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Smart Materials

Smart Materials

Selected, peer reviewed papers from the


International Conference on Smart Materials
Smart/Intelligent Materials and Nanotechnology
(Smartmat-08)
&
Selected, peer reviewed papers from the
2nd International Workshop on
Functional Materials and Nanomaterials
(IWOFM-2)

Edited by

Tawee Tunkasiri

TRANS TECH PUBLICATIONS LTD


Switzerland UK USA

Copyright 2008 Trans Tech Publications Ltd, Switzerland


All rights reserved. No part of the contents of this book may be reproduced or transmitted in any
form or by any means without the written permission of the publisher.
Trans Tech Publications Ltd
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http://www.ttp.net
Volumes 55-57 of
Advanced Materials Research
ISSN 1022-6680
Full text available online at http://www.scientific.net

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PREFACE

This proceedings collects all the invited and contributing articles presented at the
International Conference on Smart Materials-Smart! Intelligent Materials and Nano
Technology (SmartMat-'08) and also the 2nd International Workshop on Functional
Materials and Nanomaterials (IWOFM-2). The main theme of the conference covers
intelligent/smart materials and their applications and aims to cross-fertilise these
materials with nanomaterials. The main topics of conference are: materials devices,
processing applications, modeling and characterization of a wide range of materials,
piezoelectric ceramics/polymers, magnetostrictive materials, smart structural materials
and composites, electrooptics and other photonic systems, carbon and other nanotubes,
new nano and micromaterials, biomedical materials, sensors and other smart materials.

Honorary Advisory Committee


C.N.R. Rao
L. Eric Cross
Thomas R. Shrout
Anthony K. Cheetham

Jawaharlal Nehru Center for Advanced Scientific Research


(JNCR), India
Penn State University, USA
Penn State University, USA
University of California at Santa Barbara, USA

Organizing Committee
Chair :
Tawee Tunkasiri
Co-chairs :
Director
Mongkon Rayanakorn
General Secretary :
Gobwute Rujijanagul

Chiang Mai University, Thailand


National Metal and Materials Technology Center (MTEC), Thailand
Dean of Faculty of Science, Chiang Mai University
Chiang Mai University, Thailand

Committee Members
Robert Molloy
Narin Sirikulrat
Jerapong Tontrakoon
Pitt Supaphol
Benya Cherdhirunkorn
Somnuk Sirisoonthorn

Chiang Mai University, Thailand


Chiang Mai University, Thailand
Chiang Mai University, Thailand
Chulalongkorn University, Thailand
Thammasat University, Thailand
MTEC, Thailand

International Advisory Board


Kenji Uchino
Ahmad Safari
Susan Trolier-McKinstry
Ron Stevens
Tadashi Takenaka
Kenneth MacKenzie
Brian Tighe
David Cann
Xiaoli Tan
Zhu Weigung
David Hall
Steve Milne
Jin Hyeok Kim
Sin, Byoung-Chul
John Wang
Nguyen Xuan Phuc
B.V.R. Chowdari
Enge Wang
Wen-Bin Liau
Yoshio Bando
Arshad Bhatti

Penn State University, USA


Rutgers University, USA
Penn State University, USA
Bath University, UK
Tokyo University, Japan
Victoria University of Wellington, New Zealand
Aston University, UK
Oregon State University, USA
Iowa State University, USA
Nanyang Technological University, Singapore
The University of Manchester, UK
Leeds University, UK
Chonnam National University, Korea
Dong-Eui University, Korea
National University of Singapore, Singapore
Institute of Materials Science, Vietnam
National University of Singapore, Singapore
Institute of Physics, Beijing, China
National Taiwan University, Taiwan
National Institute for Materials Science, Japan
The Commission on Science and Technology for
Sustainable Development in the South, Pakistan

Local Organizing Committee


Tawee
Gobwute
Jerapong
Narin
Supon
Manoch
Wim
Rattikorn
Sukanda
Apinpus
Arnon
Anucha
Wandee
Sukum
Wanwilai
Pornrat
Robert
Torranin
Pitt
Benya
Somnuk
Somprasong
Rachada
Pichet

Tunkasiri
Rujijanagul
Tontrakoon
Sirikulrat
Ananta
Naksata
Nhuapeng
Yimnirun
Jiansirisomboon
Rujiwatra
Chaipanich
Watcharapasorn
Thamjaree
Eitssayeam
Chaisan
Wattanakasiwich
Molloy
Chairuangsri
Supaphol
Cherdhirunkorn
Sirisoonthorn
Sreekaew
Wongsuwan
Tepsuwan

Suppatad
Nuntana
Apiroj
Mongkol
In-thorn
Kamonpan
Jirawan
Duangpon
Yongyutt
Phisanu
Athipong
Uraiwan
Anocha
Thongsuk
Prachya
Burapa
Worawut
Gannaga
Chompunuch
Sarawute
Theerachai
Narathip
Singhadej

Dangkreung
Thamtamala
Lhegyong
Supa
Booncheue
Pengpat
Upanunt
Laksawat
Laosiritaworn
Chiawkhun
Ngamjarurojana
Intatha
Munpakdee
Triyachaipanich
Malasri
Paejui
Sreesukkham
Satittada
Puchmark
Thountom
Bongkarn
Vittayakorn
Tangjuank

Table of Contents
Preface
Committees
Piezoelectric Actuators 2008: Key Factors for Commercialization
K. Uchino
Tailored Intelligent Materials
R.P. Tandon
Origin of P-E Hysteresis Offsets in Compositionally Graded Ba(1-x)SrxTiO3 Thick Films
J. Barrel, E. Stytsenko, M. Viviani and K. MacKenzie
Nanosized Titania, a Smart Material or is it just Clever?
R. Stevens, D. Regonini, C.R. Bowen and A. Jaroenworaluck
Magnetic Nanoparticles as Smart Heating Mediator for Hyperthermia and Sorbent
Regeneration
N.X. Phuc, N.A. Tuan, N.C. Thuan, V.A. Tuan and L.V. Hong
Defining Structure in Electrospun Polymer Fibres
G.R. Mitchell, M. Belal, F.J. Davis, D.E. Elliott, M. Kariduraganavar, S.D. Mohan, R.H. Olley
and S. Sen

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I. Piezoelectric Ceramic/Polymers
Sonocatalyzed Ammonothermal Preparation of Fine Lithium Niobate Powders
A. Rujiwatra, N. Thammajak, Y. Chimupala and P. Laoratanakul
Effectively Doping of Rare Earth Additives in Sol Gel Derived PZT Ceramics
S.K. Asl and S.K. Asl
Micro- and Macroscopic Observations of the Microtexture, the Dielectric and Piezoelectric
Properties in Bulk and Multilayer Pb (Zr, Ti)O3
N. Binhayeeniyi, A. Dasaesamoh, J. Khakong, P. Khaenamkaew and S. Muensit
Effect of Annealing on the Structure and Dielectric Properties in PZT-PCoN Ceramics
N. Vittayakorn, N. Chaiyo, R. Muanghlua, A. Ruangphanit and W.C. Vittayakorn
Phase Evolution and Physical Properties of (1-x)BZT-xBFN Ceramic System
H. Maimon, S. Eitssayeam, U. Intatha, T. Tunkasiri and G. Satittada
Relationships between Processing Parameters and Properties of PZT Ceramics
C. Puchmark and G. Rujijanagul
Synthesis of Conducting Polymer Films by Plasma Polymerization Process
W. Bhanthumnavin, P. Kamphiranon and B. Paosawatyanyong
Chemical Synthesis and Characterization of ZnTiO3 Powder Prepared by the
Coprecipitation Oxalate Method
P. Pookmanee, J. Yotasing and S. Phanichphant
Dielectric and Piezoelectric Properties of B2O3 and SnO2 Doped Barium Titanate Ceramics
N. Tawichai and G. Rujijanagul
Ferroelectricity of (1-x)(Bi0.5Na0.5)TiO3 xBa(Ti0.95Zr0.05)O3 Solid Solution Ceramics
N. Sawangwan, J. Tontrakoon, S. Sirisoonthorn and T. Tunkasiri
Effect of Calcination Temperature on Phase and Morphology of Sol-Gel Derived PZTN
Powders
C. Sangsubun, A. Watcharapasorn and S. Jiansirisomboon
BaMnTiO3 Synthesized by the Oxalate and Impregnation Methods
P. Pookmanee, P. Ketwong and S. Phanichphant
Ammonothermal Preparation of Barium Zirconate Fine Powders
S. Wannapaiboon and A. Rujiwatra
Effect of Al2O3 Addition on Dielectric, Piezoelectric and Ferroelectric Properties of
0.2Pb(Zn1/3Nb2/3)O30.8Pb(Zr1/2Ti1/2)O3 Ceramics
A. Ngamjarurojana, S. Ananta and R. Yimnirun
Microstuctural Study and Properties of 0.8PZT-0.2BT Ceramics Using a Two-Stage
Sintering Procedure
W.C. Vittayakorn

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Smart Materials

Effects of Manganese Addition on Phase Formation, Microstructure and Electrical


Properties of Barium Titanate Ceramics
J. Tangsritrakul, M. Unruan, P. Ketsuwan and R. Yimnirun
Induced Internal Bubble Shapes Affected Piezoelectric Behaviors of PVDF Films
D. Suwansumpan, H. Manuspiya, P. Laoratanakul and A.S. Bhalla
Dielectric Properties Enhancement in Polybenzoxazine Composite at Multi-Frequency
Range
N. Krueson, H. Manuspiya, P. Laoratanakul and H. Ishida
Effect of Thermal Treatment on Dielectric Properties of 0.8Pb(Zr1/2Ti1/2)O3 0.2Pb(Co1/3Nb2/3)O3 Ceramics
A. Prasatkhetragarn, S. Ananta, R. Yimnirun and D.P. Cann
Influence of Fabrication Processing on Perovskite Phase Formation of KNN-BZT
M. Sutapun, R. Muanghlua, C.C. Huang, D.P. Cann, W.C. Vittayakorn and N. Vittayakorn
Effect of Lead Nickel Niobate Substitution on Phase Transitions of Lead Zirconate
Ceramics Prepared by the Solid State Reaction Method
S. Wirunchit, P. Laoratanakul and N. Vittayakorn
Synthesis, Crystal Structures, Phase Transition Characterization and Thermal Properties of
the (1x)PbZrO3-xPb(Co1/3Nb2/3)O3 Solid Solution System
W. Banlue, R. Muanghlua, W.C. Vittayakorn and N. Vittayakorn
Effects of Zr/Ti Ratio on the Structure and Ferroelectric Properties in PZT-PZN-PMN
Ceramics near the Morphotropic Phase Boundary
R. Muanghlua, S. Niemchareon, W.C. Vittayakorn and N. Vittayakorn
Impedance and Dielectric Properties of Nb-Doped Pb(Zr0.52Ti0.48)O3 Ceramics
P. Ketsuwan, A. Ngamjarurojana, Y. Laosiritaworn, S. Ananta, R. Yimnirun and D.P. Cann
Dielectric and Piezoelectric Properties of Zirconium-Doped Bismuth Sodium Titanate
Ceramics
A. Watcharapasorn and S. Jiansirisomboon
Structural and Morphologies of (1-x)BaTiO3-xBaFe0.5Nb0.5O3 Solid Solution
S. Eitssayeam
Fabrication of 0-3 Non-Lead Based Piezoceramic/Polymer Composites Using Suction
Technique
T. Sareein, W. Thamjaree, W. Nhuapeng and T. Tunkasiri
Microstructures of Zirconium Titanate Powders and Ceramics Prepared by Solid-State
Mixed Oxide Method
C. Puchmark and P. Tipparak
Preparation and Properties of B2O3-Doped Ba(Zr0.07Ti0.93)O3 Ceramics
P. Jarupoom, G. Rujijanagul, K. Pengpat and T. Tunkasiri
Characterization of LiNbO3 Powder Prepared by Citrate Gel Method
S. Onnom, D. Wongratanaphisn, P. Supaphol, P. Udomsamuthirun, T. Nilkamjon, S. Radrang, S.
Sonkrua and S. Payoogthum
X-Ray Absorption Spectroscopy Study of Ba1-xSrxTiO3 (x = 0.0-0.2) at the Ti-K and Ba-LIII
W. Somphon and S. Srilomsak
Synthesis of Na0.5Bi0.5TiO3 Submicron Particles in Molten Salt
P. Setasuwon and S. Kijamnajsuk
Effects of Starting Materials on Molten Salt Synthesis of Bi4Ti3O12
P. Setasuwon and S. Kijamnajsak
Effect of ZrO2 Doping on Crystal Structure, Microstructure and Phase Transition of Lead
Titanate Ceramics
P. Sittiketkron, S. Sukkho and T. Bongkarn
Fabrication of Barium Stannate Tatanate Ceramics via Combustion Technique
C. Wattanawikkam and T. Bongkarn
The Effect of Excess PbO on Crystal Structure and Microstructure of (Pb0.925Ba0.075)TiO3
Ceramics
T. Bongkarn and R. Sumang
The Preparation of Barium Stannate Titanate Ceramics via Solid State Reaction Method
T. Bongkarn and W. Khiawwangthong
Preparation of Barium Strontium Titanate Ceramics via Combustion Method
T. Bongkarn and C. Wicheanrat

