-root
y-axis, and (b) in the range 10-48 2, logarithmic y-axis.
That the SBN phase was detected in the 4SBNF material is a significant finding. Under
laboratory XRD there was no evidence of a second phase (Figure 6.1) and yet was visible
in SEM. EDAX analysis on the second phase in 4SBN (Chapter 5, Section 5.5), however,
found that this structure was potassium and barium rich, which is not the correct ratio of
elements for an SBN phase. This proves that the SBN phase found in this case is not
necessarily SBN, but a phase comprising of a very simliar tetragonal tungsten bronze type
(TBT) structure.
Following this discovery, data for the 2 and 3 SBNF materials were reinvestigated,
including the SBN phase. This was not productive even though the unidentified peaks
were in similar positions to those for the SBN peaks (Figure 6.3). It is possible that the
amount of second phase in the 2SBNF and 3SBNF samples is lower than 1%, which is the
limit of resolution in the TOPAS program.[194]
6.3 Summary of Data from Refinements
6.3.1 Phase Content

The refinements gave a good indication of the orthorhombic and tetragonal phases
coexisting in the NKN-SBN system. The resulting phase proportions in (100-x)NKN-xSBN
+ 0.45wt% Fe2O3 samples are summarised in Table 6.1 and Figure 6.8. Phase content is
accurate to 1% in Topas refinements.[194] It is clear that samples with 0.5 and 1 mol%
addition have the highest tetragonal to orthorhombic ratio and the highest GOF value,
indicating that these samples warrant further investigation.
Table 61. The phase content for xSBNF refinements, including GOF values.
x% SBN Orthorhobic (%) Tetragonal (%) TBT (%) GOF
0 100 0 0 3.61
0.5 85 15 0 3.02
1 79 21 0 4.36
2 91 9 0 2.64
3 92 8 0 2.99
4 82 15 3 2.58
The data are illustrated in Figure 6.8. It is clearly seen that as SBN is added to the iron-
doped NKN, the orthorhombic nature of the structure decreases as the tetragonal
component increases; this is clearly influenced by the SBN, which has tetragonal TBT
structure. Although the 1SBNF has a 20% tetragonal component, its presence was only
revealed by high resolution synchrotron XRD.
As SBN doping increases to 2 and 3 mol% there is a reduction in tetragonal component to

~10% and corresponding increase in the orthorhombic component. As noted in Chapter
5, the samples prepared with 2-4 mol% SBN have the optimal electrical properties. At this
doping level the samples exhibit the largest orthorhombic component and indeed the
4SBNF sample also contains a TBT phase to the level of 3%.
100
90
80
70
% phase content
60 orthorhombic
50 tetragonal
40 TBT phase
30
20
10
0
0 1 2 3 4
x% SBN
Figure 6.8. Phase Content in NKNF as a function of x mol% SBN addition.
This is in agreement with the SEM for xSBNF formulations. Figure 6.2 clearly shows
second phases (shown as light grey and white patches within a dark grey NKN matrix);
although 2 and 3 SBNF showed second phases, these were very small and sparse, so no
conclusive EDAX data could be drawn. As these are not detected by sunchrotron XRD, the
phases are too small to be detected and thus are not deemed significant enough to warrant
further attention.
6.3.2 Lattice Parameters
6.3.2.1 Orthorhombic Phase

The lattice parameters for the orthorhombic phase are shown as a function of SBN
addition in Table 62 and Figure 6.9. The overall effect of the SBN doping gives rise to a
decrease in the b parameter (at a rate of 0.0006 per 1 mol% addition, and an average
increase in the a (and c) parameter of 0.0012 per 1 mol%. This shows that the
pseudocubic cell changes significantly as a result of SBN addition.
Table 62. Pseudo-cubic parameters for orthorhombic phase in xSBNF (accurate to 5dp)
x SBN a b
0 3.944337 4.002125
0.5 3.944066 4.001212
1 3.944789 4.001336
2 3.947180 3.999996
3 3.948753 4.000606
4 3.947859 3.999075
4.01
4.00
3.99
a' = c'
3.98
b'
3.97
3.96
3.95
3.94
0 1 2 3 4
x% SBN
Figure 6.9. The pseudocubic lattice parameters for the orthorhombic region of xSBNF. The
cuboid represents the shape of the unit cell (not to scale)
6.3.2.2 Tetragonal Phase

The tetragonal pseudocubic lattice parameters are shown in Table 63 and Figure 6.10.
They are clearly different from the orthorhombic lattice parameters. The tetragonal
pseudocubic lattice parameters change dramatically with composition. At low levels of
SBN additions a > b, but from 2% SBN b > a. These changes are significant as the
ferrooelectric properties are enhanced (as discussed in Chapter 5) in the 2-4 mol% SBN
region. For example, 2SBNF exhibits a Pr and EC of 25 C/cm2 and 8.8 kV/cm.
Table 63. Pseudo-cubic parameters for tetragonal phase in xSBNF (accurate to 5dp)
x SBN a b
0 - -
0.5 3.981284 4.005615
1 3.979612 4.007148
2 3.989798 3.975777
3 3.990946 3.974705
4 3.985617 3.972295
4.015
4.010
4.005 a' = c'

b'
4.000
3.995
3.990
3.985
3.980
3.975
3.970
0 1 2 3 4
x% SBN
Figure 6.10. Pseudocubic lattice parameters for the tetragonal region of xSBNF as a function
of SBN addition. Cuboids represent the shape of the unit cell (not to scale)
It is difficult to directly compare this data with other equivalent studies. Seo et al reported
tetragonal parameters for 5 mol% addition SrTiO3 (ST) to NKN (a = b = 3.39 and c = 3.75
); they are significantly smaller than values found in this study, although Seo et al. do not
indicate whether they relate to a pseudocubic unit cell, nor report data for undoped NKN.
Ahn et al. reported the coexistence of orthorhombic and tetragonal phases when
BaTiO3 (BT) was added to NKN.[195] For addition levels between 3 and 6 mol%, both
phases were detected. For 96NKN-4BT, the tetragonal parameters were a = 3.9663(4)
and c = 4.0126(6) and samples contained 67.4 % tetragonal component.[195] This is
significantly higher than the 15% tetragonal component found in this study for 4SBNF,
although lattice parameters are not grossly different.
6.3.2.3 Tungsten Bronze Type Phase
This phase was only refined in the 4SBNF formulation. The parameters for this are a =
3.948327(11) , b = 5.640070(17) and c = 5.670146(17) . This is based upon the SBN
structure applied to the refinement, however cannot be SBN due to the deficiency of
strontium in the second phases found by EDAX analysis (see Chapter 5, Section 5.5).
6.4 Chapter Summary

By use of synchrotron X-ray diffraction, second phases were detected and identified. In
the 4SBNF formulation a tetragonal tungsten bronze phase was identified; comprising 3%
of the sample. More generally, a tetragonal NKN phase was detected in all SBN doped
samples, coexisting with the orthorhombic NKN matrix. This tetragonal phase was found
to be present at levels up to 20% (for samples prepared with 1 mol% SBN).
Single phase NKNF exhibited an orthorhombic strcuture, as expected, with pseudo-
cubic parameters a = c = 3.94437 and b = 4.002125 . Lattice parameters for both
phases are given in Tables 6-2 and 6-3, as a function of SBN addition.
The most accurate refinements in the system were achieved for samples prepared with
2-4 mol% SBN, which showed an orthorhombic to tetragonal phase ratio of 9:1 for 2 and 3
SBNF; the 4SBNF samples contained significantly less orthorhombic phase, only 82%
along with 15% tetragonal (the remaining 3% was a tetragonal TBT phase).
The 2-4 SBNF formulations exhibit enhanced electrical properties (see Chapter 5) and the
lattice parameters change significantly with composition. Low (< 2%) SBN doping
generates a tetragonal unit cell with a large b lattice compared to a (and c). Higher
doping ( 2%) leads to a smaller b lattice parameter relative to a (and c) and it is this
structure of unit cell that is associated with enhanced electrical properties.
7 DEVELOPMENT OF A ROUTE TO PRODUCE ORIENTED NKN
THICK FILMS
7.1 Introduction
The method of tape casting is a relatively new approach to manufacturing textured
electroceramics. It is well known that single crystal ceramics have superior electrical
properties due to the lack of defects in their microstructure,[128, 134, 196] but they are,
however, difficult to grow and thus very expensive to produce.
There has been much effort into texturing ceramics in order to produce ceramics
that have electrical properties much like those of the single crystal, rather than bulk
ceramics that are most commonly produced. This chapter involves the development of an
orientation procedure for NKN ceramics to investigate whether thick film tape casting
multi-layering (up to 200m thickness) is a reliable and viable manufacturing procedure
for enhanced electrical properties.
The tape casting process is a relatively new process in this field; a few other research
groups have investigated the Templated Grain Growth (TGG) approach for NKN. These
include the Toyota group in Japan,[15-16] and a group in America spearheaded by Gary
Messing and Susan Trolier-McKinstry, the latter published their first findings in
2010.[197]
A method of orienting NKN developed by Saito and Takao (Japan) uses precursor
particles, most commonly those of plate-like Sodium Niobate (NN, NaNbO3) particles.[198]
As NN is one of the end members of NKN (those of NaNbO 3 and KNbO3), the NN can be
utilised to produce oriented NKN. The same group also attempted oriented NKN
production using KN precursor particles.[144] In order to produce both these template
particles, plate-like precursor particles, K4NbO17 [144, 198] or Bi2.5Na3.5Nb5O18 (BNN)
were produced to form the NN and KN template particles.[15, 118, 142, 144]
Other templates that have been used to orientate NKN, or other lead-free
perovskite materials, have been plate-like Bi4Ti3O12, SrTiO3 and BaTiO3; and acicular
(needle-shaped) Sr2Nb2O7, Al2O3-B2O3 and PbNb2O6.[138, 182-183, 199]
In order to produce oriented NN particles, Bismuth Sodium Niobate (BNN,

Bi2.5Na3.5Nb5O18) plate-like particles first need to be produced. These are converted into
NN particles using a topochemical process. This procedure was first reported by Saito et
al. (from the Japanese Toyota group) in 2004.[15] They reported that NKN can be
oriented using a Reactive Templated Grain Growth (RTGG) process using NN particles.
The resulting oriented NKN was found to have enhanced electrical properties in terms of
d33 of 416pC/N. This was a significant achievement in producing NKN-based materials
with such a high piezoelectric d33 constant.
It should be noted, that all published accounts of BNN and NN particle production, are very
vague in terms of experimental details. The following procedures have been developed
and investigated as independent research. The approach has been developed to ensure
optimal results with minimal raw material wastage. Therefore all stages were undertaken
in small batches and work on a small scale, which should be possible to scale up on a
production line.
Full details of the optimal processing route developed are given in Section 3.2.2.
7.2 The Production of BNN Particles
7.2.1 Crucible Selection

The first step of making Bi2.5Na3.5Nb5O18 (BNN) particles was to identify the most suitable
crucible. Initially, small pellets of BNN mixture were heat treated at 1100C on a variety
of crucible substrate materials (magnesia, alumina and platinum foil) to test if the material
would react with the oxides. The pellets reated severely with all the substrates, including
the platinum foil.
For BNN and NN particle production the Toyota research group use Platinum
crucibles,[15] whereas the research group of Gao Feng et al. in China use alumina
crucibles.[127] On this basis, small crucibles (no larger than 40mm high) of quartz,
alumina and platinum containing BNN were heated at 1100C. The results are shown in
Figure 7.1. The BNN mixture reacted with the alumina crucible, and proved difficult to
remove from it. The quartz crucible did not react with the BNN mixture, however the
product was visibly less yellow. This is possibly due to loss of Bismuth from the mixture.
The platinum crucible showed little signs of reaction with the mixture and the contents
retained the bright yellow colour. The BNN mixture was also relatively straightforward to
remove from the crucible using sonication techniques.
This shows that Platinum crucibles are evidently more suitable for processing
BNN. Consequently, Platinum crucibles were used for all stages of the production.
(a) (b) (c)
Figure 7.1. BNN particles heat treated under identical conditions, using (a) quartz, (b)
alumina and (c) platinum crucible.
7.2.2 Preparation of BNN particles

Raw powders Bi2O3, Na2CO3 and Nb2O5 were vibratory milled together and sintered to
produce plate-like BNN particles. The full experimental procedure is given in Section
3.2.2. The initial procedure involved mixing the raw powders together and mixing with a
1:1 salt to oxide ratio with NaCl. Zhang et al. reported an optimal BNN sintering
temperature of 1130C to achieve the largest well defined BNN particles.[141] In this
investigation, however, the initial starting temperature was 1100C produced particles
shown in Figure 7.2. The particles (observed before the hot washing stage) are clearly
visible, although highly agglomerated. Individual particles are of sizes up to 20m in size,
which is comparable to that reported in the literature.[16, 142] Figure 7.2 shows evidence
of particle melting in the large agglomerates, suggesting the sintering temperature should
be lowered.
Figure 7.2. BNN particles before hot washing stage, sintered at 1100C.
Furthermore, the partial loss of the yellow colour from the pre-sintered mixture
suggesting possible loss of bismuth during sintering, led to a reduction of the sintering
temperature to 1050C. The resulting BNN particles, shown in Figure 7.3, are better
defined and slightly larger (up to 25m in size) than those shown in Figure 7.2. EDAX
analysis of the particles (Table 7.1) shows the chemical composition to be equivalent to
Bi2.30Na2.83Nb5.16O18.29. Although this is not the exact Bi2.5Na3.5Nb5O18 composition expected
for BNN, it is very close.
(a) (b)
Figure 7.3. BNN particles sintered at 1050C, before hot washing stage. X denotes the area
under EDAX investigation.
Table 71. The EDAX data for a pre-hot-washed BNN particle.
Element Atomic %
O (K) 64.01
Na (K) 9.91
Nb (L) 18.05
Bi (M) 8.04
These particles were then hot washed 8 times and examined again by SEM. The resulting
micrographs are shown in Figure 7.4. There are clearly square plate-like particles visible,
with sizes ranging 5-25 m. EDAX results are shown in Table 7.2, where the effective
composition is Bi2.32Na2.80Nb5.65O17.79. This is still not the exact composition expected for
BNN, as there is a deficiency in the amount of sodium. This is difficult to adjust however,
due to the presence of excess sodium in the system during the molten salt synthesis (MSS)
process.
(a) (b)
Figure 7.4. SEM micrographs showing BNN particles sintered at 1050C after hot washing.
X denotes the area under EDAX investigation.
Table 72. The EDAX data for a hot-washed BNN particle.
Element Atomic %
OK 62.28
Na K 9.81
Nb L 19.79
Bi M 8.12
7.2.3 The Effect of Salt to Oxide Ratio

In the literature, different salt to oxide ratios are reported. Zhang et al report the optimum
ratio to be 1:1,[141] however Chang et al prefer a 3:2 ratio.[142] This aspect needed to be
investigated to define the optimal route for BNN particle production.
Figure 7.5 shows the BNN particles produced under the same conditions as the previous
samples, but with a 3:2 salt to oxide ratio, instead of the 1:1 utilised previously. Both
sintering temperatures of 1050 and 1100C were used to allow for direct comparison with
the earlier results. Figure 7.5 shows images of the material before hot washing. It is clear
that the particles are not well defined as plate-like structures and are not completely
formed.
(a) (c)
(b) (d)
Figure 7.5. SEM micrographs showing BNN particles using the 3:2 salt:oxide ratio (a,b)
sintered at 1050C, and sintered at 1100C (c, d).
It is clear from Figure 7.6 that a temperature of 1100C is too high for BNN particle
production, as the yellow colour of the powder is significantly reduced, showing loss of
bismuth from the system. Thus BNN production using the initial powders need a lower
temperature than that reported by Zhang et al.[141]
(a) (b)
Figure 7.6. BNN powder using 3:2 salt:oxide ratio used in alumina crucibles, sintered at (a)
1050 and (b) 1100C.
From these initial investigations (summarised in Table 7.3), it was found that the optimal
conditions to produce BNN particles were: a platinum crucible, with a 1:1 salt to oxide
ratio for the MSS route and a sintering temperature of 1050C. Repeated batches of BNN
particles were made using these conditions ready for the next stage of the process.
Table 73. Resulting data from BNN particles in this investigation.
Tsint (C) Salt:Oxide Particle Size Desired Structure?

1100 1:1 < 20m Melted and agglomerated
1100 3:2 < 25 m Yes, but faceted
1050 1:1 < 25 m Yes
1050 3:2 < 20m Yes, but faceted
7.3 The Production of NN Particles

The hot-washed BNN particles were mixed with Na2CO3 in a stoichometric ratio and added
to NaCl using a 1:1 salt to oxide ratio for the molten salt synthesis (MSS) method. They
were stirred together and again heat treated in the furnace for 8 hours at 1050C. This
process was developed from the initial details reported by the Toyota group.[145]
According to Saito et al.[15] a topochemical reaction occurs and the Bismuth in the system
is displaced by the Sodium to produce NaNbO3 plate-like particles.
After heating the BNN particles with Na2CO3 and NaCl for 8 hours at 1050C, the platinum
crucible was filled with deionised water and heated on a hotplate for 30 minutes at 80C.
Some of the resulting solution was taken from the crucible using a pipette, and put onto a
glass slide. After evaporating to dryness, the product was examined by SEM (Figure 7.7).
Figure 7.7. SEM micrographs of initial NN particles from solution at (a) low and (b) high
magnification.
Table 74. The EDAX data for chemical compositions of Figure 7.7 (Spectrum 3).
Element Atomic %
O (K) 69.18
Na (K) 18.17
Nb (L) 12.64
The largest platelets visible in Figure 7.7 are NaCl salt crystals from the flux used in the
MSS process. EDAX analysis of a smaller grain showed the presence of sodium and
niobium (Table 7.4). This equates to NaNbO3 which is being produced; a good indicator
that that NN particles are forming. It must also be noted, that there was no sign of bismuth
oxide. This shows evidence of successful topochemical Bi to Na conversion.
As the MSS method was yielding NN particles, additional batches were produced in the
platinum crucible at 1050C. The resultant product was placed in a beaker of deionised
water and sonicated to agitate and separate the particles with minimal damage. They
were then hot washed at 80C until there was no reaction with dilute silver nitrate
(meaning there were no longer Cl ions present, and the salt flux has been successfully
removed). A small sample of the resultant particles was distributed on an SEM stub and
examined by SEM (Figure 7.8). EDAX analysis confirmed the particles comprised of
sodium and niobium close to the desired ratio for NaNbO3.
Figure 7.8. SEM micrographs showing an NN particle sintered at 1050C.
In order to assess the effect of sintering temperature on NN particle production, another

batch of BNN particles was mixed with NaCO3 in the way previously described, but then
sintered at 1100C. After following identical procedure, there was little evidence of the
particles after eight hot washing and filtering steps. Sections of filter paper were cut and
examined by SEM. Although particles were visible in between the fibres of the filter paper,
they were significantly smaller than those prepared by sintering at 1050C, showing that
larger particles form more easily at the lower sintering temperature.
The optimal procedure for successfully converting BNN particles to NN particles is use of a
platinum crucible and sintering temperature of 1050C, like the BNN procedure. This
resulted in particles approximately 15m wide and 0.5m thick, directly comparable to
the particles produced by the Toyota group in 2004.[15] The technique developed yields
products similar to those reported in the literature[16, 124, 141] and so is potentially
viable for subsequent tape casting.
7.4 Development of Tape Casting Procedure
7.4.1 Tape Casting Method Development

Tape casting can be undertaken in many ways (see Section 2.4.1.1). It was found that the
optimal consistency of the desired slurry was close to that of Tippex correction fluid; this
slurry was used for the trial casting experiments. As the available tape casting facility
required a minimum of 200ml of slurry, two related micro procedures were developed
requiring only 2ml slurry.
The first arrangement is illustrated in Figure 7.9. A block of 100 x 50 x 15mm stainless
steel was milled to provide a slot of 20 x 55 x 0.1mm. The slot provides the track into
which the slurry is poured and cast using a glass slide. This procedure, however, does not
allow for multiple tapes to be cast from the same slurry (before drying out) because there
is only one track available. This method has severe limitations in terms of tape thickness
and the rate of production of tapes. Here, only one tape may be cast from the slurry as
there are no further die to utilise.
Figure 7.9. Schematic illustration of the block casting procedure.
The second procedure involves the use of parallel tracks on a glass slide. Initially,
different types of adhesive tape were used to make the tracks: sellotape, parcel tape,
masking tape, scotch tape, and duct tape. It was found that masking tape gave the optimal
tape for 100m thick slurry of correction fluid, and was the easiest to utilise. Alternative
substrates were tested but glass slides proved the most effective. The optimal procedure
is shown in Figure 7.10.
Figure 7.10. Schematic illustration of the glass slide casting procedure.
7.4.2 Slurry Development
In order to cast particles within the NKN matrix for templated grain growth (TGG), the
particles and NKN matrix needed to be cast from a slurry. The slurry needs three main
additives: binder, solvent and plasticiser. The binder, some form of polymer, is utilised to
bind the particles and powders together in low concentrations, typically less than 10% by
volume. It should also be soluble in an inexpensive solvent, which together must volatilise
during heat treatment, leaving no residues in the film after sintering. Binders need to be
flexible yet tough, and so polymers with long chain molecules are utilised. Popular binders
include poly(vinyl chloride), polystyrene, poly(vinyl acetate) and polymethacrylates.
Plasticisers are added to the slurry to enhance flexibility of the film , such that the
tape can be readily removed from the substrate.
(a) (b) (c) (d) (e)
Figure 7.11. Results of various methods of producing slurry; how they formed tapes using
the glass slide casting process.
Multiple experiments were undertaken to define the optimum balance of the three
additives. The quantities recommended by Mistler et al. were used as a basis for initial
fractions of each additive,[125] as shown in Table 7.6. In fact this resulted in a highly
viscous slurry, which was not easy to cast, shown as Figure 7.11a. Consequently, the
amounts of slurry additives were adjusted (shown as Figure 7.11(b-e)), until optimised
performance was achieved. The resulting slurry was cast and subsequently removed
relatively easily, and was used in the later experiments (Figure 7.11d).
Table 75 Volume fractions of components in test slurries.
Slurry Suggested initial Amount used in

Chemical
Additive amount (g) [125] optimised slurry (g)
Binder PVB (Butvar 3.0 3.0
Solvent Ethanol-Toluene 35.0 35.0
Plasticiser Dibutyl Phthalate 5.6 5.6
Powder NKN-5LN and 6LN 100 60
7.4.3 Cast Tape Quality Control