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Advanced Materials Research Vols. 55-57

Effect of MnO2 Impurity on the PZT-PMN System Ceramics for Piezoelectric Transformer
Y. Suwan, A. Niyompan, R. Tipakontitikul and P. Laoratanakul
Effect of Excess PbO on Crystal Structure, Microstructure and Phase Transition of Lead
Titanate Ceramics
W. Tangkawsakul, P. Sittiketkron and T. Bongkarn
Effects of Calcination Temperatures on Phase and Morphology Evolution of
(Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 Powders Synthesized via Solid-State Reaction and Combustion
Technique
A. Thongtha, K. Angsukased and T. Bongkarn
Phase Formation and Microstructure of PBZT Powders Prepared via Mixed Oxide Method
T. Bongkarn and C. Thiangchit
Effect of Calcination Temperatures on Microstructure and Phase Formation of
Ba(Zr0.25Ti0.75)O3 Powders
T. Bongkarn, N. Phungjitt and N. Vittayakorn
Fabrication of Lead Barium Titanate Ceramics via Conventional Solid-State Mixed Oxide
Technique
T. Bongkarn and P. Panya
Fabrication of Barium Zirconium Titanate Ceramics Using Ultrasonic Ball Milling
Technique
W. Thamjaree, W. Nhuapeng and T. Tunkasiri
Ferroelectric and Mechanical Properties of PZT-PZN-PNN Ceramics
S. Nabunmee, N. Vittayakorn, D.P. Cann and G. Rujijanagul
Antiferroelectric Lead Zirconate Ceramics with Nanoparticle Alumina Additions
C. Puchmark, S.J. Milne and G. Rujijanagul
Morphotropic Phase Boundary of Lead-Free Piezoelectric Ceramics from BNT- KN System
N. Pisitpipathsin, W. Koontasing, S. Eitssayeam, U. Intatha, G. Rujijanagul, K. Pengpat and T.
Tunkasiri
Formation of NaNbO3 Crystals in Dielectric Glass and Glass-Ceramics of a Na2O-Nb2O5Al2O3-SiO2 System
S. Thongsaeng, A. Niyompan, R. Tipakontitikul and K. Pengpat
Ferroelectric and Dielectric Aging Effects of Fe3+/Nb5+ Hybrid-Doped Barium Titanate
Ceramics
S. Prasertpalichat, M. Unruan, J. Tungsritrakul and R. Yimnirun

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II. Magnetostrictive Materials


Effect of Calcination Conditions on Phase Formation and Characterization of BiFeO3
Powders Synthesized by a Solid-State Reaction
C. Silawongsawat, S. Chandarak, T. Sareein, A. Ngamjarurojana, S. Maensiri, P. Laoratanakul, S.
Ananta and R. Yimnirun
Effect of Calcination Conditions on Phase Formation and Characterization of BiFeO3BaTiO3 Powders Synthesized by a Solid-State Reaction
S. Chandarak, T. Sareein, A. Ngamjarurojana, S. Maensiri, P. Laoratanakul, S. Ananta and R.
Yimnirun

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III. Shape Memory Alloys


Assessment of Mechanical Properties and Transformation Behavior of Locally-Made Ni-Ti
Alloys Used in Orthodontics
N. Chiranavanit, A. Khantachawana, N. Anuwongnukroh and S. Dechkunakorn
Effect of Direct Electric Resistance Heat Treatment on Mechanical Properties of NiTi
Orthodontic Arch Wires
W. Kiattiwongse, A. Khantachawana and P. Santiwong

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IV. Actuator and Sensor Materials


Materials of Nanocrystalline Sr1-xBaxBi4Ti4O15 for Piezoelectric Sensor
N.A.A. Manaf, M.M. Salleh and M. Yahaya
Electrical Conductivity of Poly(3,4-Ethylenedioxythiophene)-Poly(Styrenesulfonate)
Coatings on Polyacrylonitrile Nanofibers for Sensor Applications
M. Panapoy, M. Saengsil and B. Ksapabutr

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Smart Materials

SiO2-Multiwalled Carbon Nanotube Base Gas Sensor


S. Jesen, S. Ruangphet and S. Cheirsirikul
Application of the PEGDE Modified Silk Fibroin Membrane to an Amperometric Glucose
Biosensor
P. Moonsri, S. Watanesk, R. Watanesk, H. Niamsup, Q. Cheng and R.L. Deming
Enhanced the Performance of Fluorescence Gas Sensor of Porphyrin Dye by Using TiO2
Nanoparticles
N.H. Yusoff, M.M. Salleh and M. Yahaya
Determination of Mn Site in BaTiO3 by X-Ray Absorption Spectroscopy
R. Yimnirun, J. Tangsritrakul, S. Rujirawat and S. Limpijumnong
Changes in Ferroelectric Properties of 0.7PMN0.3PT Ceramic with Compressive Stress
M. Unruan, R. Wongmaneerung, Y. Laosiritaworn, S. Ananta and R. Yimnirun
Scaling Behavior of Dynamic Hysteresis in Hard PZT Bulk Ceramics under Influence of
Compressive Stress
N. Wongdamnern, A. Ngamjarurojana, S. Ananta, Y. Laosiritaworn and R. Yimnirun
Gas-Sensing Property Evaluation of Reactively Sputtered Chromium Oxide Thin Films
C. Oros, A. Wisitsoraat, P. Limsuwan, M. Horpathum, V. Patthanasettakul and A. Tuantranont
Effect of Platinum Impregnation on ZnO Tetrapods for Ethanol Sensor
N. Hongsith and S. Choopun
Ethanol Sensing Characteristics of ZnO Nanostructures Impregnated by Gold Colloid
E. Wongrat, P. Pimpang, N. Mangkorntong and S. Choopun
Structural and Optical Study of Nano-Structured CdS-CBD Thin Films on CdTe Substrates
Grown by Various Temperatures Deposited
C. Suwattanaphiboon, N. Suttisiri, E. Hoonnivathana and C. Kunsombat
Spectroscopys Studies of Iron Phthalocyanine Thin Films
O. Chamlek, S. Pratontep, T. Kerdcharoen and T. Osotchan
Feature Difference of Interaction between Various Organic Solvent Vapors and Metal
Phthalocyanines Coated on Quartz Crystal
T. Hongkachern, W. Suwannet, R. Jaisutti, S. Pratontep and T. Osotchan

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V. Smart Structural Materials and Composites


Stability of Liquid Al Foams by Oxidised Al Powders
S. Asavavisithchai
Transparent Glass Ceramics from 65LiNbO3-35SiO2 Glass Composition
P. Prapitpongwanich, R. Harizanova, C. Rssel and K. Pengpat
Surfactant-Templated Synthesis of Modified Porous Clay Heterostructure (PCH)
K. Srithammaraj, R. Magaraphan and H. Manuspiya
Evaluation the Manufacturing Process of Silk/Gelatin Electrospun Membrane
C.Y. Chao, C.W. Lou, C.T. Lu, C.C. Huang and J.H. Lin
Influence of ZnO Content on Film Morphology and Device Performance of MEH-PPV/ZnO
Hybrid Solar Cells
K. Kasemsuwan, T. Suvewong, V. Pavarajarn and C. Thanachayanont
Water Absorption and Phase Transition of Calcium Carbonate in the Sea Water Mussel
(Anadara Granosa)
W. Siriprom, W. Onreabroy and P. Limsuwan
Temperature Effect on Chicken Egg Shell Investigated by XRD, TGA and FTIR
K. Naemchanthara, S. Meejoo, W. Onreabroy and P. Limsuwan
Structural and Optical Properties of Zn0.8Co0.2O Ceramics
S. Sujinnapram, W. Onreabroy and T. Nantawisarakul
The Effect of Organic Modificaition Method onto Montmorillonite on Mechanical
Properties of Natural Rubber
C. Thongpin, N. Tangchantra, P. Kaewpetch, J. Dejkun and A. Chartsiriwattana
Thermal Stabilization of PVC Using Organic Modified Montmorillonite
C. Thongpin, N. Tangchantra, A. Kositchaiyong, R. Sagnuanmoo, J. Jantham and A. Sooksa-ard
Thermal Conductivity of Ceramic Fibres at High-Temperatures
M. Anis-ur-Rehman
Effect of WC Addition on Phase Formation and Microstructure of TiC-Ni Composites
N. Wora-uaychai, N. Poolthong and R. Tongsri

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Effect of Reaction between Fe and Carbide Particles on Mechanical Properties of Fe-Base


Composite
S. Chakthin, N. Poolthong and R. Tongsri
Copper Powder Extrusion: A Smart Processing for Energy and Environment Conservation
R. Wichianrak, N. Thavarungkul, N. Poolthong and R. Tongsri
Toughening of PZT Ceramics by In Situ Complex Structures
N. Thongmee, A. Watcharapasorn and S. Jiansirisomboon
Fabrication and Characterization of Sol-Gel Derived PZT/WO3 Ceramics
T. Sreesattabud, A. Watcharapasorn and S. Jiansirisomboon
Influence of Annealing Temperature on the Properties of Nanostructure ITO Thin Films
Prepared by Ion-Assisted Electron Beam Evaporation
A. Pokaipisit, M. Horprathum and P. Limsuwan
Effect of Carbon Addition on Dielectric Properties of 0-3 PZT-Portland Cement Composite
N. Jaitanong, K. Wongjinda, P. Tammakun, G. Rujijanagul and A. Chaipanich
Effect of Polarization on the Microstructure and Piezoelectric Properties of PZT-Cement
Composites
A. Chaipanich and N. Jaitanong
Magnetic Hysteresis Properties in Dilute Ising Ultra-Thin-Film: Monte Carlo Investigation
Y. Laosiritaworn
Mechanical Properties and Microstructure of Aramid/Al2O3/Epoxy Resin Laminated
Composites
S. Kumfu, W. Nhuapeng, W. Thamjaree and T. Tunkasiri
Manufacturing Process and Property Analysis of Sound Absorption Sandwich Board
C.W. Lou, P. Chen and J.H. Lin
Novel Manufacturing Process for Tencel/Chitosan/Pectin Composite Dressing
C.K. Lin, C.W. Lou, C.T. Lu, C.C. Huang and J.H. Lin
Thermoplastic Polyurethane (TPU) Honeycomb Air Cushion Combined with Polylactic
Acid (PLA) Nonwoven Fabric for Impact Protection
C.H. Lee, C.W. Lou, W.H. Hsing, I.J. Tsai and J.H. Lin
The Effects of Thermal Consolidation Methods on PET Nonwoven Composites for Thermal
Insulation Use
C.W. Lou, C.W. Lin, C.C. Lin, S.J. Li, I.J. Tsai and J.H. Lin
Manufacturing Processing of Polylactic Acid Braids as Artificial Bone Matrix
C.W. Lou, C.T. Lu, C.C. Huang, H.Y. Wang and J.H. Lin
Manufacturing Process and Property Evaluation of Functional Composite Yarn-Dyed
Woven Fabrics Made from Bamboo Charcoal/Stainless Steel and TPU
C.I. Huang, C.I. Su, C.W. Lou, W.H. Hsing and J.H. Lin
Manufacturing and Stab-Resisting Properties of Compound Fabric Reinforced Using
Recycled Nonwoven Selvages
J.M. Chen, J.C. Hsieh, C.W. Lou, W.H. Hsing, H.J. Yang and J.H. Lin
Manufacturing Process and Practical Examination for a 3D Structural Geocell Made from
Recycled PET Fibers
W.H. Hsing, J.C. Hsieh, C.W. Lin, C.W. Lou, P.T. Liu and J.H. Lin
Manufacture and Performance Evaluation of Elastic/Bamboo Wrapped Yarn
S.P. Chang, C.M. Lin, C.W. Lou, W.H. Hsing and J.H. Lin
Evaluation of Manufacturing Technology and Characterization of Composite Fabric for
Stab Resistant Materials
C.C. Lin, C.W. Lou, W.H. Hsing, W.H. Ma, C.M. Lin and J.H. Lin
PET/PP Blend with Bamboo Charcoal to Produce Functional Composites: Evaluation of
Functionalities
J.H. Lin, C.W. Lou, J.M. Chen, C.T. Hsieh and Z.H. Liu
The Effect of Processing Parameters on Properties of Bi2GeO5 Glass Ceramics
P. Kantha, S. Sirisoonthorn and K. Pengpat
Photo-Induced Superhydrophilic TiO2 Films Deposited by DC Reactive Magnetron
Sputtering at Room Temperature
M. Horprathum, P. Chindaudom, V. Patthanasettakul, S. Rotbuathong, P. Eiamchai and P.
Limsuwan