From the work on bulk materials (see Section 7.5) it was shown that lithium niobate (LN)
is a suitable dopant for NKN; significantly enhanced electrical properties were observed at
5-6% doping levels. A sample of 94NKN-6LN slurry was produced and cast. The depth of
6LN tape parallel and perpendicular to the casting direction was measured using a
Contracer. By dragging a needle along the surface of the slide and tape, height differences
can be recorded. It was not possible to undertake the same test for the metal die casting
due to the lack of a reference height.
Figure 7.12a shows the thickness of the cast tape in different directions. Although
the depth is not even, the height difference measured along the length of the cast section is
16.2 m, giving an average depth of tape is 53.3 m (8.1 m). This is an acceptable
thickness for thick film casting.
(a)
(b)
Figure 7.12. The thickness of 6LN tape cast on a glass slide (a) along the length and (b)
across the width of the slide.
The thickness across the width of the tape was also examined; an exemplar of the width is
given as Figure 7.12b. It is evident that there is a raised section at the sides; this is
expected as it is like the meniscus, where the slurry is attracted to the surface of the
masking tape that makes the casting track. Along the main width of the tape, there is
relatively uniform thickness of average 54.8 m (4.1 m) for this section, although the
average for all width measurements was 53.6 m. This is concurrent with the average
thickness along the length of tape, and so is the average tape thickness for this method.
7.5 Doping NKN with LiNbO3 (LN)

Before tape casting of the NKN-LN system could commence, a study of LN doping in NKN
using the conventional mixed oxide route was undertaken. The starting powders were
weighed and mixed according to their stoichiometric ratio to produce 95NKN-5LN.
Samples were dried and wet milled for 24 hours then calcined at 850-930C for 4 hours.
The calcined powder was doped with CuO (0-0.8 wt%) and wet milled for 24 hours before
drying and pressing at 100MPa and sintered at 850-1100C (180C/hour) for 2-18 hours.
(a) (b)
Figure 7.13. P-E hysteresis behaviour of (a) NKN + 0.2 wt % CuO and (b) 95NKN-5LN 0.8
wt% CuO (from Azough et al).[200]
Calcination at 930C and additions of 0.8 wt% CuO to 5LN were optimal to achieve a 95%
theoretical density with a very low sintering temperature of 890C. This result was
published in 2011.[200] XRD data showed that this structure had orthorhombic and
tetragonal phases coexisting in the material, as expected for this MPB formulation.[33,
162] Resulting hysteresis data for 0.2 wt% CuO doped NKN and 0.8 wt% CuO doped 5LN
are shown in Figure 7.13. Copper doping in NKN leads to properties of Pr = 18 C/cm2
and EC = 15 kV/cm (Figure 7.13a). These properties are similar to those reported by Moon
et al. for 1 mol% CuO doping in NKN, although in the present study the remnant
polarisation is 4 C/cm2 higher.[201]
The 0.8 wt% CuO doped 5LN sample, however, has a significantly higher Pr of 27
C/cm2 and EC = 10 kV/cm. These values are higher than previous investigations of
5LN.[111, 121] A higher Pr value of 28 C/cm2 was found for 0.4 wt% CuO.
7.6 Tape Casting of Copper-Doped 5LN and 6LN Compositions

95NKN-5LN and 94NKN-6LN powder samples doped with 0, 0.4 and 0.8wt% CuO were
prepared using the mixed oxide route described in Section 3.2.1. Copper oxide was added
as a sintering aid, as it has proven effective.[33, 83, 202] The powders were mixed with
the slurry additives shown in Table 7.6. The full experimental procedure is described in
Section 3.2.2.5. Tapes of thickness 20-30m were prepared by the glass casting method
(Figure 7.10).
For the 95NKN-5LN + 0.4wt% CuO bulk material, the optimum sintering temperature was
found to be 1090C.[200] Sintering temperatures in the range 1030-1150C were utilised
for film production. The resulting tapes were cut into sections and investigated by XRD
and SEM.
A micrograph of undoped 95NKN-5LN (Figure 7.13a) show that a 1030C sintering

temperature results in a grain size of 1 m but there is evidence of liquid phase present.
When the sintering temperature was increased to 1060C, the grains size increased to 3
m. There was no evidence of liquid phase although the grains are faceted and not of the
desired microstructure. This is shown in Figure 7.14b, where the grains are still relatively
small and have not sintered and densified, as seen with successful thick films. For the
highest sintering temperature of 1090C (Figure 7.14c) there was a significant change in
the microstructure. The grains were fully formed, rectangular in shape with some
evidence of abnormal grain growth - some being over 12m in size. This microstructure is
similar to that obtained in the bulk material.[200]
When 0.4wt% CuO was added to the 5LN as a sintering aid, there were significant changes
in the microstructure (Figure 7.14d-f); a 1030C sintering temperature was sufficient to
generate fully formed grains typically 3m in size. This is much larger than for samples
prepared without the CuO doping at the same temperature (Figure 7.14a). When the
sintering temperature was decreased to 1000C, sintering was not complete and the
microstructure was similar to that shown in Figure 7.14a. This shows that the CuO lowers
the sintering temperature by approximately 30C.
When the 5LN + 0.4wt% formulation was sintered at 1060C and 1090C, there was
evidence of abnormal grain growth (Figure 7.14e) and combinations of abnormally large
grains with fully formed smaller grains in between (Figure 7.14f).
(a) (d)
(b) (e)
(c) (f)
Figure 7.14. SEM micrographs of 95NKN-5LN + x wt% CuO single tapes (thickness 20-30m)
sintered at different temperatures.
X-ray diffraction spectra for the Copper-doped 5LN films are shown in Figure 7.15. All the
spectra show fully formed NKN with an orthorhombic structure, even for samples sintered
at 1000C. This is expected as bulk samples of this composition can be sintered at
temperature as low as 890C.[200]
In the 002 / 200 double peaks at 45 2 (Figure 7.15) the first peak is higher than
the second, confirming that an orthorhombic phase is the dominant structure.[98, 157]
This is true for samples sintered at all temperatures, showing that orthorhombic NKN is
fully formed.
101
110
1090C
1060C
1030C
001
001
1000C
002
200
112
211
Intensity
101
201
210
111
15 20 25 30 35 40 45 50 55 60
two theta
Figure 7.15. Diffraction patterns of 95NKN-5LN + 0.4wt% CuO at various sintering

temperatures.
7.7 Film Thickness

In order to investigate the effect of film thickness, a constant sintering temperature of
1030C was employed. The masking tape film casting method yields tapes of
approximately 50 m thick, which after sintering are 25-35 m thick. In order to produce
thicker films, two different methods were utilised:
(i) The first method involved slicing the tape into strips approximately 8-10mm wide
and stacking them on top of each other and pressing them before sintering. This
method allows any thickness of film to be produced.
(ii) The second method involves casting a film on a slide, allowing it to dry, then
applying another layer of masking tape at each side to increase the channel
depth and casting another film on top of the first film. This double-cast method is
more time-consuming than the first technique. In principle this method can be
repeated many times.
Since the MPB of the NKN-LN binary system lies between the 5 and 6 mol% LN
compositions, it is clear from the XRD data that orthorhombic and tetragonal phases
coexist in the system. This presents difficulties in accurately defining changes in the
system and the unit cell parameters. It was decided to focus on the 94NKN-6LN
composition, as there is a higher degree of tetragonality in the system, although both
structural phases are still present.
Single and double cast tapes of 6LN + 0.4wt% CuO were prepared. The XRD spectrum of
the single tape (Figure 7.16) shows the double peaks at 22 and 45 2 are of the same
height. This shows that both orthorhombic and tetragonal phases coexisting in the
material.[101, 109, 180-181] This type of microstructure is expected in 95NKN-5LN, not
94NKN-6LN, formulations.
The XRD spectrum for double-cast tape is significantly different (Figure 7.16). In
the double peaks, particularly those between 44 and 58 2, the second peak is higher
than that of the first, indicating a high degree of tetragonality. This is expected for the
94NKN-6LN composition. There is also evidence of an orthorhombic phase coexisting in
the structure, denoted by the double peak, showing that this composition is close to the
MPB (which enables enhanced electrical properties in perovskite ceramics). It is also
significant that the 001/ 100 peak at 22 2 is much lower for the single tape than for the
double tape, with reference to the large 110 / 101 peak at 32 2. This shows clear
differences between the structure for the two tapes; the double-cast material develops a
structure that is comparable with that for bulk samples of the same composition.
double tape
110
101
single tape
001
100
002
200
Intensity
112
211
102
201
210
111
15 20 25 30 35 40 45 50 55 60
two theta
Figure 7.16. Diffraction spectra of 94NKN-6LN + 0.4wt% CuO single and double-cast tapes,
both sintered at 1030C.
The XRD spectra for double cast tape and a double stacked and pressed sample of 6LN +
0.4 wt% CuO were identical, showing both methods formed fully sintered 6LN structures.
SEM analysis of the stacked sample showed a uniform thickness throughout with a flat
surface, unlike that of the double cast sample. As the double cast method was more time
consuming, the stacking method was employed for the remainder of the study.
7.8 Tape Casting Oriented 94NKN-6LN Tapes using NN particles
In order to create oriented samples, the previously made (oriented) NN particles were
added to the slurry before the mixing stage, and then cast as before. Saito et al. reported
adding 5 at% particles,[16] however Gao et al. reported the addition of 30% particles to be
optimum for NBT-BT compositions.[143] In view of the differences in the literature, initial
experiments used 10 wt% particles added to the slurry for each composition. The aim was
to use the oriented NN plate-like particles as templates to react with the matrix
composition and thus encourage orientation of the matrix during sintering. A schematic
diagram of the process is shown in Figure 7.17.
Figure 7.17. Schematic diagram of the RTGG process [after Zhao et al.].[183]
7.8.1 Preparation of Tapes with Addition of 10% NN Particles
7.8.1.1 Orienting 6LN + 0.4 wt% CuO Composition

The NN particles were added at the level of 10 wt% to the matrix composition 6LN + 0.4
wt% CuO to form the slurry, which was cast and dried; tapes were subsequently cut and
sintered. The initial sintering temperature was 1030C as this was adequate for the same
composition without the presence of particles. Fired samples were examined by SEM,
shown in Figure 7.18. The plan view Figure 7.18(a) shows template particles (indicated
by the arrows) between the sub-micron sized matrix grains, suggesting they have not
reacted at this temperature. The cross-sectional view of the tape (Figure 7.18b) indicates
significant agglomeration of the template particles.
(a) (b)
Figure 7.18. SEM micrographs of 94NKN-6LN + 0.4 wt% CuO single cast tape sintered at
1030C, (a) plan view, and (b) cross-sectional view of tape. Yellow arrows indicate visible
particles.
This type of agglomeration was also reported by Kimura et al. when they added Ba 6Ti17O40
particles to Bi0.5Na0.5TiO3-BaTiO3 (BNTBT). They overcame this by using a dispersant in
order to ensure homogeneity in the slurry and a good alignment during the tape casting
process, which was a successful undertaking (before (a) and after (b) use of dispersant
shown in Figure 7.19).
Figure 7.19. SEM micrographs showing microstructures of NBTBT thick films (a) using no
dispersant, and (b) using dispersant (after Kimura et al).[133]
To overcome the agglomeration in this study, a dispersant (that is, a surfactant in solution
with a solvent) was employed. The NN particles were mixed with BASF Dispex A40
dispersant and further sonicated. After drying, the particles were added to the slurries
and processed according to the standard experimental methods. Initially, films were
prepared from 94NKN-6LN + xwt% CuO (with 10% NN), where x is 0, 0.4 and 0.8. After
casting and sintering at 1030C, the product was of the same colour as the original tape,
yet very brittle.
SEM (Figure 7.20a) and XRD revealed underdeveloped sintering. The yellow
arrows indicate the template particle visible in the sintered tapes. Consequently, the
sintering temperature was increased to 1090C. Whilst there was some improvement in
densification, there was still very limited reaction between the template particles and the
matrix (Figure 7.20b). When the sintering temperature was increased further to 1120C,
it was clear that large grains developed at this higher temperature (Figure 7.20c,d),
typically 5m in size (compared to 1m in Figure 7.20a,b) and there was no evidence of
template particles suggesting that they had reacted with the matrix.
In the side elevation view of the 1120C sample, shown in Figure 7.20d there was
evidence of alignment of the grains in the casting direction, with some grains, growing to
15m in length.
(a) (b)
(c) (d)
Figure 7.20. SEM micrographs of single tapes cast of composition 94NKN-6LN + 0.4wt% CuO
+ 10%NN particles sintered at temperatures of (a) 1030C, (b) 1090C and 1120C (c) top
view and (d) cross-section. Yellow arrows show template particles.
Accepting that the 1120C sintering temperature yielded good quality samples, the next
stage was to form thicker samples. This was done by cutting identically sized tapes,
stacking them upon one another and pressing them before sintering. This method allows
tapes of any thickness to be produced. Initially, four tapes were pressed together to give a
total thickness of approximately 100-130m, and then eight tapes to give thickness of 200-
250m. The results, after sintering such tapes at 1120C, are shown in Figure 7.21.
The microstructures contrast with those for single tape (Figure 7.20). In the four layered
sample, shown in Figure 7.21(a-c), there are fully grown grains, with some abnormal grain
growth (Figure 7.21a); the side view (Figure 7.21b,c) shows cubic grains in a fully
densified layer 90m thick, with no sign of interlayer defects.
In the eight layered sample (Figure 7.21d-f), there was no sign of these large grains
in the tape; template particles are evident within the micron grain-sized matrix. In side
view (Figure 7.21e,f), however, the layers have densified and are successfully bonded
together, giving a full thickness of 225m. At high magnification (Figure 7.21f) there are
suggestions that some particles within the matrix are just beginning to react with the
matrix grains. This indicates that layering and pressing the tapes to make thicker samples
is detrimental to the microstructure, leading to different microstructural behaviour to
single tapes of 25-30m thickness.
(a) (d)
(b) (e)
(c) (f)
Figure 7.21. SEM micrographs showing the top and side views of 94NKN-6LN + 0.4wt% CuO
+ 10%NN particles sintered at 1120C, with four layers (a-c) and eight layers (d-f). Yellow
arrows indicate visible template particles.
For the eight layered samples, the highest sintering temperature examined was 1150C.
This is very high for NKN production as sodium and potassium are volatile at such high
temperatures, and readily form liquid phases. Indeed, when eight layered tape was
sintered at 1150C, the tape reacted with the platinum foil substrate and became attached.
Representative micrographs are shown in Figure 7.22.
Whilst there is some abnormal grain growth the matrix grains have increased in
size to typically 2 m, which is larger than in samples sintered at lower temperatures, and
the film is approaching full densification. In the side view (Figure 7.22c,d), the thickness
of the tape is 210m, but the particles, again, have not fully reacted with the matrix and so
full orientation has not been achieved.
(a) (b)
(c) (d)
Figure 7.22. SEM micrographs of the top and side views of an eight layered 94NKN-6LN +
0.4wt% CuO + 10%NN particles, sintered at 1150C. Yellow arrows indicate visible template
particles.
XRD spectra of these samples sintered at 1090-1150C are shown in Figure 7.23. The
spectrum for the 1150C sample is significantly different to samples sintered at lower
temperatures. The (100) peak at 22 2 for the 1150C sample is lower than the same
peak in the 1090C sample, and conversely the 45 2 peak (1150C sample) is
significantly higher than for the samples sintered at lower temperatures. As the ratio of
the peaks has changed significantly, it suggests the development of orientation in the
sample. The SEM images confirm that grains are larger and more fully formed at 1150C
than the lower temperatures, although the template particles are not fully reacted and
integrated with the matrix. However, the disadvantages of such high sintering
temperatures are because of sodium and potassium volatility and that the sample reacted
with the platinum substrate.
002
200
0.4CuO_1150C
0.4CuO_1120C
0.4CuO_1090C
Intensity
001
100
110
101
102
201
210
112
211
20 25 30 35 40 45 50 55 60
Two Theta
Figure 7.23. XRD spectra for 94NKN-6LN + 0.4wt% CuO + 10 wt% NN particles, 4x layer
pressed tapes sintered at 1090, 1120 and 8x layer pressed tape sintered at 1150C.
The increase of the (200) peak intensity, and also its shape, is a direct result of <100>
texturing.[130, 134] The split peak shape shows tetragonal phase, which is expected for
this composition. A similar result was obtained by Yilmaz et al. where the diffraction
patterns of 94.5% (Na0.5Bi0.5)TiO3 - 5.5% BaTiO3 ceramics are significantly modified (in
terms of peak intensity ratios) that show successful texturing in the ceramic (after 12
hours sintering time); a Lotgering factor of 96% was achieved.[139] This is illustrated in
Figure 7.24. (The Lotgering factor, f, is explained and defined in Section 2.4.1). This exact
effect is also seen in here, and so shows successful orientation has been accomplished.
Figure 7.24. XRD diffraction patterns for NBTKT with random orientation (blue) and with
5% added SrTiO3 template particles added (pink) (from Yilmaz et al).[139]
F was calculated for the 1150C sintered 6LN + 0.4 wt% CuO + 10 wt% NN particles
sample and compared to a sample of the same formulation without NN particles made
with the mixed oxide route (sintered at 890C); a factor of 67% was found. The two
spectra are shown in green (6LN + 0.4 wt% CuO bulk sample) and blue (6LN + 0.4 wt%
CuO + 10 wt% NN) in Figure 7.25. The f value 67% indicates a high orientation, and
shows that the tape casting method developed in this investigation does work.
A comparison can be made with the work of Takao et al. on the orientation of Cu-
doped NKN.[16] They reported that 1 mol% CuO doping to NKN resulted in an orientation
of 93%, which is very high; other properties include a density of 95% and grains of sizes
10-20 m. Their samples were sintered at 1100C, which is 50C lower than that required
in the present study, though Takao et al. used a pure oxygen atmosphere (as opposed to an
atmosphere of normal air utilised in this case). This, however, is not a direct comparison
as the tapes under investigation here are Li-doped, which have not been reported
elsewhere.
1150 C - 10% NN particles

1030 C - no particles
890 C - bulk sample
Intensity (a.u.)
15 20 25 30 35 40 45 50 55 60 65 70 75
two theta
Figure 7.25. Comparison of XRD diffraction profiles of 94NKN-6LN + 0.4 wt% CuO (a) double
cast sintered at 1030C, and (b) 8x layered tape with 10 wt% NN particles added, sintered at
1150C.
The electrical properties of the 1150C sintered sample was tested as it exhibited the
desired orientation. As described previously, the sample reacted with the platinum foil
substrate, and so the foil was used as one of the electrodes. The other side of the sample
was covered in silver paste as normal (see Section 3.3.7) and silver wires were attached
using silver paste. Capacitance and impedance data were collected.
The relative permittivity data for this textured sample is shown in Figure 7.26. At 10 kHz
the relative permittivity at room temperature is 300. The inset in Figure 7.26 shows that
there is a transition at approximately 70C, which is the TO-T. The Curie temperature is at
~440C. This is slightly lower than that reported for bulk NKN; Guo et al. reported
94NKN-6LN to have a TC of 468C.[203]
500 1 kHz
2000
450 10 kHz
100 kHz
400
1 MHz
1500 350
300
r
250
1000
200
0 50 100 150 200 250 300 350 400
500
0
0 50 100 150 200 250 300 350 400 450
Temperature ( C)
Figure 7.26. Permittivity data for 94NKN-6LN + 0.4 wt% CuO + 10% NN particles, as a
function of applied frequency. Inset shows 1-400C range under closer inspection.
There was a problem with impedance measurements in that the switching between lower
and higher frequencies was discontinuous. This is shown in Figure 7.27. There was
enough of the main arc to extrapolate a semi-circle to determine the lower frequency data.
The data was modelled using the ZView program.[204] An exemplar fitting (for 545C) is
shown as Figure 7.28.
1.4
485 C
1.2
505 C
1.0
525 C
0.8 545 C
" (km)
0.6
0.4
0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
' (km)
Figure 7.27. Cole-Cole plot data for 94NKN-6LN + 0.4 wt% CuO + 10% NN particles, as a
function of temperature (485 545 C)
The green line in Figure 7.28 shows the modelled semi-circle of the Cole-Cole plot from the
impedance data. By modelling the data, the resistance and capacitance can be calculated.
At a temperature of 545C the resistance was 25 k and capacitance 21.6 pF. For textured
samples, there is no published impedance data given for direct comparison. According to
Yang et al. NKN + 0.25 mol% CuO prepared by the conventional mixed oxide route has a
resistance of 20.[205] This shows that 6LN doping gives thick film (thickness 210 m)
properties comparable to bulk NKN.
Figure 7.28. Cole-Cole impedance plot fitting for 94NKN-6LN + 0.4 wt% CuO + 10 wt% NN
particles, at temperature 545C. Blue spots and red line denote data, green line denotes
fitted semi-circle model
7.8.1.2 Orienting 6LN + 0.8 wt% CuO Composition

In view of the effect of the amount of CuO addition on NKN-LN microstructure
development (ref earlier section 7.5), a similar investigation was undertaken with tapes
prepared from 6LN + 0.8wt% CuO powder with 10% NN particles added. Using the multi-
layering pressing procedure, the single layer casting followed by cutting and stacking
allows more tapes to be prepared, and allows for a higher degree of options of
multilayering and potentially a higher degree of orientation in one layer.
Four layered samples were made and sintered at 1030, 1090 and 1120C. The 1030C
sintering temperature was again too low, the tape did not change colour after sintering
and was very brittle. SEM confirmed that particles were sub-micron in size.
The sample sintered at 1090C exhibited superior microstructure. Figure 7.29 shows
micrographs of single and 4 layered samples which had been sintered at 1090C. As with
the 0.4 wt% copper-doped samples, it would appear that the additional tape thickness is
detrimental to the microstructure, so a higher temperature is needed to produce high
quality thicker samples. A similar conclusion was also reached in Section 7.8.1.1.
(a) (b)
(c) (d)
Figure 7.29. Comparison of single and four-layered 6LN + 0.8 wt% CuO + 10% NN particles
samples sintered at 1090C.
Figure 7.30 shows micrographs of 94NKN-6LN + 0.8wt% CuO + 10%NN ceramics

produced from four layered tapes. It is clear that the sample still exhibits a very small
grain under one micron in size. Thus for thick film casting, higher levels of CuO doping is
not beneficial as a sintering aid. Subsequent work continued with 0.4wt% copper doping.
(a) (b)
Figure 7.30. SEM image of four-layered 6LN + 0.8 wt% CuO + 10% NN particles sample
sintered at 1120C showing (a) as-fired surface and (b) side elevation view.
7.8.2 Adding 15% NN Particles