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Smart Materials

Temperature Dependence of Optical Constants of Silver Film Studied by In Situ


Spectroscopic Ellipsometry
S. Rojebuathong, P. Chindaudom, W. Luangtip, M. Horphatum, P. Eiamchai, V.
Patthanasetthakul and P. Limsuwan
Investigation of Aluminium Diffusion into an Amorphous Silicon Thin Film at High
Temperature by In Situ Spectroscopic Ellipsometry
W. Luangtip, S. Rotbuathong, P. Chindaudom, M. Horphatum, V. Patthanasetthakul, P. Eiamchai
and T. Srikirin
Self-Cleaning Properties of TiO2 Films Deposited by Reactive Magnetron Sputtering Using
Smooth D.C. and Pulsed D.C. Source
S. Pudwat, P. Rakkwamsuk and S. Damrongrattana
Fabrication of Double Layers of Aramid Fiber/Alumina/Epoxy Resin Laminate Composite
Using Low-Pressure Technique
W. Nhuapeng, S. Kumfu, W. Thamjaree and T. Tunkasiri
Fabrication of Ferroelectric Bismuth Titanate Glass-Ceramic by Incorporation Method
K. Pengpat
The Influence of Total and Oxygen Partial Pressures on Structure and Hydrophilic
Property of TiO2 Thin Films Deposited by Reactive DC Magnetron Sputtering
S. Chaiyakun, A. Buranawong, T. Deelert and N. Witit-anun
Characterization of Anatase and Rutile TiO2 Thin Films Deposited by Two Cathodes
Sputtering System
N. Witit-anun, P. Rakkwamsuk and P. Limsuwan
Ferroelectric Glass-Ceramics from the PbO-Bi2O3-GeO2 System
A. Munpakdee, K. Pengpat, T. Tunkasiri and D. Holland
Composites Base on Geopolymer Matrices: Preliminary Fabrication, Mechanical Properties
and Future Applications
T.D. Hung, D. Pernica, D. Kroisov, O. Bortnovsky, P. Louda and V. Rylichova

445

449
453
457
461
465
469
473
477

VI. Electro-Optics
High Capacity Packet Switching with a Soliton Pulse in a Nonlinear Micro Ring Resonator
S. Mitatha, K. Dejhan, S. Thongmee and P.P. Yupapin
Attosecond Pulse and Beyond Generation Based on Multi-Stage Micro Ring Resonators
S. Mitatha, K. Dejhan, S. Chaiyasoonthorn and P.P. Yupapin
Entangled Photon Generation in a Nonlinear Micro Ring Resonator for Quantum Key
Distribution Use
C. Sripakdee, K. Sarpat, W. Suwancharoen and P.P. Yupapin
Temperature Dependent Photoluminescence of ZnSe/Alq3 Hybrid Heterostructure
W. Pecharapa, P. Potirak and W. Yindeesuk
Light Scattering in Poly(Methyl Methacrylate) Hybrid Sheet Filled by Titanium Dioxide
Nanocrystals Prepared by High Electric Field Assisted Spray Pyrolysis Process
B. Ksapabutr, P. Anukoolwittaya and M. Panapoy
Improvement of UV Protection Properties in Poly(Methyl Methacrylate) Sheet Coated by
Titanium Dioxide/ Poly(Methyl Methacrylate) Hybrid Film
M. Panapoy, P. Wannasut and B. Ksapabutr
Packet Switching Start-Stop Bits Generation Based on Bifurcation Behavior of Light in a
Micro Ring Resonator
N. Pornsuwancharoen, J. Kumbun and P.P. Yupapin
Construction and Evaluation of the Fiber-Optic Sensor System for Chemical Vapor
Detection
M. Kittidechachan, I. Sripichai, W. Supakum, S. Thuamthai, S. Angkaew and P. Limsuwan
Fluoride and Antimony-Doped Tin Oxide Film by Spray Pyrolysis
R. Buntem, P. Kraisingdecha and W. Sadee

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489
493
497
501
505
509
513

VII. MEMS
Improving Sensitivity of p-n Junction Temperature Sensor by Carrier Lifetime
Modification
A. Poyai, E. Ratanaudomphisut, J. Supadech, N. Klunngien, C. Hruanan and S. Sophitpan

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Novel Design of a Micro Gyroscope Based Birefringence Measurement for Sensor


Applications
P. Phiphithirankarn, P. Yabosadee, W. Suwancharoen and P.P. Yupapin

521

VIII. Carbon and Others


Finite Element Modeling of van der Waals Interaction for Elastic Stability of Multi-Walled
Carbon Nanotubes
C. Thongyothee and S. Chucheepsakul
Improvement of Mesopore Structure of Resorcinol and Formaldehyde Carbon Cryogels by
Acid Solution
K. Kraiwattanawong, P. Kitchaiya, A. Neramittagapong, P. Praserthdam and H. Tamon
Optimization of Chemical Vapor Deposition Synthesis Conditions for Multiwall Carbon
Nanotube by Statistical Analysis of Experiment
P. Saiprasert, D. Koolpiruck and S. Chiangga
Mechanochemical Treated Multi-Walled Carbon Nanotubes for Incorporation of Metal
Ions
U. Rinzin, P. Singjai, P. Wilairat and S. Meejoo
Synthesis of Coil-Like Shape CNTs by Thermal CVD Method
U. Pakdee, N. Suttisiri, E. Hoonnivathana and S. Chiangga
Attachment of Metal Oxide Nanoparticles on Carbon Nanotubes with Different Oxidation
Levels
C.T. Hsieh and J.Y. Lin
Microstructure and Characterizations of Portland-Carbon Nanotubes Pastes
T. Nochaiya, P. Tolkidtikul, P. Singjai and A. Chaipanich
Mechanical Properties of Hemp Fiber Composites with Carbon Nanotubes Reinforcement
H. Longkullabutra, W. Nhuapeng, W. Thamjaree and T. Tunkasiri
The Diamond Crystal Nucleation by Combustion Activation CVD
Y. Wongprasert, R. Muanghlua and K. Sato
Growth Conditions for Carbon Nanotubes and Helical Nanofibers on Copper Substrates
Using Sparked Catalysts
B. Toboonsung and P. Singjai
Electronic Structure of Straight and T-Shape Singled-Wall Carbon Nanotube Junctions: A
Molecular Quantum Mechanics Study
A. Udomvech and T. Kerdcharoen

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533
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549
553
557
561
565

IX. New Nano


Structural Evolution in the Processing of Fe/ BaFe12O19 Nano Composite via Mechanical
Alloying
A.G. Ataie and R. Nikkhah-Moshaie
Oxygen Control on Nanocrystal-AlON Films by Reactive Gas-Timing Technique R.F.
Magnetron Sputtering and Annealing Effect
W. Bunjongpru, S. Porntheeraphat, N. Somwang, P. Khomdet, C. Hruanun, A. Poyai and J.
Nukeaw
Photocatalytic Decolorization of Red Dye in Aqueous ZnO-TiO2 Suspensions
S.K. Asl, S.K. Sadrnezhaad and M. Keyanpour-Rad
Electrode Properties of Nanostructured and Amorphous Mg1.75Nb0.25Ni Compound
Produced by Mechanical Alloying
S.F. Kashani Bozorg, M. Mohri and A. Ebrahimi-Purkani
Direct Synthesis of Anisotropic Metal Particles by Ink Jet Printing Technique
R. Kitsomboonloha, T. Bera and J. Dutta
Chitosan Clad Manganese Doped Zing Sulphide Nanocrystallites for Biolabeling
S. Baruah, G. Tumcharern and J. Dutta
The Effects of Substrate Temperature on Optical Properties and Surface Morphology of
Nickel Phthalocyanine Thin Films Grown by Organic Evaporator System
P. Inchidjuy, S. Pukird and J. Nukeaw
Electrical Characterization of Diamond-Like Carbon Films Synthesized by Plasma
Enhanced CVD Technique
B. Paosawatyanyong, K. Honglertsakul, N. Rujisamphan and W. Bhanthumnavin

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597

Smart Materials

Effects of Gold Nanoparticles on the Fabrication of Red Colored High Refractive Index
Lead Glass
P. Dararutana, J. Dutchaneephet, P. Chetanachan, P. Wathanakul and N. Sirikulrat
Fabrication of Zirconia Nanofibers Using Zirconatrane Synthesized by Oxide One-Pot
Process as Precursor
M. Panapoy and B. Ksapabutr
Mechanical Property Evaluation of ZnO Thin Films Using Nanoindentation and Scanning
Probe Microscope
T.H. Fang and S.H. Kang
Influences of Zr4+ and Polyacrylamide on Structural and Optical Properties of ZnO
Nanoparticles Prepared via Microwave Irradiation
P. Pisitsak and R. Magaraphan
Functionalized Porous Clay Heterostructure for Heavy Metal Adsorption from Wastewater
R. Tassanapayak, R. Magaraphan and H. Manuspiya
Niobium and Antimony-Modified Titanium Dioxide/Epoxy Thin Film for Proton Exchange
Membrane Fuel Cell
T. Kuanchaitrakul, S. Chirachanchai and H. Manuspiya
Improvement of Hydrophobic Properties of the Electrospun PVA Fabrics by SF6 Plasma
Treatment
A. Thongphud, B. Paosawatyanyong, P. Visal-athaphand and P. Supaphol
Microstructure and Characterizations of Portland-Bottom Ash-Silica Fume Cement Pastes
W. Wongkeo, W. Thawornson and A. Chaipanich
Investigation of Nanomaterials Prepared by Thermal Evaporation of Carbon-ZnO
Mixtures
D. Polsongkram, P. Kasian, P. Limsuwan, U. Tipparach, S. Samran, L. Chow and S. Pukird
Synthesis and Characterization of Nanostructured Materials Prepared from SiO2 and GeO2
Mixture by Carbon Assisted Method
P. Chamninok, P. Kasian, P. Limsuwan, U. Tipparach, S. Samran, L. Chow and S. Pukird
Zn2TiO4 Nanostructures Prepared by Thermal Oxidation Method
T. Santhaveesuk, D. Wongratanaphisan, N. Mangkorntong and S. Choopun
CuO Nanostructure by Oxidization of Copper Thin Films
P. Raksa, A. Gardchareon, N. Mangkorntong and S. Choopun
Synthesis of SiO2 Nanopowder from Rice Husk Ash
A. Ruksudjarit and G. Rujijanagul
Preparation of Nano-Crystalline Boehmite as a Gamma-Alumina Source for the Production
of Na.beta-Al2O3 Solid Electrolyte
P. Pimsorn, R. Tipakontitikul, A. Niyompan, N. Kanchanarat and T. Tunkasiri
Synthesis and Characterization of Zinc Oxide Nanocrystals by Solid-State and Solvothermal
Techniques
C. Satienpattanakoon, D. Yiamsawas, W. Kangwansupamomkon and R. Nuisin
Fabrication of Gold Nanocubes by the Electrochemical Method
C.J. Huang, P.H. Chiu, Y.H. Wang and K.L. Chen
Synthesis of Gold Nanodogbones by the Seed Mediated Growth Method with Addition of
Vitamin C Solvent
P.H. Chiu, C.J. Huang, Y.H. Wang and C.H. Chen

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X. Molecular Actuator and Sensor Materials


Chiral Helices in a 3D Network of Zn2(en)V2O7 (en = Ethylenediamine)
S. Krachodnok, K.J. Haller and I.D. Williams
Time-of-Flight Measurement of Poly(3-Hexylthiophene) Thin Films
M. Sittishoktram, U. Asawapirom and T. Osotchan
Optical Properties of Metal Free and Metal Phthalocyanine by Molecular Band Calculation
S. Pengmanayol and T. Osotchan

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XI. Biomedical/Bioresponsive
Design and Preparation of a Bioresponsive Hydrogel for Biomedical Application as a
Wound Dressing
C. Witthayaprapakorn, R. Molloy, K. Nalampang and B.J. Tighe