As samples prepared with both 0.4 wt% and 0.8 wt% CuO doped 94NKN-6LN showed
some degree of orientation after sintering at high temperatures, the amount of NN particle
addition was increased from 10 to 15%. This aim was to increase the degree of
orientation in the samples. Single tapes were cast, and it should be noted that the
template particles were coated in surfactant before processing.
Samples prepared with 0.4 wt% CuO doping were very difficult to remove from the glass
slides after casting, and were very brittle, unlike the flexible tapes cast for 10% particles.
However the 0.8 wt% doped tapes were easy to recover after casting. For this reason the
latter were employed in the remainder of this part of the investigation.
110
101
1120C
1090C
Intensity
001
100
002
200
112
211
102
201
210
20 25 30 35 40 45 50 55 60
two theta
Figure 7.31. XRD Spectra for 94NKN-6LN + 0.8wt% CuO + 15 wt% NN particles, 4 layer
pressed tapes sintered at 1090 and 1120C.
The XRD data in Figure 7.31 shows there is minimal difference between the samples
sintered at 1190 and 1120C from 0.8 wt% copper-doped tapes. They both exhibit
tetragonal structure. They also show more second phase peaks than those found for 10%
NN samples (Figure 7.23). Ideally these peaks would not be detected at all, due to the
reaction with the NKN matrix composition and the desired homogeneity and a oriented
single phase. This shows that the processing technique needed to be altered to promote
reactions between the tapes.
Feng et al. reported the variation of properties in relation to NN template particle

addition.[82] Although this is for a different composition, that of 93NKN-7LT (LiTaO3) the
effect of over 5 mol% addition of particles shows a fully tetragonal structure; the (001),
(110), (102) and (112) peaks disappeared (so there are single peaks as opposed to the
split double peaks observed here). This is shown in Figure 7.32. It must be noted that
their investigation did not involve tape casting but the material was pressed and sintered
as in the conventional mixed oxide route.
Figure 7.32. XRD diffractogram for 93NKN-7LT-xNN particles (here NKN is denoted as KNN)
[from Feng et al}.[82]
Feng et al. also noted a second phase distinguishable between 25 and 35 degrees 2. This
is of K2Li3Nb5O15 which are marked in as diamonds in Figure 7.32. Hence some of this
phase occurs in the present samples.
This K2Li3Nb5O15 phase (structure shown as Figure 7.33e) occurs due to the strain
in the lattice when Na+ ions are sitting in the K+ A-site and causes octahedral tilting of the
Oxygen ions, illustrated in Figure 7.33c. Some of the spaces surrounding the A-site ions
can open or close slightly (Na+ and K+ have ionic radii 0.97 and 1.33 )[84] to form larger
pentagonal interstitial sites, thus forming smaller triangular sites (clearly shown in Figure
7.33d) which the smaller Li+ ions can occupy when diffused into the lattice (Figure 7.33e).
Although this is a viable structure in Lithium-doped NKN, it must be noted that it is found
in very small quantities in the XRD diffraction data throughout this investigation. Due to
the small amounts detected, no further investigation into this phase was undertaken.
Figure 7.33. Schematic showing the evolution of K3Li2Nb5O15 structure from NKN (from Feng
et al.)[82]
7.9 Chapter Summary
This chapter was devoted to a new and novel processing route for textured NKN. An RTGG
approach has been developed to produce NKN-based tapes with orientation along the
<100> direction, using small amounts of material, which can later be upscaled once a
suitable formulation has been developed. In the first stage, platinum crucibles were found
to be effective for BNN and NN particle production.
For BNN precursor production, the optimal processing route for molten salt synthesis
(MSS) involved a sintering temperature of 1050C for 2 hours in an NaCl medium using a
salt to oxide ratio of 1:1. Resulting particles were up to 25 m in size, although the
average was 15 m.
In order to convert these pre-cursor particles to NN template particles, a sintering
temperature of 1050C for 8 hours was required (salt to oxide ratio 1:1). Resulting
particles were approximately 15 m wide and 0.5 m thick.
A simple low-cost method for casting thick films was developed. This involved making a
track from masking tape along the sides of a glass slide, allowing a small amount of
slurry to be deposited onto one side and cast across the track using the side of another
glass slide. The optimal amount of slurry components (binder, solvent and plasticiser)
was 40% to 60% NKN powder. 95NKN-5LN formulations showed that 0.4 wt% CuO
doping was a successful sintering aid, which allowed a 30C reduction in the sintering
temperature.
For 94NKN-6LN composition, 0.4 wt% CuO was also the optimum addition of a sintering
aid. Sintering at 1120C yielded oriented single tapes, although the temperature had to be
increased to 1150C for layered tapes. After sintering, single tapes were approximately 20-
30 m thick, and layered samples were up to 250 m thick.
A Lotgering orientation factor of 67% was achieved for the 1150C sintered eight layered
sample. This tape exhibited dielectric properties of TC = 440C and TO-T = 70C, and a
resistance of 25 k and capacitance 21.6 pF.
8 CONCLUSIONS
8.1 SBN doping of NKN

The use of SBN as a dopant for NKN is novel. It was found to be beneficial when used with
the addition of 0.45 wt% Fe2O3 as a sintering aid. Initial results indicated that 4 mol% SBN
addition define the single phase solubility limit. Laboratory XRD (Chapter 5) and a higher
resolution diffraction study (Chapter 6) showed that there was in fact a second phase
present in such materials; this was also observed (in smaller amounts) in lower SBN
formulations. A second phase was visible in SEM imaging, where the phase was potassium
rich; in 4SBNF another phase was found which was barium rich.
All compositions showed orthorhombic structures when investigated by
laboratory XRD; at 4 mol% SBN addition, the orthorhombic and tetragonal phases
coexisted in the system. Synchrotron XRD showed that in reality the two phases were
coexisting in all SBN-doped formulations, in 1SBNF there was up to 20%. The structure of
the second phase, particularly that observed in 4SBNF, was refined as a tungsten bronze
type (TBT) structure, but not that of SBN. This was present in 3% of the 4SBNF sample,
with parameters a = 3.948327(11) , b = 5.640070(17) and c = 5.670146(17) .
Additions of 2-4 mol% SBN achieved the highest densification, yielding over 96%
theoretical density. The addition of SBN caused the transition temperatures to decrease,
TC by 14.7C and TO-T by 9.0C per 1 mol% addition; initial values for NKNF were 234C
and 457C, respectively. The value of the relative permittivity at TC decreased as SBN was
added.
NKNF exhibits a Pr of 22 C/cm2 and EC of 16.5 kV/cm, a higher remnant
polarisation than that found for undoped NKN (Pr = 18.8 C/cm2 and EC = 9.65
kV/cm).[95] The optimal formulation is 2SBNF, which exhibits Pr = 25 C/cm2 and EC =
8.8 kV/cm. 24 hour sintering of 2SBNF enables it to withstand larger electric fields
before breaking down (60 kV/cm as opposed to 40 kV/cm).
Samples prepared with 2SBNF and 3BNF addition exhibit the highest resistivities of 4.7
and 5.0 km, respectively. The 4SBNF formulation has significantly lower resistivity of
= 0.27 km, although this is still higher than that for NKNF (0.08 km). The 2SBNF and
3SBNF formulations were associated with the highest activation energies of 1.16 eV.
NKNF, in comparison, had a much smaller activation energy of 0.60 eV, showing SBN
addition causes the resistivity of NKN to nearly double. Matsudo et al. reported an
activation energy for NKN as 0.65 eV at temperatures above 390C.[190]
In conclusion, the 2SBNF formulation exhibits superior properties to NKN and NKNF, with
TO-T = 210C, TC = 427C, Pr = 25 C/cm2 , EC = 8.8 kV/cm and Q = 1.16 eV. It comprises
approximately 90% orthorhombic to 10% tetragonal phases coexisting in the structure. In
2SBNF, the orthorhombic phase has pseudo-cubic parameters a = c = 3.947180 , and b
= 3.999996 ; the tetragonal has a = c = 3.989798 , and b = 3.975777 .
8.2 Synchrotron Analysis of NKN-based Formulations

The Rietveld refinement computer modelling program Topas was utilised to determine
the structures of the phases present in copper-doped and LiTaO3-doped NKN.
8.2.1 Synchrotron Analysis for Cu and Nb doped NKN

The results for the 99.5NKN-0.5CuO + 0.6wt% Nb2O5 solid sample were different to that
for the same formulation as a powder. The solid sample underwent two polymorphic
phase transitions, at ~300C and ~515C, up to 100C higher than expected. The second
phase transition at 515C was between two tetragonal phases; the one above 515C was
associated with a significantly larger unit cell volume as the a(and thus c) parameters
increased to a size that was near to cubic. Average pseudo-cubic parameters for each
phase are: orthorhombic a = c = 4.06245 , and b = 3.97616 , tetragonal (300-520C) a
= c = 4.99557 , and b = 4.0363 , and high temperature tetragonal (>500C) a = c =
4.9519 , and b = 4.4941 .
The powder of the same formulation exhibited more phase transitions, although smaller
ones. This is partly due to the complete transparency of the sample in powder form. The
structure started as orthorhombic (<140C, a = c = 4.10680 , and b = 4.02620 ), and
the tetragonal phase introduced at 140C (a = c = 5.02694 , and b = 4.00747 ), where
the orthorhombic phase decreased in amount (a = c = 4.05845 , and b = 3.93863 ). At
360C the orthorhombic unit cell increased (a = c = 4.10285 , and b = 3.97435 ) whilst
the tetragonal phase changed to a = c = 4.92752 , and b = 4.06810 .
P-E hysteresis loops were recorded for this copper doped formulation, and resulted in Pr =
19.9 C/cm2 and EC = 13.5 kV/cm. The remnant polarisation is only slightly higher than
that for NKN (18.8 C/cm2).[95]
8.2.2 Synchrotron Analysis of 94NKN-6LT
Addition of 6 mol% LiTaO3 to NKN leads to the development of a tetragonal structure,
although it is still on the MPB with orthorhombic and tetragonal phases coexisting in the
system.[33, 162] This was confirmed at lower temperatures (20-200C) where both
phases were detected using Rietveld refinement. A tetragonal phase was observed
throughout the temperature range (20-500C) average pseudo-cubic parameters a =
4.98349 and b = 4.01715 . The a parameter found here is significantly larger than
that reported by Saito and Takao.[112]
With increasing temperature above 200C, the orthorhombic phase disappears and the
material is entirely tetragonal. There is a transition to cubic at approximately 390C , and
at slightly lower temperatures orthorhombic phase was again detected (340-390C) which
has not previously been reported.
At low temperatures (20 - 200C) an orthorhombic phase with average parameters
of a = 4.0916 and b = 4.0172 was detected and refined. It was again detected just
before the tetragonal to cubic transition at 390C (340 390C), with a slightly smaller
unit cell volume. The existence of an orthorhombic phase just before the transition to a
cubic structure has not been detected previously in synchrotron studies of NKN.
8.3 Tape Casting of LN-doped NKN
8.3.1 Tape Casting Procedure Development

A new process for tape casting was introduced and developed to minimise powder
wastage. It allows formulations to be investigated in small batches, which is useful and
cost-effective for developmental research. A track was formed on a glass substrate,
using masking tape to provide a casting area approximately 50 m thick. Slurry was
poured onto one side and cast with the side of a glass slide, which acts as a doctor blade in
the tape casting process.
For the slurry, it was found that the optimal amount of slurry components (binder,
solvent and plasticiser) was 40% to 60% NKN powder.
8.3.2 Orientation using NN Template Particles

In order to produce oriented NN particles, BNN precursor particles were produced using
molten salt synthesis (MSS). The optimal method involved a sintering temperature of
1050C for 2 hours in a weight to weight ratio of NaCl to BNN mixture. Resulting particles
were on average 15 m diameter.
These BNN pre-cursor particles were converted to NN template particles, at a
sintering temperature of 1050C for 8 hours. Resulting particles had the same
morphology as the BNN particles, approximately 15 m wide and 0.5 m thick., which are
comparable to the literature.[15]
8.3.3 CuO doped NKN-LN Tape Casting Development