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Modification of Thai Silk Fibroin Scaffolds by Gelatin Conjugation for Tissue Engineering
J. Chamchongkaset, S. Kanokpanont, D.L. Kaplan and S. Damrongsakkul
Substitution of Iron in Preparation of Enhanced Thermal Property and Bioactivity of
Hydroxyapatite
S. Meejoo, W. Pon-On, S. Charnchai and T. Amornsakchai
Processing, Mechanical Property Development and In Vitro Hydrolytic Degradation Studies
of a Poly(L-Lactide-co--Caprolactone) Monofilament Fibre for Potential Use as an
Absorbable Surgical Suture
P. Chooprayoon, J. Siripitayananon, R. Molloy, S. Bunkird, T. Soywongsa and A. Tariyawong
Differential Expression of Osteogenic Differentiation in Human Umbilical Cord Whartons
Jelly-Derived Mesenchymal Stem Cells Treated with Demineralized Bone
D. Dhitiseith and S. Honsawek
Development of a Protein-Filled Conduit for Peripheral Nerve Regeneration
K. Yingsukwattana, S. Agthong, R. Mongkonnavin, Y. Tabata and S. Kanokpanont
Electrical Properties and Microstructures of P2O5-CaO-Na2O Glasses
N. Raengthon, K. Pengpat and T. Tunkasiri
Ultrastructural Characterization of Liposomes Using Transmission Electron Microscope
P. Chetanachan, P. Akarachalanon, D. Worawirunwong, P. Dararutana, A. Bangtrakulnonth, M.
Bunjop and S. Kongmuang
Cholesteryl Cetyl Carbonate as a Smart Material for Drug Delivery Application
N. Aeinlang, T. Srichana and S. Songkro
Preparation and Drug Release Studies of Chitosan/Methoxy Poly(Ethylene Glycol)-bPoly(D,L-Lactide-co-Glycolide) Nanocomposite Films for Use as Controlled Release Drug
Delivery
N. Niamsa, M. Srisa-ard, Y. Srisuwan, N. Kotsaeng, Y. Baimark, N. Narkkong and W. Simchuer
Study on Morphology and Thermal Stability of Nanoporous Silk Fibroin Films
Y. Srisuwan, N. Kotsaeng, Y. Baimark, N. Narkkong and W. Simchuer
Preparation and Characterization of Poly(D,L-Lactide) and Silk Fibroin Nanocomposite
Microparticles for Potential Use in Tissue Engineering
N. Kotsaeng, Y. Srisuwan, Y. Baimark, N. Narkkong and W. Simchuer
Zwitterionic and Charge-Balanced Polyampholyte Copolymer Hydrogels
D. Campbell and B.J. Tighe

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693
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701
705
709
713

717
721
725
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XII. Speciality Polymer with Controlled Microstructures


Morphology of Electrospun Mats of Soy Protein Isolate and its Blend
M. Phiriyawirut, N. Rodchanacheewa, N. Nensiri and P. Supaphol
Novel Three-Component Blends Based on Poly(L-Lactide)
S. Juikham, A.J. Amass and B.J. Tighe
Chemical Resistant Improvement of Natural Rubber and Nitrile Gloves by Coating with
Hydrophobic Film
N. Atthi, O. Nimittrakoolchai, W. Jeamsaksiri and S. Supothina
Effect of Nano-Porous Alumina Filler on Thermal and Electrical Transport Properties of
Solid Polymer Electrolyte (PEO)12LiBF4
H.M.J.C. Pitawala, M.A.K.L. Dissanayake, V.A. Seneviratne, B.E. Mellander and I. Albinsson
Characterization and Thermal Properties of Sol-Gel Processed PMMA/SiO2 Hybrid
Materials
A. Buasri, K. Liangraksa, T. Sirisom and N. Tangkachalakul
Surface Treatment of Polystyrene Films with Inductively Coupled Plasma System
R. Nakhowong, T. Srikhirin and T. Osotchan
Ring-Opening Polymerization of -Caprolactone Using Novel Tin(II) Alkoxide Initiators
A. Kleawkla, R. Molloy, W. Naksata and W. Punyodom

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XIII. Others Smart Materials


Investigation of the Strain Hardening and Bauschinger Effect of Low and High Strength
Steel Application in Drawbead-Tester by Experiment and Numerical Simulation
K. Sirivedin, K. Krueger, V. Thoms, D. Suesse, R. Mueller and M. Schatz
Extraction of Defect in Doping Silicon Wafer by Analyzing the Lifetime Profile Method
W. Pengchan, T. Phetchakul and A. Poyai

761
765

Smart Materials

Preparation and Properties Indium Tin-Oxide Thin Films by RF Sputtered for


Photodetectors
I. Srithanachai, K. Nutaman, A. Rerkratn, S. Niemcharoen and S. Supadech
High Resolution X-Ray Diffraction and Raman Scattering Studies of Cubic-Phase InN
Films Grown by MBE
S. Kuntharin, S. Sanorpim, H. Yaguchi, Y. Iwahashi, M. Orihara, Y. Hijakata and S. Yoshida
Effect of Palladium on Photocatalytic Activity of SnO2 Nanoparticles
R. Janmanee, P. Pirakitikulr, N. Wetchakun, C. Liewhiran and S. Phanichphant
Computational Study on Thermodynamic and Structural Properties of ZSM-5 Doped by
Al/Fe and Al/P
S.B. Pongsai and S. Hannongbua
Synthesis and Characterization of PLA-Based Aliphatic-Aromatic Copolyesters: Effect of
Diols
M. Namkajorn, A. Petchsuk, M. Opaprakasit and P. Opaprakasit
Synthesis and Characterization of Degradable Poly(Ethylene Terephthalate-co-Lactic Acid)
and its Blends
P. Sriromreun, M. Opaprakasit, A. Petchsuk and P. Opaprakasit
Sintering Behavior of the "-Alumina Solid Electrolyte for Battery Applications
A. Niyompan, K. Srisurat, R. Tipakontitikul, K. Pengpat and T. Tunkasiri
Improved Electrical Conducting Wires for SOFCs
M. Masomtob, K. Wongtida, J. Charoensuk and S. Charojrochkul
Defect-Induced Properties of Doped Alpha Alumina Samples
P. Jantaratana, P. Dararutana, W. Wongkokua, S. Pongkrapan and P. Wathanakul
Preparation of IR Reflective Green Pigment
T. Thongkanluang, P. Limsuwan and P. Rakkwamsuk
Thermoelectric Properties of BixSbyTezSew Nanocomposite Materials
V. Kosalathip, T. Kumpeerapun, S. Migot, B. Lenoir and A. Dauscher
Simple Thermoelectric Module
T. Kumpeerapun, H. Scherrer, V. Kosalathip and I. Sripichai
Behaviour of Various Glass Seal for Planar Solid Oxide Fuel Cell
N. Punbusayakul, W. Wongklang, K. Wongtida, J. Charoensuk and S. Charojrochkul
InGaPN/GaP Lattice-Matched Single Quantum Wells on GaP (001) Grown by MOVPE
D. Kaewket, S. Sanorpim, S. Tungasmita, R. Katayama and K. Onabe
Effect of Substrate-Surface Orientation on the N Incorporation in GaAsN Films on GaAs
Grown by MOVPE
P. Klangtakai, S. Sanorpim, S. Kuboya, R. Katayama and K. Onabe
Synthesis and Thermoelectric Properties of CoSb3-yTey
S.C. Ur and I.H. Kim
Sulphate-Based Flame-Retardant for Handmade Mulberry Paper
W. Naksata and M. Naksata
Lead-Free Ferroelectric Material: Dysprosium Doped Bi4Ti3O12
N. Thongmee, A. Watcharapasorn and S. Jiansirisomboon
Sinterbility of (Bi4-xLax)Ti3O12 Ceramics
P. Siriprapa, A. Watcharapasorn and S. Jiansirisomboon
Hydrothermal Synthesis of Zinc Oxide (ZnO) Microparticle
P. Pookmanee, S. Khuanphet and S. Phanichphant
ESR and Optical Absorption Spectra of Copper (II) Ions in Glasses
J. Kaewkhao, S. Rhianphumikarakit and N. Udomkan
Enhancement of the Photocatalytic Performance of Ru-Doped TiO2 Nanoparticles
K. Wetchakun, N. Wetchakun and S. Phanichphant
Magnetic Properties of Mn Doped NiO
E. Swatsitang and A. Pimsawat
Biosurfactant Production from Palm Oil Using Sequencing Batch Reactors: Effect of Cycle
Time
O. Huayyai, S. Chavadej, R. Rujiravanit and M. Abe
Cost Effective Natural Adsorbent for Fluoride Removal
S. Janta, S. Watanesk, R. Watanesk and S. Thiansem

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Advanced Materials Research Vols. 55-57

Effect of Bi2O3 Content on the Properties of Bi2O3-BaO-B2O3 Glass System


J. Kaewkhao, A. Pokaipisit and W. Chewpraditkul
Synthesis, Phase Formation and Characterization of Co4Nb2O9 Powders Synthesized by
Solid-State Reaction
N. Chaiyo, R. Muanghlua, A. Ruangphanit, W.C. Vittayakorn and N. Vittayakorn
A Study of the Effects of Processing Conditions on Mechanical Properties of
Polypropylene/Multiwall Carbon Nanotube Nanocomposites Using Design of Experiments
N. Duangphattra and C. Aramphongphun
Influence of Substrate Temperature on Some Properties of Close-Spacing Thermally
Evaporated CdTe Thin Films
T. Gaewdang, N. Wongcharoen, P. Siribuddhaiwon and N. Promros
Effects of Potassium Fluoride Salt Additive on the Sintering Temperature and Dielectric
Properties of BaFe0.5Nb0.5O3 Ceramics
U. Intatha, K. Sathitada, S. Eitssayeam, K. Pengpat, G. Rujijanagul, P. Thavornyuttakarn and T.
Tunkasiri
Effect of ZrO2 Doping in Physical Properties of Barium Iron Niobate Ceramics
U. Intatha, S. Eitssayeam, K. Pengpat, G. Rujijanagul and T. Tunkasiri
Production and Characterization of Polyhydroxyalkanoates (PHAs) from Inexpensive
Substrates by Alcaligenes Latus
C. Thammawong, K. Thongkhong, K. Iamtassana, A. Sharp and P. Opaprakasit
Controlled-Release Material for Urea Fertilizer from Polylactic Acid
J. Papangkorn, C. Isaraphan, S. Phinhongthong, M. Opaprakasit and P. Opaprakasit
Application of Artificial Neural Network to Calculate Curie Temperature of Ferromagnetic
Materials
W.S. Laosiritaworn
Controlled-Release Materials for Fertilizer Based on Lactic Acid Polymers
N. Jintakanon, P. Opaprakasit, A. Petchsuk and M. Opaprakasit
Fragrant Finishing of Cotton Fabric Using -Cyclodextrin
M. Nakpathom, B. Somboon and S. Changpradit
Use of Hydroxypropylmethylcellulose as Thermo-Responsive Flocculant in Skim Natural
Rubber Latex
N. Moonprasith, S. Loykulnant and C. Kongkaew
Microstructure and Interfaces of Thin Film Capacitors on Base Metal Foils
T. Dechakupt, G. Yang, I.M. Reaney, C.A. Randall and S. Trolier-McKinstry
Influence of Structural and Electrical Properties of ITO Films on Electrochromic Properties
of WO3 Films
K. Aiempanakit, S. Dumrongrattana and P. Rakkwamsuk
Effect of DC Power on Structural and Hydrophilic Activity of TiO2 Films
C. Salawan, A. Muakngam, B. Sukbot, K. Aiempanakit and S. Dumrongrattana
Oily Soil Detergency under Microemulsion Conditions: Effects of Oil Loading and
Surfactant Adsorption
R. Kaewpukpa, S. Chavadej and J.F. Scamehorn
Ferroelectric Properties of Sn-Doped PZTPNN Ceramics
K. Sutjarittangtham, U. Intatha, S. Eitssayeam and G. Rujijanagul

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Advanced Materials Research Vols. 55-57 (2008) pp 1-9


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.1

Piezoelectric Actuators 2008: Key Factors for Commercialization


K. Uchino
Intl Center for Actuators and Transducers,
The Penn State University, University Park, PA 16802,
and Micromechatronics Inc., State College, PA 16803, USA
Keywords: piezoelectric actuators, SWOT analysis, Five force model, internal & external
environmental analysis

Abstract: 2008 marks the 30th year after the piezo-actuator boom started. The basic required
technologies seem to be maturing and a drastic cost reduction period started. It is time to review the
development history, analyze the present problems, and find the strategies to move forward to wide
commercialization of the piezo actuator, as the key electro-mechanical component in the 21st
century. This paper is Part II of the review paper Piezoelectric Actuators 2006 presented
previously [1], which covered various application areas of actuators, from information
technology/robotics, bio- and medical engineering, to ecological and energy technologies. If the
reader has not read this article, it is recommended to so first.
Introduction
1978-80 is an important period, namely the start-up to piezoelectric actuators. The two inventions,
(1) lead magnesium niobate-lead titanate based hysteresis-free electrostrictor, and (2) cofired
multilayer actuator technology by the Penn State group, triggered the piezoelectric actuator area.
The terminologies, piezoelectric actuators and Micromechatronics were introduced by K.
Uchino during this time period.
Patent Trend
The breakdown of patent disclosures filed in Japan from 1972 to 1984 and from 1988 to 1990 is
shown in Figs. 1(a) and 1(b), respectively [2]. Note that device application concepts constitute most
of the patents in Fig. 1(a), while only about one quarter of the patents are related to this area in Fig.
1(b). This tendency is generally observed in the development of any device. Once the basic design
is proposed, various prototype devices are fabricated and application patents are filed. However, as
the actual commercialization is promoted, the focus shifts to the optimization of the designs, cheap
and efficient manufacturing processes, and new drive/control methods. Since the technologies have
been maturing in 90s for the first generation products, the patent breakdown is shifted again to
applications recently, which means the diversification of the piezo-actuator product lines, in other
words the dawn of second generation products.
In general, taking into account the difficulty in overcoming the reliability requirements such as
operating temperature range and lifetime, we engineers recognize the development pecking order
in the sequence like Camera > Office equipment > automobile. Since the multilayer actuator
(MLA) has been already utilized for the diesel injection valve, we could say that the piezoelectric
actuator technology development has already gotten into its maturing period. Further, we can say
that the industrial competition has started in sharing the market by reducing the actuator price
drastically, which is not only related with the manufacturing technology development (cheaper and
more efficient manufacturing), but also with the industrial managerial and strategic decision.
Namely the Cash-Cow product period, according to the Boston Consulting Group product lifecycle analysis [3].

Smart Materials

Fig. 1 Breakdown of patent disclosures filed in Japan with respect to technical


contents: (a) 1972- 1984 (508 patents) and (b) 1988- 1990 (550 patents).

Analysis Tools
From these senses, there are various constraints for commercializing piezoelectric actuators. We
will discuss these key factors, taking into account the several recent product developments. We will
adopt standard MBA tools; SWOT (Strength-weakness-opportunity -threat) Analysis and
Porters Five Force Model, in this article. The details can be learned in the authors new book,
High-Tech Entrepreneur[4].
Figure 2 shows the basic concept of SWOT Grid. The horizontal axis is a measure of StrengthWeakness of the firm (your company), while the vertical axis is a measure of Opportunity-Threat of
the industries (piezo-actuator area). The former is called internal environment analysis, and the
latter is called external environment analysis. All the companies are positioned in one of these
four domains, where the reader can find the suggested strategy which those companies should take.
Though the piezo-actuator industries have a better Opportunity in general (Domain I or II), if the
competitive electromagnetic motor took a larger share in a particular device, the external
environment becomes Threat (Domain III or IV). STEP (Social/cultural, Technological,
Economic, and Political) four forces are considered as external factors in this article.

Fig. 2 General concept of the SWOT grid.

Fig. 3 Michael Porters Five Force model of


competition.

Figure 3 shows the concept of Porters Five Force model for internal environment analysis [5].
We will start from this internal environmental analysis, first, followed by the external
environmental analysis.

Advanced Materials Research Vols. 55-57

ITERAL EVIROMETAL AALYSIS


Rivalry among Competing Firms
Figure 4 (a) shows the head structure of the Epson Mach ink-jet printer, here the so-called cut&-bond technology was initially used by the supplier, Philips, to manufacture the PZT unimorph
[6]. Three years later, NGK, Japan developed the cofiring technology to manufacture the PZT
unimorph on the zirconia ink chamber substrate, and took over the supplier position from Philips.
The cofiring technology provided a dramatic reduction of the manufacturing cost of the printer
head, in addition to the performance improvement; that is, the unnecessary vibration of the ink
chamber was suppressed. As the reader may know, Philips piezo-device division was closed soon
after losing this large customer, Epson. This episode teaches us the importance of continuous effort
on developing a new technology, because every product has a lifecycle.

(a)

(b)

Fig. 4 Piezoelectric ink-jet printer heads: (a)


conventional unimorph-type and (b) new
multilayer type.[6]

Development of Substitute Products


Though the responsivity of a piezo-actuator in the Epson printer head (Fig. 4(a)) is much faster
than the competitive Canon bubble-jet printer, the resolution of the piezo-unimorph printer head is
lower than the bubble-jet type, because the unimorph covering area is rather large. In order to
realize much finer nozzle arrangement, Epson developed the piezo-multilayer type as shown in Fig.
4(b) [6]. This arrangement provides finer resolution and quicker speed. Though it is costlier than
the unimorph type, this development is strategically important to compete with Canons printers.
The most competitive substitute of the piezoelectric actuator is the electromagnetic (EM)
motors. Figure 5 compares our micro ultrasonic motor (USM, 1.5 mm x4 mm long) with an EM
motor (used in a cellular phone) with a similar output power level (50 mW). Note significant
difference in volume and weight by a factor of x20. Also 10 times higher torque and the efficiency
of the USM are superior to the conventional EM motor. Though the USM is a Threat to the EM
motors in terms of performance at present, historically lower price of the EM type is a big Threat
to the piezo-actuator.

Smart Materials

Fig. 5 Comparison between the piezo-ultrasonic


motor (1.5 mm) and the EM motor, with a
similar power level.

Entree of #ew Competitors


With expanding the applications and market of the piezo-actuators, original raw-material
suppliers (up-stream industry) such as cement, chemical, and even steel companies moved into the
piezo-actuator business. On the other hand, original customers (down-stream industry) such as
computer, home and office electronics companies started to manufacture the actuators. Prosthetic
arm manufacturers and measuring equipment companies already started to make USMs, which may
be threats to the present piezo-actuator industry. However, this might be a good opportunity to
find collaborative business partners.
Bargaining Power of Suppliers
The internal electrode material of choice of the conventional ceramic multilayer (ML) devices
were Ag/Pd, as it was in capacitors. However, owing to the Russian economy crisis in the late
1990s, palladium price increased dramatically with a peak in 2000, 10 times higher than 1990
(Figure 6). Because of this raw material cost change, capacitor industries started to use Ni (Base
metal) internal electrode. Though the price of Pd is stabilized now, the effort on the cheaper
material usage is continuing. This is an example how the Threat should be transformed to an
Opportunity The necessity creates the technology. The piezo-actuator industry is a little behind to
shift to use widely the Cu internal electrode. The piezo-industries are still using Ag/Pd or Pt for the
internal electrodes. EPCOS recently started to commercialize the Cu embedded ML actuators for
the diesel injection valve application, in which the actuator cost is the major bottleneck at present
[7].

Fig. 6 Palladium price change with year.

Bargaining Power of Consumers


The consumers power depends on the application area. In the IT/office equipment application
area, the customers of piezo-actuators are giant electronic companies, who have strong bargaining
power against the component companies; as such, we are a price taker. Thus the current
development target is how to reduce the production cost to meet the customers desire. ML
actuators and USMs need to be manufactured for much less than US$3 per piece in these days for
cellular phone applications. For the robotic applications, monitoring how the nano-technology is

Advanced Materials Research Vols. 55-57

expanding, as such, how nano-positioning is demanded will be the key to estimate the future market
size. Consecutively the market size will determine the actuator price (performance/cost-oriented).
In the bio/medical area, the price is not a very important factor, but the specs (merely performance)
such as very low drive voltage and confined size are critical in designing. The piezo-actuator
community are fortunately a price fixer in this area. Finally, environmental business is obviously
expanding in these days. Accordingly, the demand for the actuators/transducers in the area is
quickly increasing. Since it is still in the prototype production stage, there is no threat from
customers (skimming price period), but the actuator manufacturer needs to obtain the attraction
from the customers.

Total Cost

Slope = Raw material cost

Equipment
Cost
Slope = Raw material cost +
Labor fee

Production Quantity

Fig. 7 Total cost calculation comparison for the multilayer


product among a tape-cast equipment automatic
production and a cut-and-paste manual production.

EXTERAL EVIROMETAL AALYSIS


Economic Forces
Figure 7 illustrates the manufacturing cost calculation processes for the ML actuators with tapecast automatic equipment and with a cut-&-bond manual production process. For the tape-casting
equipment, the initial investment (fixed cost of equipment = $300K) is expensive, with a low slope
of variable cost (just raw materials cost) as a function of production quantity. On the other hand, the
cut-&-bond process requires a steep slope of variable cost provided by the labor fee in addition to
raw materials cost. We can find an intersection between these two lines (point T in Fig. 7). This
product quantity is the threshold above which the equipment installation starts to provide a better
profit.
Others

6%

13%
Tungsten bronze
type compound

34%
Bi-layered type
compound

20%

(Na,K)NbO3 type
compound

(Bi1/2Na1/2)TiO3 type
compound

27%

Fig. 8 Patent disclosure statistics for lead-free


piezoelectric ceramics. (Total number of
patents and papers is 102).

Because the labor fee is expensive in a developed country, introduction of a tape-casting facility
is usually recommended, when the production quantity exceeds only 0.1 million pieces per year.
However, due to the lower labor cost in a developing country such as Thailand and China, this

Smart Materials

production threshold quantity is dramatically high, about 2 million pieces in the multilayer (ML)
actuator production. If the production quantity is 1 million pieces, the manual production process in
these countries with line-workers labor is actually cheaper. This is the globalization motivation for
a corporation to set their factory or find an OEM partner in a foreign country.

Fig. 9 Strain curves for oriented and


unoriented (K,>a,Li)(>b,Ta,Sb)O3
ceramics.[8]

Political/Legal Forces
21st Century is called The Century of Environmental Management. We are facing serious
global problems such as the accumulation of toxic wastes, the Greenhouse Effect of Earth,
contamination of rivers and seas, lack of energy sources, oil, natural gas etc. In 2006, European
Community started RoHS (Restrictions on the use of certain Hazardous Substances), which
explicitly limits the usage of lead (Pb) in electronic equipments. Basically, we may need to regulate
the usage of lead zirconate titanate (PZT), most famous piezoelectric ceramics, in the future.
Japanese and European community may experience governmental regulation on the PZT usage in
these 10 years. Pb (lead)-free piezoceramics have started to be developed after 1999. Figure 8
shows statistics of various lead-free piezoelectric ceramics. The share of the papers and patents for
bismuth compounds (bismuth layered type and (Bi,Na)TiO3 type) exceeds 61%. This is because
bismuth compounds are easily fabricated in comparison with other compounds. Figure 9 shows the
current best data reported by Toyota Central Research Lab, where strain curves for oriented and
unoriented (K,Na,Li) (Nb,Ta,Sb)O3 ceramics are shown [8]. Note that the maximum strain reaches
up to 1500 x 10-6, which is equivalent to the PZT strain. Refer to the review paper on Pb-free
piezoelectrics by Tsurumi [9].

Piezoelectric Actuator

Control Valve

Displacement
Amplification Unit
Injector Body
Nozzle

Fig. 10 Common rail type diesel injection valve with


a piezoelectric multilayer actuator.[10]

Advanced Materials Research Vols. 55-57

RoHS seems to be a significant threat to piezoelectric companies, who have only PZT piezoceramics. However, this is an opportunity for the company which is preparing alternative piezoceramics to exchange the piezoelectric device share. Diesel engines are recommended because by
replacing the regular engine cars the purification energy can be saved, which was contributing to
global warming problem. However, the conventional diesel engine generates toxic exhaust gases
such as SOx and NOx. In order to solve this problem, new diesel injection valves were developed by
Siemens with piezoelectric ML actuators. Figure 10 shows a common rail type diesel injection
valve [10].

Piezo Stack Price

Thin Layer ML

Discrete & EDU Cost

High Energy (High


Current Capacitance)

Low Energy (Low


Current Capacitance)

Thick Layer

Fig. 11 Drive voltage dependence of piezo-stack


price and the electronic driver cost.[10]

Technological Forces
Specifications
COPAL developed a piezo-bimorph shutter for a Minolta dual-zoom camera purpose in late
1980s [11]. The original design required the drive voltage of 120V, which was rejected by Minolta,
because an additional voltage supply was required in a camera. The solution was to increase the
drive voltage by thickening the PZT plate, rather than to decrease the drive voltage, which the
reader may anticipate. The final bimorph was designed to be driven by 240V, which was a strobe
voltage supply originally installed in a camera. The drive voltage of an actual electronic component
is decided by the battery specifications: 1.5, 3, 9, 12, 240 V.
Cost Minimization
Some researchers are working to reduce the drive voltage by reducing the layer thickness of
piezoelectric multilayer actuators. However, it is not recommended for the large ML actuators for
diesel injection valve control applications in diesel automobiles (Figure 10). Figure 11 graphs the
piezo-stack price and its electronic driver cost as a function of drive voltage [10]. The ML actuator
price increases with reducing its drive voltage (i.e., reducing its each layer thickness), while the
driver cost increases with increasing the voltage. The minimum total cost is obtained around 160 V,
leading the layer thickness of 80 m. This a-sort-of standard thickness can be derived from the
cost minimization principle, but not from the performance. Note that 20 m layer thickness is not
difficult technologically in ML actuators nowadays.
Social/Cultural Forces
Though piezoelectric transformers (PT) were used on trial in the color TVs in 1970s, serious
problems were found in the mechanical strength (collapse happened in the device) and in heat
generation in color TVs, leading to the termination of production for two decades. However, recent
laptop computers with a liquid crystal display requiring a very thin, and electromagnetic-noise free
transformer to start the glow of a fluorescent back-lamp have accelerated the development after
1990s. This is a good example how the social demand creates the technology development (needspush).
The best technology device does not mean the best-seller device. Best-seller is related with the
consumer attitude and social trends. Table 1 tabulates the Japanese consumer attitude changes with
time. Compared to the technological trends in 1980s, lighter, thinner, shorter and smaller, we can

Smart Materials

say that beautiful, amusing, tasteful and creative will be the keywords in 2000s [12]. The present
bestseller cellular phones are based on their sophisticated function and artistic design, rather than
the technology. Artistic sense should be added in the device development (Sci-Art [13]) in the 21st
Engineering Renaissance era.
Table 1 Social/consumer attitude trends in Japan with time
in these several decades.
1960's