The optimal CuO addition for single layered 5LN as a sintering aid was 0.4 wt%, reducing
the sintering temperature by 30C. In order to produce thicker films, individual films were
stacked and pressed before sintering, to produce films up to 250 m thick (for eight
layers). When NN particles were introduced, a sintering temperature of 1120C was
required to achieve a visibly oriented microstructure. An eight layered sample of the same
formulation required 1150C to accomplish orientation, which resulted in 67% texturing,
giving dielectric properties of TC = 440C and TO-T = 70C, and a resistance of 25 k and
capacitance 21.6 pF. In comparison to NKN, the Curie temperature is higher but TO-T is
significantly lower (NKN has TC and TO-T of 420C and 200C respectively).[29] Yang et al.
reported NKN + 0.25 mol% CuO prepared by the conventional mixed oxide route has a
resistance of 20,[205] showing the present 6LN thick film is at least comparable to bulk
NKN. In fact the film exhibits higher resistance than a bulk sample of NKN.
9 RECOMMENDATIONS FOR FURTHER STUDY
9.1 NKN-SBN System

Electron backscattered diffraction (EBSD) could usefully be undertaken on NKN and NKN
doped samples in order to investigate texturing and grain orientation of the samples.
Although conventionally processed samples are not formally textured directly, some
degree of orientation can be observed and therefore EBSD investigations would be a
valuable starting point.
Inagaki et al. reported that three types of domain walls are present in NKN: 60, 90 and
180.[206] Detailed TEM investigations of SBN-doped NKN could be undertaken to
investigate the nature of domain structures and how they vary as a function of SBN
addition. This could be extended to investigate domain switching in SBN-doped NKN in in-
situ, in the presence of an electric field, and simultaneously by x-ray diffraction. This
technique has already been undertaken on undoped NKN by Hall et al. in 2010.[207]
A priority for further work should be the determination of the TBT phase observed in
4SBNF in Chapter 6. Resolving the second phases visible in SEM images for formulations
prepared with 2-4 mol% SBN addition would usefully advance understanding of NKN. As
higher resolution analysis is required, it is recommended that samples (such as 4SBNF)
are examined by neutron diffraction.
In order to determine the exact composition of NKN-doped formulations, atomic

absorption methods could be used. As NKN is soluble, the sintered compositions could be
compared to the intended stoichiometric calculations.
A relatively new approach to NKN production is the use of spark plasma sintering (SPS).
This process eliminates grain growth as complete rapid sintering can be undertaken in the
matter of minutes due to the high ramping rate, short soaking time and lower sintering
temperatures, which is especially useful in NKN as it suppresses the volatilisation of
sodium and potassium in the system. Zhen et al. reported achieving densities of above
99% theoretical in NKN using this SPS technique, which resulted in enhanced dielectric
permittivity and piezoelectric constant properties of 700 and 148 pC/N, respectively.[208]
9.2 NKN-LN System
NKN-LN is a highly investigated system. However, the tape casting aspect is relatively
new. The most promising 6LN formulations should be upscaled and tested on full-sized
tape casting equipment in order to be able to collect full electrical data for the materials.
TEM should also be employed to investigate the domain structures in the oriented tapes
produced.
Feng et al. reported a maximum relative density of 98% theoretical when 3-5% NN
particles were added to NKN samples. However these samples were not tape cast, but
pressed and sintered after NN particle addition.[82] The work should be developed to
define the optimal amount of NN particles to be added to the tape slurry. Previous studies
suggest the optimal amount varies between 5 and 30%.[82, 127]
The addition of NN particles to NKN using conventional mixed oxide processing route
could also be explored. Feng et al. reported that addition of 1 mol% NN particles to
93NKN-7LT improved the properties.[82] Such an investigation could be undertaken with
6LN and 6LT samples.
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APPENDIX 1 - FIGURES
Figure 1.1. Number of publications cited in refereed journals based on lead-free
piezoceramics (between 1050 and November 2008) (from Rdel et al).[3] .............................. 10
Figure 1.2. Piezoelectric coefficient Curie Temperature comparison of PZT materials to

BaTiO3 (BT), BNT and NKN based materials in the literature (from Shrout and Zhang).[18]
.............................................................................................................................................................................................. 10
Figure 2.1. Schematic diagram showing different polarisation mechanisms in a material

(from Moulson and Herbert).[35] ...................................................................................................................... 14
Figure 2.2. Schematic diagrams showing how charge can store on capacitor plates in
vacuum (a) and how a dielectric material (grey) in between them can play a role (b) (from
Moulson and Herbert).[35].................................................................................................................................... 15
Figure 2.3. Polarisability of dielectric constant ( r) and loss (r) as a function of

frequency (after Moulson and Herbert).[35] ............................................................................................... 16
Figure 2.4. Structure of PZT cubic Perovskite (left) and how it is affected in its tetragonal
form to create a dipole under applied electric field (right) (from Callister).[43] ..................... 17
Figure 2.5. Schematic of k parameter (after van randeraat & setterington).[41] .................... 19
Figure 2.6. Variation of r of BaTiO3 as a function of temperature. Corresponding phase

structures are also provided (after Richerson).[2] ................................................................................... 20
Figure 2.7. The displacements of ions in BaTiO 3 that occur in the cubic-tetragonal
transition (from Moulson and Herbert).[35] ............................................................................................... 21
Figure 2.8. The initial surface charges in a material when spontaneously polarised (right)
and how energy is preserved through 180 domains (left) (from Moulson and
Herbert).[35] ................................................................................................................................................................. 22
Figure 2.9. Schematic diagrams showing (a) how a polycrystalline ferroelectric material
splits into 90 and 180 domains (from Moulson and Herbert).[35] and (b) domain walls in
tetragonal BT (A-A are 90 walls, B-B are 180 walls) (from Jona and Shirane).[42] .......... 22
Figure 2.10. The stress energy in grains in terms of grain size, accompanied by the domain
structure visible in the corresponding grains (from Arlt).[57] .......................................................... 23
Figure 2.11. Schematic of typical ferroelectric P-E hysteresis loop, including diagrams
showing the domain orientation at various points (from Damjanovic).[60] .............................. 24
Figure 2.12. Exemplar impedance plot for yttria-stablised zirconia, showing the three
possible contributions for polarisation processes (from Moulson and Herbert).[35] ........... 25
Figure 2.13. Illustration showing the electrode-ceramic interface cross-section, with

respective equivalent circuits (from Waser).[64] [el is the electrode-ceramic interface, b is
the bulk and gb is the grain boundary contribution] ............................................................................... 26
Figure 2.14. An example of (a) a series-parallel circuit which could produce the
impedance plot in part (b) (after Moulson and Herbert.).[35] ........................................................... 26
Figure 2.15. The cubic unit cell of Perovskite BaTiO3 (after Richerson).[2] ............................... 27
Figure 2.16. Phase diagram for PZT, showing various properties of PZT at different
compositions and the PZT MPB (in green) (after Lee and Bell).[67] .............................................. 28
Figure 2.17. The phase structures, polarisation temperatures and transition temperatures
of Barium Titanate (after Moulson and Herbert).[35] a and c are parameter lengths of the
unit cell, and P is the polarisation direction ................................................................................................. 30
Figure 2.18. The phase diagram of the BaO-TiO2 system, with BaTiO3 MPB shown in green
(after Jaffe).[39] ........................................................................................................................................................... 31
Figure 2.19. Graph depicting the change in Curie temperature of BT with x mol% of each
dopant on the Ba site (from Yanagida).[40] ................................................................................................. 32
Figure 2.20. The dielectric constant hysteresis behaviour of KN with respect to

temperature (after Megaw).[48] ........................................................................................................................ 33
Figure 2.21. Typical antiferroelectric hysteresis behaviour (after Uchino).[4] ........................ 33
Figure 2.22. Diagram showing the lattice prarmeters of NN (after Jona and Shirane).[42]
Volume cube root indicated in green ............................................................................................................... 34
Figure 2.23. Dielectric Constant, , Saturation Polarisation, P s, and Ec values for LN as a

function of temperature (from Jona and Shirane).[42] .......................................................................... 35
Figure 2.24. The phase diagram of the NN-KN solid solution system (after Jaffe et al).[39]
.............................................................................................................................................................................................. 37
Figure 2.25. Revised phase diagram for NKN including phase structures (after Baker et
al).[86] Dotted lines indicate change in tilting. ........................................................................................... 38
Figure 2.26. NKN P-E hysteresis behaviour according to (a) Ichiki et al.[92] and (b) Zhang
et al.[31] ........................................................................................................................................................................... 38
Figure 2.27. P-E Hysteresis for (Na0.5K0.5)(Nb0.995Mn0.005)O3 with different cooling rates
(see text) (from Inagaki et al).[89] ................................................................................................................... 40
Figure 2.28. XRD diffractograms of (a) orthorhombic and (b) tetragonal NKN, with peak
identification (after Skidmore et al.).[98] ...................................................................................................... 41
Figure 2.29. Diffraction profiles of <100> and <200> peaks for (1-x)NKN-xLi0.5Bi1.5TiO3
ceramics, at areas of interest (a) 20 2 25 and (b) 44 2 48 (from Jiang et al).[101]
.............................................................................................................................................................................................. 41
Figure 2.30. Density and relative density of (Na0.52+xK0.48)0.942Li0.058NbO3 with 0 x 0.035

(from Li et al).[99] ...................................................................................................................................................... 43
Figure 2.31. (a) Piezoelectric d33 and Qm values, and (b) P-E hysteresis behaviour for
94NKN-6BT + 1 mol% CuO (from Lin, Kwok and Chan.[83]................................................................ 44
Figure 2.32. XRD profiles of (a) (Na0.5K0.5)1-xLixNbO3 (after Niu et al)[114] and (b)
Li0.058(Na0.521+xK0.48)0.942NbO3 (after Li et al).[99] ....................................................................................... 46
Figure 2.33. Piezoelectric and dielectric properties for Li 0.058(Na0.521+xK0.48)0.942NbO3 (from