Heavier
Thicker
Longer
Larger

-----

Ship manufacturing
Steel industry
Building construction
Power plant (dam)

1980's

Lighter
Thinner
Shorter

----

Smaller

--

Printer, Camera
TV, Computer
Printing
Communication period
time
"Walkman"
Air conditioner

2000's

Beautiful-Amusing
Tasteful

---

Creative

--

Well-known brand
apparel
T.V. game
Cellular phone
(private
"Culture"
commun.)center
Made-to-order shoes

COMPETITIVE STRATEGY
Middle 1980s, Mr. Akio Morita, former president of SONY Corporation, responded to a
criticism from an American journalist concerning the lack of creativity on the parts of Japanese
researchers by saying Japanese researchers are good at chasing and imitating the original idea for
commercialization, but they in general lack creativity. Mr. Morita suggested that there should be
three types of creativity with respect to Research & Development at SONY: The U.S. people are
focusing only on technological creativity. But the people must understand there are two more
creativities; product planning creativity and marketing creativity, which are equally important for
commercial success.
Matsushita Panasonic's famous color TV technology (black stripe for creating better color
resolution), for example, has indeed been transferred from Philips. However, even though the idea
came from Philips, they could not commercialize it with their supporting technologies. Matsushita,
on the other hand, succeeded in commercializing the idea after an intensive three-year development
on it. Of course, it is up to the reader to decide which company is at a higher level with respect to
science and technology. It is, however, apparent that only Matsushita obtained a large profit from
this TV development.
This article puts more stress on the planning and marketing creativities on piezoelectric
actuators, rather than technological creativity.
Last two comments from the author:
Market Research
From the market research result for 80 Japanese component industries in 1992, tiny motors in
the range of 5 8 mm are highly required in these 10 years for office and factory automation
equipment, and the conventional electromagnetic motors are rather difficult to produce with
sufficient energy efficiency. Ultrasonic motors whose efficiency is insensitive to size are superior in
this micro-motor area. Regarding the linear actuators, the customers demands are simple: 100 m
stroke, 100 N force with 100 sec response [14].
Michael Porters Competitive Strategy
Porters competitive strategies [5] include: (1) cost leader, (2) differentiation, and (3) focus,
categorizing successful companies into 4 domains illustrated in Table 2. NEC-Tokin is still a
leading company in the piezo-actuator area. They are targeting small ML actuators for cellular
phone applications (focus) with mass-production facility at the lowest cost (cost-leader). EPCOS
and Denso are targeting large ML actuators for the diesel injection valve application. These are
cost leaders. On the contrary, Physik Instrumente is taking a differentiation strategy with

Advanced Materials Research Vols. 55-57

customer-oriented prestigious price setting. Their product-lines are rather wide based on a
reasonably large company size. Cedrat and Noliac are taking also differentiation strategy, but
keeping relatively concise product-lines, with focused applications and customers.
The competitive strategies are also different depending on the application areas. Cost-leader
is definitively required in the information, office equipment and the robotics area. On the contrary,
the strategy of differentiated product with prestigious price is the norm in the bio- and medical
engineering field. The development of a focused target product is now essential in ecological and
energy applications.
It is now your companys choice on which development strategy should be taken.
Table 2 Porters competitive strategies, and the example
corporations, corresponding to the categories.
General Target
Cost leader

None

Differentiation

Physik
Instrumente

Focused Target
NEC-Tokin
EPCOS, Denso
Nihon Ceratec
Cedrat
Noliac

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

K. Uchino: Proc. New Actuator 2006 (Bremen, June14-16, A1.0, p.48, 2006)
K. Uchino: Micromechatronics (CRC/Dekker, NY, 2003)
D. A. Aaker: Developing Business Strategies (John Wiley & Sons, NY, 1984)
K. Uchino: High-Tech Entrepreneur, (Taylor & Francis, FL [in printing])
M. Porter: Competitive Strategy: Techniques for Analyzing Industries and Competitors (Free
Press, NY, 1980)
N. Kurashima: Proc. Machine Tech. Inst. Seminar, MITI, Tsukuba, Japan (1999)
F. Boecking and B. Sugg: Proc. New Actuator 2006 (Bremen, June14-16), A5.0, p.171 (2006)
Y. Saito: Jpn. J. Appl. Phys. Vol 35 (1996), p. 5168.
T. Tsurumi: J. Japan. Ceramic Soc., p. 40 (2005)
A. Fujii: Proc. JTTAS Meeting on Dec. 2, Tokyo (2005)
Minolta Camera, Product Catalog Mac Dual I, II
Y. Hirashima: Product Planning in Feeling Consumer Era (Jitsumu-Kyoiku Publ., Tokyo,
1986).
M. Fusakul: Proc. 5th Intl Conf. on Intelligent Mater. (ICIM2003), State College, PA, June
14 17 (2003).
Japan Tech. Transfer Assoc., Standard Comm. Report (1991)

Advanced Materials Research Vols. 55-57 (2008) pp 11-14


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.11

Tailored Intelligent Materials


R. P. Tandon
Department of Physics and Astrophysics, University of Delhi,
New Delhi-110007 India
rptandon9@physics.du.ac.in
Keywords: smart material, intelligent systems, sensors and actuators.

Abstract: Use of smart intelligent materials is gaining great prominence in the domain of
underwater acoustics, defense and environmental engineering. Piezoelectric ceramics such as PZT
have found applications in MEM hydrophones to high power sonars. These are also finding
widespread use in active noise cancellation in the industrial applications. This paper will cover
these topics and also use of ER fluids and shape memory alloys will be reviewed. This will be
followed by the authors own contribution made for the field of piezo-composites for the
applications in hydrophones and other underwater devices.
Introduction
The recent wars in the Middle East have proved that the battle grounds are turning to be fields for
trial of advanced weapons, technologies. Use of smart materials and devices have provided
extraordinary capabilities to equipments and have enhanced the survivability and endurance of the
men and machines. These developments have been possible due to the emergence of new smart and
intelligent materials. The smart materials can sense and respond in an ordered manner such as a
piezoelectric material. By designing and engineering the materials to respond or behave in an
orderly and predictable manner, under several stimuli or constraints making them intelligent
bringing them closer to biological systems. The intelligent materials used in conjunction with
suitable electronics have led to the development of plethora of devices which until few years ago
appeared to a science fiction[1-4]. One of the immediate beneficiarys of these devices is the health
care system. Using these intelligent materials the disease can be diagnosed from a remote areas and
treated via a satellite. Even surgery can be performed from remotely located surgeons. Soldiers are
provided with smart shirts equipped with numerous sensors which control heat flow, hazard
protection, and monitor vital body parameters.
The concept of air car made of composites and having adjustable wings has been demonstrated
in the USA. Demonstration of Scramjet cruising at a speed of 10 mach is a consequence of these
wonder materials. Enhanced use of latest sensors in cars has brought enormous comfort to the
passengers and the driverless car will be available in not too distant future.
Apart from ceramics, shape memory alloys (SMA) are finding widespread uses. These materials
remember their original shape. Several types of actuators have been developed based on SMAs.
Magneto rheological fluids have been used to make tunable elastomers with novel
magnetostrictive properties. Some of these MR and ER fluids are finding applications in
automobiles and in adaptive damping system.
Traditional piezoelectric ceramics have been used as smart materials, be it MEMs or in
underwater detection systems. Design and characterization of low frequency transducer for acoustic
tomography is discussed. The last part of the paper is devoted to Co4Cu3Ti4O12 (CCTO) of materials
with exotic dielectric properties.
Experimental results and discussions:
Piezoelectric ceramics and composites have been used for high power sonar transducers, large area
hydrophones and lately MEMS hydrophone. Because of the complexity of testing, very few groups

12

Smart Materials

have been working in this direction and most of them are from defense sector. The present author
has undertaken considerable work while working at the National Physical Laboratory, New Delhi.
Piezocomposites based on 1-3 connectivity using PZT ceramic filler (15 m and 30 m particle
sizes) and ecogel were successfully developed. These were used to fabricate tubular hydrophones
having acoustic sensitivity close to -200dB ref. 1V/Pa over wide frequency response (fig 1.).
Acoustic sensitivity was evaluated using standard B&K test set-up (fig. 2)[5] The free field
sensitivity was used by the relation[6]:
Mh = gh . t . 10-6

(1)

When converted to logarithmic form, it can be written as


20 log (Mh) [(dB ref. 1V/Pa) = 20 log(gh . t) 120]

(2)

Where t is the thickness of the piezoelement and the other notations have the usual meaning.

Fig. 1. Variation of acoustic sensitivity with frequency.


Another notable development of low frequency transducer operating in flexural mode and
generating sound of frequency of about 900 Hz. Their transducer assembly consisted of a tri laminar
structure (fig 3.) in which piezoelectric disc was sandwiched between aluminum discs and kept in
singly supported mode. The source level was measured in a water test tank and found to be 162 dB
ref 1 V/Pa with an excitation voltage of 300 Vp. The frequency of the transducer is given by the
relation
f = (813/a)*(h/a)
(3)
The motivation of this work was to make as prototype of a ocean acoustic tomography to study
the features of ocean in the area of Bay of Bengal. Further details can not be revealed.
It is interesting to watch that the growth of automobile and aerospace industry is being aided by
piezoelectric ceramics, shape memory alloys (SMA) and ER fluids. Fuel injection systems based on
piezoelectric stack actuators are replacing conventional magnetic systems due to their rapid
response and the possibility to drive any desired profile of valve displacement. This technology has
reduced the fuel consumption by 20 %. Numerous other sensors such as knock sensors, active

Advanced Materials Research Vols. 55-57

13

vibration reduction are the recent ones to join the list of other sensors already deployed in the
expensive cars for the added comfort of the passengers.

Fig. 2. Set up for measuring acoustic sensitivity.


of hydrophones.

Fig. 3. Design of a trilaminar low


frequency flexural transducer.

Health monitoring and damage detection concepts have already attracted the attention of several
researchers in the recent past using piezoelectric material as the sensing element. The study of wear
detection of train wheels is already in the advanced stage of development. These developments are
best illustrated by NASAs aircraft morphing program being carried out at Langley Research Centre
in which several optical fibre sensors have been used for in-situ monitoring the mechanical integrity
and the health of airframe structure. Use of these intelligent materials combined with light weight
composite aircrafts fitted with scramjet engines will be the beginning of a new area in the history of
avionics which will make us encircle the globe in 3-4 hours while flying at 10 mach speeds.
Other materials such as electorehological fluids (ER Fluids), SMAs will also hasten the pre of
intelligent materials. ER fluids are suspensions of extremely fine non-conducting particles in
insulating fluid. The viscosity of these fluids changes reversibly by an order of 105 under
application of electric field. Their use in fast acting hydraulic valves, clutches, brakes and shock
absorbers will greatly help the automobile industry.
The development of intelligent materials has assumed great properties and lack of space does
not permit to include other sensors.
There has been already great interest in the development of materials with giant dielectric
constants. Recent research on CaCu3 Ti4O12(CCTO) ceramics has led to new hopes of synthesizing
these heterogeneous material[7,8]. Unusual semiconducting grain cores and insulating grain
boundaries give rise to very high effective dielectric constant. These materials were synthesized by
normal mixed oxide route and their dielectric properties are exhibit in figure 4. These material
posses huge dielectric constant of several thousands at room temperature and remains constant over
a wide range and then falls to low value at lower temperatures. There is significant change in
behavior with frequency. This crossover shows a Debye like physical mechanism of giant is still
elusive. Material could be of immense utility to capacitor industry and could eventually be used in
intelligent system.
Summary
Development of new tailored materials based on ceramics, composites, polymers, shape memory
alloys and ER fluids are paving way for new generation of devices for use in avionics, surveillance
and robotics. Application of nanoparticles and carbon nanotubes may further lead to highly efficient
sensors and actuators.

14

Smart Materials

Fig. 4. Variation of dielectric properties with temperature with two fixed frequencies.
Acknowledgement
The author is thankful to Director, SSPL, New Delhi for financial support to acquire some test
equipments. Thanks are also due to Mr. Tanuj Dhawan, Mr. Raman Kashyap for discussion and in
the preparation of manuscript
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

P. Muralt: Journal of Micromech. Microeng. Vol. 10 (2000), p. 136


R. P. Tandon, R. Singh, R. D. P. Sinha and S. Chandra: Ferroelectrics Vol. 120 (1991), p. 293
A. Guran et. al.: Devices and Systems, part I and II (World Scientific, 1998)
S. Nozaki and K. Takahashi: J. Intelligent Material Systems and Structures, 5 (1994) p. 136
Bruel and Kjaer, Master Catalogae, DK-2850, Denmark, Naerum, 653 (1986)
R J Ulrick: Principle of Underwater Society (New York, McGraw Hill, 1975)
M A Subramaniam, L Dong, N Duan, B A Reismer and A W Sleight: J. Solid State Chem.
Vol. 151 (2000), p. 323.
C C Homes, T. Vogt, S. M. Shapiro, S. Wakimoto and A. P. Ramirez: Science. Vol. 293
(2006), p. 673.

Advanced Materials Research Vols. 55-57 (2008) pp 15-22


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.15

Origin of P-E Hysteresis Offsets in Compositionally Graded


Ba(1-x)SrxTiO3 Thick Films
J. Barrel 1,2, E. Stytsenko 2, M. Viviani 3 and K. MacKenzie1
1

MacDiarmid Institute for Advanced Materials and Nanotechnology,


Victoria University of Wellington, P.O. Box 600 Wellington, New Zealand
2
NZ Institute for Industrial Research and Development, Lower Hutt, New Zealand
3

IENI-CNR, Via de Marini 6, Genova, 16149, Italy

Keywords: Hysteresis offset, Graded thick films


Abstract: Compositionally graded Ba(1-x)SrxTiO3 thick films were fabricated by the airflow
deposition technique. Films displayed hysteresis translation along the polarization axis when driven
by an alternating electric field. The trend of the hysteresis shift as a function of temperature is
similar to the difference of DC currents measured when a positive and negative DC electric field is
applied. The study suggests that the origin of this phenomenon lies in an asymmetry of the film
conductance due to the presence of asymmetric Schottky contacts at the BaTiO3/Ag and
Ag/Ba0.xSr1-0.xTiO3 interfaces.
Introduction
Compositionally graded ferroelectric thin films have received much attention because of their
unique and unconventional behavior and properties that are not observed in homogeneous bulk or
thin film ferroelectrics. One of the notable characteristics of the graded thin films is the translation
of the P-E hysteresis loop along the polarization axis when driven by an AC electric field. The
position of the offset in the hysteresis loop is strongly determined by the chemical composition, the
magnitude of the periodic field applied to the film and the film temperature. The temperature
dependence of the offset in the P-E hysteresis has allowed a pseudo pyroelectric coefficient to be
defined [1]. It has been demonstrated that this pseudo pyroelectric coefficient is several orders of
magnitude larger than the traditional pyroelectric coefficient and could be used in similar
applications [2]. Since the first report of hysteresis loop offset by Schubring et al. [3] in 1991
several studies have been published describing this phenomenon [1-19]. Two main theories have
been put forward to explain the mechanism of the translation of the hysteresis loop along the
polarization axis. Most investigators have described the offset as a polarization offset or charge
offset created by the gradient of polarization. On the other hand Poullain et al. [4,5] have suggested
that the permanent shift of the P-E hysteresis is due to an asymmetry of the leakage current through
the thin films induced by the compositional gradient.
In this work, hysteresis offsets in compositionally graded Ba1-xSrxTiO3 (BST) thick films were
investigated. Thick films were fabricated using an airflow deposition method at room temperature,
with subsequent sintering.
Experimental procedure
Five compositions of Ba1-xSrxTiO3 (from x=0 to x=0.5) precursor powders for deposition were
prepared by a conventional mixed oxide route. Reagent grade BaCO3, SrCO3 and TiO2 were
weighed out in stoichiometric proportions and ball milled with zirconia balls in isopropanol for 24
hours. Then the powders were dried and calcined at 1150 0C for 5 hours. The technique of thick
film deposition from airflow has been described in detail elsewhere [20]. The airflow was generated
by a commercial jet-mill (Micron Master 02-506) fed from a compressed air line at a pressure of
700KPa. Deposition was performed at room temperature on a nickel substrate. The graded thick
films were fabricated by sequentially depositing layers from precursor powders of different

16

Smart Materials

compositions. After deposition, the films were delaminated from the substrate and sintered at 1350
0
C in a BST-rich atmosphere. Energy Dispersive Spectroscopy (EDS) was performed to investigate
the chemical composition across the BST films. Samples for electrical characterization were
provided with fired-on silver electrodes. Polarization versus electric field hysteresis loop
measurements were performed at 50Hz in silicone oil using a modified Sawyer Tower circuit [21]
with a charge amplifier possessing a reference capacitor variable from 20nF to 1F and a leakage
resistor of 109. The relaxation current measurements were achieved by the application of alternate
polarity voltage pulses. Pulses with an amplitude of 16 kV/cm were applied to the samples for 1ms
with a repetition frequency of 1 Hz. The relaxation currents were recorded and the values of
corresponding total charges (sum of switching charges and non switching charges) were derived by
integration of the current relaxation curves. The switchable charges (Qsw) were calculated from
current measurement using a four pulse sequence called the positive-up, negative down (PUND)
test [22] making possible the differentiation between switchable and non-switchable charges. The
pulses had an amplitude of 4 kV/cm, a duration of 25ms, and a delay time of 150 ms. The pulse
train had a repetition frequency of 1 Hz.
Results and discussion
Films with green thicknesses between 200m and 400m were deposited. Fig. 1 shows the Sr
composition depth profile of 2 graded Ba (1-x) SrxTiO3 thick films. The films contained layers of Ba
(1-x) SrxTiO3 with x=0.6, 0.5, 0.0 and 0.5,0.4, ..0.0 respectively. The depth profiles indicate that
the deposition method produces compositional variation across the films, creating an approximately
linear gradient. Films with differences in resistivity up to two orders of magnitude were obtained
regardless of the number of layers deposited. The resistivity variation is believed to be due to the
instability of the BST-rich atmosphere during the sintering process which affected the concentration
of free carriers. Thick films exhibited hysteresis offsets along the polarization axis. The sign of the
offset was reversed when the samples were turned over.
Fig. 2 shows the dependence of the P-E hysteresis shifts on temperature when driven by a 16
kV/cm sinusoidal field at 50 Hz for BaTiO3 -Ba0.6Sr0.4TiO3 and BaTiO3-Ba0.5Sr0.5TiO3 graded thick
films. The P-E hysteresis offset became noticeable from 70C for the BaTiO3 -Ba0.5Sr0.5TiO3 graded
film and from 120C for the BaTiO3-Ba0.4Sr0.6TiO3 graded film. The hysteresis offsets increased
with temperature well above 129C, which was the highest Curie temperature of the Ba (1-x) SrxTiO3
layers. In previous work [3] the presence of a hysteresis offset above the nominal Curie temperature
has been associated with a diffuse phase transition.
A plot of the switchable charges versus temperature measured in the BaTiO3-Ba0.5Sr0.5TiO3
graded film obtained using a PUND test is shown in Fig. 3. The switchable charges diminished
above 65 C, becoming almost nonexistent above 105 C. A steady increase in the hysteresis offset
with temperature observed in the range where ferroelectric properties rapidly decline suggests that
the relation of the offset to the ferroelectric state of the material is unlikely. We also found that the
DC resistance of the film samples strongly influences the magnitude of the offset. Indeed, larger
hysteresis translations were observed in films with higher DC conductance and no hysteresis offset
was detected in films possessing the lowest conductance.

Advanced Materials Research Vols. 55-57

17

60
BaTiO3-Ba0.5Sr0.5TiO3

% Concentration of Sr

50

BaTiO3-Ba0.6Sr0.4TiO3
40
30
20
10
0
0

0.05

0.1
0.15
Depth (mm)

0.2

0.25

Fig. 1 EDS depth profile showing Sr content for 2 graded thick films.
6
70

BaTiO3-Ba0.5Sr0.5TiO3

60

BaTiO3-Ba0.6Sr0.4TiO3

5
4

50
40

30

20
1

10
0

Polarisation offset (C/cm )

Polarisation offset (C/cm )

80

50

100

150

Temperature (C)

Fig. 2 Hysteresis offset presented as the polarization offset as a function of temperature for BaTiO3Ba0.6Sr0.4TiO3 and BaTiO3-Ba0.5Sr0.5TiO3 graded thick films.
The switching currents have been measured for both bias polarities for a range of temperatures from
65 C to 140 C. Current pulses had a rise time of 100 ns, the relaxation process being complete
within 25s.
Fig. 4 shows the switching current measured for 2 different temperatures. In the paraelectric
phase at 140 C no difference in the relaxation currents was observed for both bias polarities, or
when the thick film is turned over (up position and down position) but at 65 C the currents were
not identical.
The speed of the poling process was slightly different for opposite field directions, which can be
associated with the presence of an internal field in the film. The presence of a strong internal field
in graded thick films was confirmed by hysteresis measurements of aged thick film samples. Fig. 5
shows the P-E hysteresis loop evolution for a BaTiO3-Ba0.5Sr0.5TiO3 graded film sample aged for
six months. At low field and at high field for a limited time the hysteresis loops were deformed,
similar in shape to anti-ferroelectric materials which suggests that the internal field opposes the
polarization change in both directions. This observation is consistent with theoretical work carried
out by Zhong et al. [6] suggesting that self-polarization takes place in multilayer ferroelectrics due
to electrostatic coupling between the layers. It is important to point out that the overall values of the
calculated charges obtained from PUND for both orientations of the film are identical after the full
completion of the relaxation process. Indeed, integration of the experimental current versus time
curves produced absolute values of the charges for both directions with no more than 5% difference,

18

Smart Materials

which is within the experimental error. This result indicates that no polarization offset existed in the
films.
According to these experimental observations it appears that although a self-polarization
phenomenon occurs in thick films, it cannot explain the translation of the hysteresis loop along the
polarization axis, as the latter exists far above the transition temperature.
Switchable charges (C/cm)

0.1
0.08
0.06
0.04
0.02
0
25

45

65

85

105

125

145

Temperature (C)

Fig. 3 Temperature behaviour of switchable charges for BaTiO3-Ba0.5Sr0.5TiO3 graded thick films.
0.06

Current (A)

0.05

Down position
Up position

0.04
0.03

Down position
Up position

0.02
0.01

65C
140C

0
1.5

6.5

11.5

16.5

21.5

Time (us)

Fig. 4 Relaxation currents in the BaTiO3-Ba0.5Sr0.5TiO3 graded thick film sample.


The DC currents vs temperature were measured for the BaTiO3-Ba0.5Sr0.5TiO3 graded thick film.
The current difference for both polarities of the applied DC field of 16 kV/cm was calculated and
compared with the output voltage offset when a 16kV/cm sinusoidal field was applied to the film,
as illustrated in Fig. 6. It can be seen that both current difference and voltage offset showed similar
trends. The hysteresis shift disappeared after a heat treatment of the film samples carried out at
700C in air. The annealing process creates oxygen vacancies, decreasing the p-type conductivity of
the films. This dramatically reduced the current and the current asymmetry, and as a result no
hysteresis shift is detected.
Fig. 7 shows hysteresis loops of a BaTiO3-Ba0.5Sr0.5TiO3 thick film measured at 100C. In Fig.
7a the hysteresis loop displayed a positive offset and an asymmetric shape. When the film was
turned over, all these characteristics were inverted (Fig. 7b). The sign of the electric field related to
the inflated part of the hysteresis loop was always identical to the sign of the hysteresis offset value.
Bouregba et al. [7] have suggested that asymmetrical leakage current in a ferroelectric sample leads
to this characteristic feature. It should be noted that asymmetry of the hysteresis shape has been
reported in many works found in the literature describing the P-E hysteresis offset [7-10,23]. Our
experiments showed that the asymmetry of the current in thick films also occurs in the hysteresis
measurements at a frequency of 50Hz.

Advanced Materials Research Vols. 55-57

19

Fig. 5 P-E hysteresis loop evolution for a six-months aged sample of BaTiO3-Ba0.5Sr0.5TiO3 graded
film.
The hysteresis offset was suppressed when a leakage resistor of a sufficiently low value was
connected in parallel to the measurement capacitor in the measurement circuit.
From these observations we conclude that the high leakage resistance (Rleakage) allows the
detection of a small current asymmetry by producing a DC offset of the output voltage that
manifests itself in a stable hysteresis offset. A possible explanation of the asymmetry in the leakage
current is that the compositional variation across the film could change the height of the band gap
along the film thickness leading to different barrier heights at both interfaces. Thus, the Ag/Ba0.xSr10.xTiO3 and Ba0.ySr1-0.yTiO3/Ag interfaces may form back-to-back double Schottky contacts
behaving as a Schottky diode. It has been suggested [11] that the band gap may also be affected by
the polarization gradient. However, the fact that the asymmetry of the DC current is larger in the
paraelectric phase indicates that polarization does not play a key role in the current asymmetry. The
hypothesis that the hysteresis offset could originate from the difference in barrier height at both
interfaces is supported by the inconsistency of the results published by the same team of researchers
on the same type of graded structure. Mantese et al stated in one of their early papers [14] that the
maximum pseudo- pyroelectric coefficient for a BaTiO3-Ba0.7Sr0.3TiO3 graded film was found at 4C but in another paper [1] they reported that the maximum pseudo-pyroelectric coefficient for a
film of the same composition was around 50C. The major difference between the films used in
both studies was the type of electrodes applied. The former had Au/Cr-Pt electrodes and the latter
had Au/Cr-Pt/Ti electrodes which implies different work functions at the interfaces.