Li et al).[99] ................................................................................................................................................................... 47
Figure 2.34. Lattice parameters and (angle) value for structures of (Na 0.535K0.485)1-
xLix(Nb0.8Ta0.2)O3 (0.02 x 0.07) (from Shen et al).[102] Shaded area indicates MPB
region. ............................................................................................................................................................................... 47
Figure 2.35. Schematic of the general doctor blade tape casting process (from
Richerson).[2] ............................................................................................................................................................... 49
Figure 2.36. Schematic Diagram for the waterfall casting process (from Richerson).[2] ... 50
Figure 2.37. SEM micrographs of (a) TiO2 acicular particles, and (b) plate-like BiT
particles (after Jing et al.).[127] .......................................................................................................................... 51
Figure 2.38. SEM micrographs of BiT particles (a) and the resulting BNKT microstructure
(after Jing et al,).[127] .............................................................................................................................................. 52
Figure 2.39. Hysteresis behaviour of Nb-doped BNKT thick films, showing results for
randomly oriented and textured (using BiT particles) (after Hong et al.).[129] ...................... 53
Figure 2.40. (a) The orientation of NBTBT as a function of sintering time, and (b) The
diffraction patterns for randomly oriented (blue) and 5% added SrTiO3 template particles
(pink)in NBTBT (after Yilmaz et al).[137] .................................................................................................... 53
Figure 2.41. TiO2 template particles, and the resulting BNKT microstructure (after Jing et
al).[127] ........................................................................................................................................................................... 54
Figure 2.42. Schematic diagram of the BNN topochemical conversion reaction to NN (from
Yan et al).[118]............................................................................................................................................................. 56
Figure 2.43. XRD diffraction profiles for 1 mol% CuO doped NKN (a) randomly oriented
(Tsint = 1050C) and (b) with 10% KN particles added (Tsint = 1175C) (from Saito and
Takao).[144] .................................................................................................................................................................. 58
Figure 3.1. Flow chart illustrating the processing route and characterisation techniques
used for this mixed oxide route study ............................................................................................................. 62
Figure 3.2. Flow Chart illustrating the processing and characterisation techniques used for
this tape casting study.............................................................................................................................................. 64
Figure 3.3. Schematic showing set-up of Hot Washing Procedure. ................................................. 65
Figure 3.4. Flow chart for the production of templated NKN-based oriented tapes .............. 67
Figure 3.5. Schematic illustrating the Mechanism of Metal Die Casting. ...................................... 69
Figure 3.6. Schematic Diagram of Glass Slide Casting. ........................................................................... 69
Figure 3.7. Theoretical Illustration of X-Ray Diffraction (from Callister).[43] .......................... 72
Figure 3.8. Schematic Diagram of Diamond Synchrotron (Oxford, UK), with its main
components highlighted.[12] (1)Electron gun and linear accelerator; (2) Booster
Synchrotron; (3) Storage Ring; (4) Beamlines; (5) Front End; (6) Optics Hutch; (7)
Experimental Hutch; (8) Control Cabin; (9) Radiofrequency (RF) Cabin; (10) Diamond
House ................................................................................................................................................................................ 73
Figure 3.9. Diagram of inside MRI TC-Basic furnace utilized for experiment at Darsebury
SRS, station 6.2 (from MRI).[147] ...................................................................................................................... 74
Figure 3.10. Schematic Representation of Beamline I11, showing approximate distances of
main components from source (from Thompson et al.).[13] .............................................................. 75
Figure 3.11. An original Gaussian peak fitting of observed data (dotted) and calculated
profile (linear) by Rietvelds refinement method (material unknown) (from
Rietveld).[151] ............................................................................................................................................................. 77
Figure 3.12. Schematic Illustration of how an SEM works (from University of South
Denmark).[14] .............................................................................................................................................................. 79
Figure 3.13. Representation of Sample prepared to be clamped in between two alumina

plates, in preparation for dielectric and impedance analysis.............................................................. 80
Figure 4.1. Diffraction spectra of 99.5NKN-0.5CuO + 0.6wt% Nb2O5sintered pellet sample

over 20 60 2 range, as a function of temperature (C).................................................................... 83
Figure 4.2. Diffraction spectra of 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet sample
in the 200 and 002 peak area under investigation with respect to temperature (C). .......... 84
Figure 4.3. Peak modelling for data collected at 31C for 200 and 002 peaks. The blue line
shows the observed data, and the red line shows the calculated model. ...................................... 84
Figure 4.4. Lattice parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet
sample. Symbols: Green for orthorhombic phase, red for tetragonal phase, and blue for
new tetragonal phase; circle for a, square for b and triangle for c parameters. ........................ 85
Figure 4.5. Profile Refinement for data collected at 307C. Thick blue line denotes the
tetragonal phase component of the refinement. ........................................................................................ 86
Figure 4.6. Relationship between orthorhombic Bmm2 unit cell (a0 b0 c0), tetragonal unit
cell (at bt ct) and pseudocubic unit cell (a1 a2 a3 ) with atomic positions (from Ishizawa et
al).[117] ........................................................................................................................................................................... 87
Figure 4.7. Pseudo-cubic parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 sintered pellet
sample. Symbols: Green for orthorhombic phase, red for tetragonal phase, blue for new
tetragonal phase; square for a (and c) and triangle for b parameters. The cubes show the
pseudo-cubic parameters for the phases for direct comparison. ...................................................... 88
Figure 4.8. The diffraction profiles for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 (crushed
powder) (C), as a function of temperature, at 20-60 2. .................................................................... 89
Figure 4.9. Diffraction profiles for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 (as a crushed
powder) as a function of temperature (C) at 38-43 2. ...................................................................... 89
Figure 4.10. The Rietveld refinement of the double peak at in data collected at 72C (using
orthorhombic parameters).................................................................................................................................... 90
tetragonal model, and the black line (b) shows the orthorhombic phase. ................................... 91
Figure 4.14. Phase parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 crushed powder
sample. Markers: Square for tetragonal phase and triangle for orthorhombic phase; red
for a parameter, green for b parameter and blue for c parameter. .................................................. 94
Figure 4.15. Pseudo-cubic parameters for 99.5NKN-0.5CuO + 0.6wt% Nb2O5 crushed

powder sample. Markers: Red for tetragonal phase and blue for orthorhombic phase;
square for a (and c) and triangle for b parameters. The cubes show the pseudo-cubic
parameters for the phases for direct comparison. .................................................................................... 95
Figure 4.16. P-S hysteresis behaviour for 99.5NKN-0.5CuO + 0.6wt% Nb2O5........................... 96
Figure 4.17. Diffraction profiles for 94NKN-6LT as a function of temperature (C). ............. 96
Figure 4.18. Diffraction profiles for 200 and 002 peaks for 94NKN-6LT as a function of
temperature (C). ........................................................................................................................................................ 97
Figure 4.19. The refinement of 94NKN-6LT for data collected at 30C. The top blue and
red lines denote the observed and calculated lines respectively. The thick blue line in (a)
shows the tetragonal model, and the black line (b) shows the orthorhombic phase. ............ 98
Figure 4.20. The diffraction profile for data collected at 270C, with peak broadening on
first peak.......................................................................................................................................................................... 99
Figure 4.21. The Rietveld refinement of 94NKN-6LT for data collected at 334C, the thick
black line showing the orthorhombic phase component. ..................................................................... 99
Figure 4.22. The refinement at 336C, the thick blue line in (a) showing the tetragonal
phase component, and the thick black line in (b) showing the orthorhombic phase
component. ................................................................................................................................................................. 100
Figure 4.23. Resulting lattice parameters for 94NKN-6LT powder as a function of

temperature. Markers: Green for orthorhombic phase, red for tetragonal phase and
orange for cubic phase; square for a parameters, triangle for b parameters and circle for c
parameters. ................................................................................................................................................................. 101
Figure 4.24. Pseudocubic parameters for 94NKN-6LT. Symbols: Green for orthorhombic
phase, red for tetragonal phase, and orange for cubic phase; square for a and triangle for
b parameters. The cubes show the pseudo-cubic parameters for the phases for direct
comparison. ................................................................................................................................................................ 102
Figure 5.1. (a) SEM micrograph of Na 2CO3 particle and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns. .................................................. 105
Figure 5.2. SEM micrograph of Potassium Carbonate powder. ...................................................... 106
Figure 5.3. SEM micrograph of Niobium Oxide powder and (b) X-ray diffraction spectrum
for Nb2O5 with fitting to reference data shown by stick patterns. ............................................. 107
Figure 5.4. (a) SEM micrograph of SrCO 3 particles and (b) X-ray diffraction spectrum for
SrCO3 with fitting to reference data shown by stick patterns.. .................................................... 107
Figure 5.5. (a) SEM micrograph of BaCO3 particles and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns. .................................................. 108
Figure 5.6. (a) SEM micrograph of Fe2O3 powder and (b) X-ray diffraction spectrum for
Na2CO3 with fitting to reference data shown by stick patterns.. ................................................. 108
Figure 5.7. Relative density of NKN as a function of x% Fe 2O3 additions (after

Wegrzyn).[176]......................................................................................................................................................... 110
Figure 5.8. Densities of 96NKN-4SBN (Tsint = 1140C) as a function of x wt% Fe2O3 and
ZnO addition. .............................................................................................................................................................. 111
Figure 5.9. Relative densities of (1-x)NKN xSBN + 0.45 wt% Fe2O3 (0 x 4), all sintered
at 1140C. ..................................................................................................................................................................... 111
Figure 5.10. Diffraction spectra for (1-x)NKN xSBN (0 x 4). Indexing of orthorhombic
peaks based on the work of Wu et al.[165] ................................................................................................ 112
Figure 5.11. Diffraction spectra for (1-x)NKN xSBN + 0.45 wt% Fe2O3 (0 x 4). .......... 113
Figure 5.12. SEM micrograph of thermally etched 2SBNF. ............................................................... 114
Figure 5.13. SEM micrograph of thermally etched 3SBNF. Arrows indicate herringbone
domain structures. .................................................................................................................................................. 115
Figure 5.14. SEM backscattered imaging micrographs of second phases found in polished
(a) 2SBNF and (b) 3SBNF. Yellow arrows indicate light grey second phase. .......................... 115
Figure 5.15. SEM backscattered imaging micrograph of second phases found in polished
4SBNF. Yellow arrow indicates light grey second phase, and red arrow indicates white
second phase. ............................................................................................................................................................. 115
Figure 5.16. Permittivities of (100-x)NKN-xSBN + 0.45wt% Fe2O3 (4h) (at 100 kHz), with
lower temperatures magnified, inset. ........................................................................................................... 117
Figure 5.17. The transition temperatures of (100-x)NKN-xSBN + 0.45wt% Fe2O3 (4h) .. 117
Figure 5.18. The effect of sintering time on the transition temperatures of 2SBNF. .......... 119
Figure 5.19. Hysteresis behaviour of NKN + 0.3wt% Fe2O3 (Tsint = 1090C) and 2SBNF (Tsint
= 1140C) ..................................................................................................................................................................... 120
Figure 5.20. P-E hysteresis behaviour for (100-x)NKN-xSBNF (2 x 4). .............................. 120
Figure 5.21. Hysteresis behaviour of 4SBNF at varying field strengths. ................................... 121
Figure 5.22. P-E behaviour for 2SBNF sintered at 1140 and 1160C (4h) (navy and red
respectively), and at 1140C (24h) at 40 and 60 kV/cm (green and orange respectively)
........................................................................................................................................................................................... 123
Figure 5.23. P-E behaviour for 98NKN-2SBN + 0.45wt% Fe2O3 (Tsint = 1140C, 24h) ....... 124
Figure 5.24. - plot for NKN + 0.45wt% Fe2O3, with varying temperatures (465-645C)
........................................................................................................................................................................................... 125
Figure 5.25. Resistivity spectra for (1-x)SBN + 0.45wt% Fe2O3 (4h) at 545-550C. ........... 126
Figure 5.26. Conductivity-temperature plots for (100-x)NKN-xSBNF + 0.45wt% Fe2O3,

with x = 0, 2, 3 and 4 mol% (navy, red, green, and blue respectively). ....................................... 126
Figure 5.27. Activation energies for (100-x)NKN-xSBN + 0.45wt% Fe2O3, with 4 hours
sintering time, 0 x 4. ...................................................................................................................................... 127
Figure 5.28. - plot for 98NKN-2SBN + 0.45wt% Fe2O3, with sintering times of 4, 8, 16,
24 and 72 hours at 1120C (navy, red, green, blue and purple respectively). ........................ 129
Figure 5.29. Activation energies of 98NKN-2SBN + 0.45wt% Fe2O3, as a function of

sintering time............................................................................................................................................................. 130
Figure 6.1. Laboratory XRD profiles of (100-x)NKN xSBN + 0.45wt% Fe2O3 formulations
(0 x 4) ..................................................................................................................................................................... 132
Figure 6.2. SEM micrograph of 4SBNF polished sample, showing light grey and white
second phases in a dark grey NKN matrix phase. Yellow arrow indicates light grey second
phase, and red arrow indicates white second phase. ........................................................................... 133
Figure 6.3. Synchrtoron XRD profiles of xSBNF formulations (0 x 4) ................................. 133
Figure 6.4. The refinement of NKNF as (a) the full refinement (square root y axis) and (b)
peak profiles of 10-50 degrees 2 (logarithmic y axis). The blue line shows the observed
data, the red line shows the calculated model, and the grey line below shows the difference
between the two....................................................................................................................................................... 134
Figure 6.5. The refinement of 1 SBNF. ......................................................................................................... 135
Figure 6.6. The synchrotron XRD spectrum and refined data for 3SBNF (logarithmic y-
axis)................................................................................................................................................................................. 136
Figure 6.7. Synchrotron diffraction profile for 4SBNF (a) in the range 0-46 2, square-
root y-axis, and (b) in the range 10-48 2, logarithmic y-axis. ...................................................... 136
Figure 6.8. Phase Content in NKNF as a function of x mol% SBN addition. ............................. 138
Figure 6.9. The pseudocubic lattice parameters for the orthorhombic region of xSBNF.
The cuboid represents the shape of the unit cell (not to scale) ...................................................... 139
Figure 6.10. Pseudocubic lattice parameters for the tetragonal region of NKNF as a
function of SBN addition. Cuboids represent the shape of the unit cell (not to scale) ....... 140
Figure 7.1. BNN particles heat treated under identical conditions, using (a) quartz, (b)
alumina and (c) platinum crucible. ................................................................................................................ 144
Figure 7.2. BNN particles before hot washing stage, sintered at 1100C. ................................. 144
Figure 7.3. BNN particles sintered at 1050C, before hot washing stage. X denotes the area
under EDAX investigation. .................................................................................................................................. 145
Figure 7.4. SEM micrographs showing BNN particles sintered at 1050C after hot washing.
X denotes the area under EDAX investigation. ......................................................................................... 145
Figure 7.5. SEM micrographs showing BNN particles using the 3:2 salt:oxide ratio
(a,b)sintered at 1050C, and sintered at 1100C (c, d). ....................................................................... 146
Figure 7.6. BNN powder using 3:2 salt:oxide ratio used in alumina crucibles, sintered at
(a) 1050 and (b) 1100C. ..................................................................................................................................... 147
Figure 7.7. SEM micrographs of initial NN particles from solution at (a) low and (b) high
magnification. ............................................................................................................................................................ 148
Figure 7.8. SEM micrographs showing an NN particle sintered at 1050C. ............................. 149
Figure 7.9. Schematic illustration of the block casting procedure. ............................................... 150
Figure 7.10. Schematic illustration of the glass slide casting procedure................................... 150
Figure 7.11. Results of various methods of producing slurry; how they formed tapes using
the glass slide casting process. ......................................................................................................................... 151
Figure 7.12. The thickness of 6LN tape cast on a glass slide (a) along the length and (b)
across the width of the slide. ............................................................................................................................. 152
Figure 7.13. P-E hysteresis behaviour of (a) NKN + 0.2 wt % CuO and (b) 95NKN-5LN 0.8
wt% CuO (from Azough et al).[200] .............................................................................................................. 153
Figure 7.14. SEM micrographs of 95NKN-5LN + x wt% CuO single tapes (thickness 20-
30m) sintered at different temperatures. ................................................................................................ 155
Figure 7.15. Diffraction patterns of 95NKN-5LN + 0.4wt% CuO at various sintering

temperatures. ............................................................................................................................................................ 156
Figure 7.16. Diffraction spectra of 94NKN-6LN + 0.4wt% CuO single and double-cast
tapes, both sintered at 1030C.......................................................................................................................... 157
Figure 7.17. Schematic diagram of the RTGG process [after Zhao et al.].[183]...................... 158
Figure 7.18. SEM micrographs of 94NKN-6LN + 0.4 wt% CuO single cast tape sintered at
1030C, (a) plan view, and (b) cross-sectional view of tape. Yellow arrows indicate visible
particles. ....................................................................................................................................................................... 159
Figure 7.19. SEM micrographs showing microstructures of NBTBT thick films (a) using no
dispersant, and (b) using dispersant (after Kimura et al).[131] ..................................................... 159
Figure 7.20. SEM micrographs of single tapes cast of composition 94NKN-6LN + 0.4wt%
CuO + 10%NN particles sintered at temperatures of (a) 1030C, (b) 1090C and 1120C
(c) top view and (d) cross-section. Yellow arrows show template particles. ......................... 160
Figure 7.21. SEM micrographs showing the top and side views of 94NKN-6LN + 0.4wt%
CuO + 10%NN particles sintered at 1120C, with four layers (a-c) and eight layers (d-f).
Yellow arrows indicate visible template particles. ................................................................................ 161
Figure 7.22. SEM micrographs of the top and side views of an eight layered 94NKN-6LN +
0.4wt% CuO + 10%NN particles, sintered at 1150C. Yellow arrows indicate visible
template particles. ................................................................................................................................................... 162
Figure 7.23. XRD spectra for 94NKN-6LN + 0.4wt% CuO + 10 wt% NN particles, 4x layer
pressed tapes sintered at 1090, 1120 and 8x layer pressed tape sintered at 1150C. ....... 163
Figure 7.24. XRD diffraction patterns for NBTKT with random orientation (blue) and with
5% added SrTiO3 template particles added (pink) (from Yilmaz et al).[137] ......................... 163
Figure 7.25. Comparison of XRD diffraction profiles of 94NKN-6LN + 0.4 wt% CuO (a)
double cast sintered at 1030C, and (b) 8x layered tape with 10 wt% NN particles added,
sintered at 1150C. ................................................................................................................................................. 165
Figure 7.26. Permittivity data for 94NKN-6LN + 0.4 wt% CuO + 10% NN particles, as a
function of applied frequency. Inset shows 1-400C range under closer inspection. ........ 166
Figure 7.27. Cole-Cole plot data for 94NKN-6LN + 0.4 wt% CuO + 10% NN particles, as a
function of temperature (485 545 C) ...................................................................................................... 166
Figure 7.28. Cole-Cole impedance plot fitting for 94NKN-6LN + 0.4 wt% CuO + 10 wt% NN
particles, at temperature 545C. Blue spots and red line denote data, green line denotes
fitted semi-circle model........................................................................................................................................ 167
Figure 7.29. Comparison of single and four-layered 6LN + 0.8 wt% CuO + 10% NN
particles samples sintered at 1090C............................................................................................................ 168
Figure 7.30. SEM image of four-layered 6LN + 0.8 wt% CuO + 10% NN particles sample
sintered at 1120C showing (a) as-fired surface and (b) side elevation view. ........................ 168
Figure 7.31. XRD Spectra for 94NKN-6LN + 0.8wt% CuO + 15 wt% NN particles, 4 layer
pressed tapes sintered at 1090 and 1120C. ............................................................................................. 169
Figure 7.32. XRD diffractogram for 93NKN-7LT-xNN particles (here NKN is denoted as
KNN) [from Feng et al}.[82] ............................................................................................................................... 170
Figure 7.33. Schematic showing the evolution of K 3Li2Nb5O15 structure from NKN (from
Feng et al.)[82] .......................................................................................................................................................... 170
APPENDIX 2 - TABLES
Table 21. Hysteresis Properties of pure NKN (in order of field threshold, E). ....................... 39
Table 22. Summary of properties and processing of BNN particles (optimal results) with
references. ...................................................................................................................................................................... 58
Table 31. Details of raw starting powders ................................................................................................. 61
Table 32. Samples prepared in this study. ................................................................................................. 63
Table 33. Manufacturers data for slurry additives ............................................................................... 68
Table 34. Samples under Investigation at Daresbury SRS, Station 6.2. ...................................... 74
Table 41. Summary of reported NKN pseudo-cubic parameters (at room temperature). 87
Table 42. Average lattice parameters of phases present in Cu doped NKN (sintered
pellet) ................................................................................................................................................................................ 88
Table 43. Average lattice parameters for phases present in Cu doped NKN (powder
sample)............................................................................................................................................................................. 95
Table 44. Average parameters of phases present in 94NKN-6LT. ............................................. 102
Table 51. Summary of electrical data for (100-x)NKN-xSBN + 0.45wt% Fe2O3 system, at
545C. ............................................................................................................................................................................. 128
Table 61. The phase content for xSBNF refinements, including GOF values. ....................... 137
Table 62. Pseudo-cubic parameters for orthorhombic phase in xSBNF (accurate to 5dp)
........................................................................................................................................................................................... 139
Table 63. Pseudo-cubic parameters for tetragonal phase in xSBNF (accurate to 5dp)... 140
Table 71. The EDAX data for a pre-hot-washed BNN particle. ..................................................... 145
Table 72. The EDAX data for a hot-washed BNN particle. .............................................................. 146
Table 73. Resulting data from BNN particles in this investigation. ........................................... 147
Table 74. The EDAX data for chemical compositions of Figure 7.7 (Spectrum 3). ............ 148
Table 75 Volume fractions of components in test slurries. ......................................................... 152

Thesis Sodium Potassium Niobate Based Piezoelectric Ceramics

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SODIUM POTASSIUM NIOBATE

BASED PIEZOELECTRIC CERAMICS

Year of Submission: 2012

Margaret Wgrzyn Sodium Potassium Niobate Based Piezoelectric Ceramics Page 2

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Margaret Wgrzyn Sodium Potassium Niobate Based Piezoelectric Ceramics Page 5

Synchrotron XRD studies were undertaken as a function of temperature on

Synchrotron X-ray diffraction analysis of 94 NKN-6LiTaO3 showed that tetragonal

Margaret Wgrzyn for Doctor of Philosophy at The University of Manchester

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4. Further information on the conditions under which disclosure, publication and

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1.1 General Introduction

Figure 1.1. Number of publications cited in refereed journals based on lead-free

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Figure 1.2. Piezoelectric coefficient Curie temperature comparison of PZT materials to

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NKN is a highly researched material as a lead-free piezoelectric ceramic. It is a mixture

1.2 Aims and Objectives of this Investigation

Another objective of this investigation is to develop NKN-based thick films in order to

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2.1 Electroceramic Properties

2.1.1 Dielectric Properties

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Figure 2.1. Schematic diagram showing different polarisation mechanisms in a material

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The relative permittivity, r, is a dimensionless property found in materials and is defined

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Figure 2.5. Schematic of k parameter (after van Randeraat and Setterington).[41]

Another piezoelectric parameter that must be discussed is the electromechanical coupling

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Figure 2.6. Variation of r of BaTiO3 as a function of temperature. Corresponding phase

A ferroelectric material undergoes the polarisation described in section 2.1.1, however

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equation in 1980 to allow a better fit to observed behaviour shown as

Equation 2:16,[51] and it is this that is employed in current literature.[52-

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When a ferroelectric material undergoes spontaneous polarisation, PS, a surface charge is

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2.1.4 Impedance Spectroscopy

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The Pb(Zr1-xTix)O3 phase diagram is shown in Figure 2.16. It is a solid solution of

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2.2.2 Barium Titanate (BT)

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2.2.3 Potassium Niobate, KNbO3 [KN]

The ferroelectric behaviour of KN was first reported by Matthias and Remieka in

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2.2.4 NaNbO3 [NN]

Figure 2.21. Typical antiferroelectric hysteresis behaviour (after Uchino).[4]

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Although NN was shown to be ferroelectric in 1951, with a spontaneous polarisation

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