20

Smart Materials

2.00E-06

1.00E-06
3

Voltage (V)

current (A)

1.50E-06

5.00E-07
1

0.00E+00

50

100

150

temperature (C)

Fig. 6 Hysteresis offset voltage and DC current asymmetry as a function of temperature for BaTiO3Ba0.5Sr0.5TiO3 graded thick films.
20

10

10

0
-20

-15

-10

-5

10

15

20

Polarisation (C/cm)

Polarisation (C/cm)

15

0
-20

-15

-10

-5

10

15

20

-5

-10

-15

-5

-20

-10

Electric field (kV/cm)

Electric field (kV/cm)

Fig. 7 P-E hysteresis loops of a BaTiO3-Ba0.5Sr0.5TiO3 thick film measured at 100C in a) up


position and b) down position
Fig. 8 shows the current difference as function of DC bias at 35C and 120C for a BaTiO3 Ba0.5Sr0.5TiO3 graded film. At the higher temperature the current difference reached a maximum at
a lower field. An analogy can be drawn with the maximum reversal breakdown voltage of a
Schottky diode displaying a negative temperature coefficient. The maximum value of the current
difference could explain the upper limit of the hysteresis offset observed.
8.00E-09

1.60E-06

6.00E-09

1.20E-06
4.00E-09
8.00E-07
2.00E-09

4.00E-07

Current difference (A)

Current difference (A)

2.00E-06

150 C
80 C
0.00E+00

0.00E+00
0

10

20
30
DC field (kV/cm)

40

50

Fig. 8 DC current asymmetry as a function of the applied electric field at 150C and 80C for a
BaTiO3 -Ba0.6Sr0.4TiO3 thick film.

Advanced Materials Research Vols. 55-57

21

Fig. 9 shows a simple equivalent circuit of the graded film and the influence of each component
on the hysteresis loop. Rfilm is the resistance of the film, D is a diode representing an asymmetry due
to the difference in Schottky barriers at the interfaces, RsS and Rsp are the series and parallel
resistances associated with the Schottky contacts, and Cfilm is the capacitance of the film. Since the
hysteresis offset was equally pronounced in the ferroelectric and non-ferroelectric states of the
films, polarization switching is not represented in the circuit. This circuit is consistent with an
asymmetric current dependence on Rfilm and RSchottky, therefore the magnitude of the hysteresis offset
is a function of Rfilm, RSchottky and Rleakage. Another explanation of the asymmetry is that a space
charge could be created inside the graded film during diffusion of ions at the layer interfaces.
Ashkenov et al. [23] observed a hysteresis offset in a Pt-BaTiO3-ZnO-Pt thin film and suggested
that the interface between the ZnO and BaTiO3 was the origin of space charge accumulation.
A quantitative interpretation of the offset phenomenon should take into account the leakage
which is present in any real hysteresis measurement circuit.
For a measurement circuit with no leakage a stable polarization offset will produce an
increasing voltage across the measurement capacitor until the measurement amplifier is saturated.
On the other hand, if the measurement capacitor has a leakage of RL this charge build-up will be
compensated at some point by the leakage through the resistor RL resulting in a stable voltage across
RL. Under this condition the charge leakage is equal to the charge build-up. The equilibrium voltage
across RL is

U off =

U (t )Cdt

Q(t )dt

RL =

RL .

(1)

Where is the duration of one cycle, U the voltage across the measurement capacitor, RL the

leakage resistance, and Q(t )dt the charge offset for one cycle.
0

Thus the charge offset is proportional to Uoff /RL rather than UoffC.
As this calculation shows, even a very small current asymmetry can cause a significant
hysteresis offset if the leakage resistance is sufficiently large.
a

b
Cfilm

RSs

Rfilm
RSp

Rfilm

RSs

D
Rfilm
RSp

Cfilm

Fig. 9 a) Proposed equivalent circuit of a graded thick film and b) the influence of its components
on the P-E hysteresis.

Summary
The P-E hysteresis offset observed in Ba(1-x) SrxTiO3 graded thick films is unlikely to be related to
an asymmetry of the ferroelectric polarization but rather due to the rectifying characteristics of the
film samples. We suggest that the asymmetry of the current manifesting itself as a DC voltage
across the measurement capacitor is the origin of the hysteresis translation. This current asymmetry
could be induced by the difference in Schottky contacts at the graded film interfaces.

22

Smart Materials

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]

F. Jin, G.W. Auner, R. Naik, N. W. Schubring, J. V. Mantese, A. B. Catalan and A. L.


Micheli: Appl. Phys. Lett. Vol. 73 (1998), p. 2838.
J. V. Mantese, N. W. Schubring and A. L. Micheli: Appl. Phys. Lett. Vol. 79 (2001), p. 4007.
N. W. Schubring, J. V. Mantese, A. L. Micheli, A. B. Catalan, and R. J. Lopez: Phys. Rev.
Lett. Vol. 68 (1992), p. 1778.
G. Poullain, R. Bouregba, B. Vilquin, G. Le Rhun, and H. Murray : Appl. Phys. Lett. Vol. 81
(2002), p. 5015.
G. Poullain, R. Bouregba, B. Vilquin, G. Le Rhun, and H. Murray : Appl. Phys. Lett. Vol. 83
(2003), p. 811.
S. Zhong, S. P. Alpay, and J. V. Mantese: Appl. Phys. Lett. Vol. 87 (2005), p.102909-1.
R. Bouregba, G. Poullain, B. Viquin, and G. Le Rhun : J. Appl. Phys. Vol. 93 (2003), p. 5583.
D. Bao, X. Yao, and L. Zhang: Appl. Phys. Lett. Vol. 76 (2000), p. 2779.
I. Boerasu and L. Pintilie: Appl. Phys. Lett. Vol. 77 (2000), p. 2231.
D. Bao, N. Mizutani, X. Yao, and L. Zhang: Appl. Phys. Lett. Vol. 77 (2000), p. 1203.
R. Bouregba, G. Le Rhun, and G. Poullain: Integr. Ferroelectr. Vol. 70 (2005), p. 67.
J. V. Mantese, N. W. Schubring, A. L. Micheli and A. B. Catalan: Appl. Phys. Lett. Vol. 67
(1995), p. 721.
J. V. Mantese, N. W. Schubring, A. L. Micheli and A. B. Catalan: Appl. Phys. Lett. Vol. 71
(1997), p. 2047.
M. S. Mohammed, G. W. Auner, R. Naik, J. V. Mantese, N. W. Schubring, A. L. Micheli and
A. B. Catalan: J. Appl. Phys. Vol. 84 (1998), p. 3322.
S. Zhong, S. P. Alpay, Z.-G. Ban and J. V. Mantese: Appl. Phys. Lett. Vol. 86 (2005), p.
092903.
Z.-G. Ban, S. P. Alpay and J. V. Mantese: Phys. Rev. Vol. B 67 (2003), p. 184104.
W. Fellberg, J. V. Mantese, N. W. Schubring and A. L. Micheli: Appl. Phys. Lett. Vol. 78
(2001), p. 524.
J. V. Mantese : Appl. Phys. Lett. Vol. 83 (2003), p. 809.
M. Marvan, P. Chvosta and J. Fousek: Appl. Phys. Lett. Vol. 86 (2005), p. 221922.
E. Stytsenko and M. Daglish: Mat. Res. Soc. Symp. Proc. Vol. 666 (2001), p. F10.5.1.
C. B. Sawyer and C. H. Tower: Phys. Rev. Vol. 35 (1930), p. 269.
D. H. Chang, Y. S. Yoon, and S. J. Kang: J. Korean Phys. Soc. Vol. 38 (2001), p. 277.
N. Ashkenov, M. Schubert, E. Twerdowski, H. Wenckstern, B.N. Mbenkum, H. Hochmuth,
M. Lorenz, W. Grill and M. Grundmann: Thin Solid Films Vol. 486 (2005), p. 153.

Advanced Materials Research Vols. 55-57 (2008) pp 23-26


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.23

Nanosized Titania, a Smart Material or Is It Just Clever?


R. Stevensa, D. Regoninia, C.R.Bowena and A. Jaroenworaluckb
a

Department of Mechanical Engineering, University of Bath, Bath, BA2 7AY, UK


b

MTEC, 114, Paholyothin Rd.,Pathumthani 12120, Thailand

R.stevens@bath.ac.uk, angkhanj@mtec.or.th, c.r.bowen@bath.ac.uk

Keywords: titanium oxide, phase change, powder, nanotubes.

Abstract. Titanium oxide (TiO2) nanopowders can be reproducibly formed by hydroxylation of


titanium organic complexes. The crystallisation to anatase and rutile can be controlled by systematic
calcination and a complex range of properties optimized for specific applications. Characterisation of
the powders has been undertaken using advanced physical techniques. The morphology of the TiO2
powders is determined by solution concentration and precipitation phenomena, particularly
temperature and stirring regime. However the fine powders have limitations in terms of processing
flexibility particularly when nanostructured and organised features are desired, due to their fine
particle structure and inability to be sintered without undergoing complete phase change. Anodising
titanium metal can overcome these difficulties and under appropriate conditions semi-ordered
nanotubes of TiO2 have been prepared. These can be heat treated to develop the phase of choice,
anatase or rutile. A mechanism for the formation of the nanotubes has been proposed which is based
on the linkage of pores developed in the anodized oxidation product. The pores are driven to into
alignment by the applied potential and link up to form the tubular structures. A degree of control of
the tube size and wall thickness is shown possible by control of applied voltage. The nanotubes have
been investigated using SEM, TEM, XRD and Raman spectroscopy to elucidate the structure and
postulate the formation mechanism.
Introduction
Titanium oxide has been used for many years in the form of fine powder for applications such as a
white colourant in paint and in the cosmetic industry particularly as a sunscreen, where the UV
absorbtion properties are of importance. The dioxide TiO2 is the most stable of the oxides although
many lower oxides exist. TiO2 is commonly found in two forms anatase and rutile with a much less
common intermediate structure, brookite.

Figure 1. TiO2 crystal structures: rutile (a), anatase (b) and brookite (c), showing the arrangement of the TiO62octahedral in space. J. R. Smith, University of Colorado .http://ruby.colorado.edu/~smyth/min/tio2.html

To an extent, the properties of titania are dependent on the crystal structure and the phase which
develops on calcining, and are summarized in Table 1.

24

Smart Materials

Table 1. Various TiO2 polymorphs and some of their physical properties


Crystal System

Density

Optical

Refractive

(g/cm3)[1,2]

Band-Gap (eV) [2]

Index [2]

Rutile

tetragonal

4.13-4.26

3.0

2.72

Brookite

orthorhombic

3.99-4.11

3.11

2.63

Anatase

tetragonal

3.79-3.84

3.19

2.52

Results and Discussion

Titanium dioxide is a natural n-type wide band gap semiconductor, and because of its photo-stability
has been successfully utilised in photo-catalysis, photo-splitting of water, and photo-voltaic devices
such as dye-sensitised solar cells. For the same reason it is often added as a sunscreen protection to
cosmetics and, more generally, to light sensitive materials because it adsorbs UV radiation. TiO2 is
also widely used in gas-sensing devices due to electrical or optical properties changing upon
adsorption.

5nm
----

(a)

(b)

(c)

Figure 2. TiO2 powder prepared by chemical precipitation from titanium ethoxide by hydroxylation,
calcined and viewed using high resolution TEM (a). Titanium dioxide T 20, after calcination at
various temperatures for 3 h (b) XRD curves and (c) Raman spectroscopy.
The small grains of nanocrystals are stable (Fig.2a) and consist of anatase at low temperatures.
According to XRD the anatase forms form the gel at ~400OC, Fig. 2(b) whereas Raman spectroscopy
which is less particle size dependent indicates the presence of anatase at 300OC, Fig. 2(c). A more
sensitive technique, high voltage electron diffraction has shown the anatase to be present at 200OC.
In order to facilitate the fabrication of devices the TiO2 is required in suitable shapes. Nanotubes have
been fabricated in both aqueous and organic electrolytes by the anodisation of titanium metal. The
method employs a sulphate bath with a small addition of fluorine ions, to break down the thermally
formed protect oxide on the surface of the metal. The chemistry of the processes involved has been
summarized in an excellent review by Grimes and his team who have made major contributions to
understanding the phenomena [3].
The titanium metal is made the anode in an electrochemical cell and the voltage increased gradually to
15-40V. Competing processes operate and a film consisting of oxide and hydroxide forms. The
processes are identified as:1. Field-assisted oxidation
Ti + 2H2O TiO2 + 2H2
2. Field-assisted dissolution
Ti4+ + 6F TiF62
3. Chemical dissolution
TiO2 + 6F + 4H+ TiF62- + 2H2O

Advanced Materials Research Vols. 55-57

25

The oxide gel that forms on the surface of the Ti metal when examined in the electron microscope
is shown to consist of a coral like structure with extensive porosity linked by the remnant gel. The
structure is thought to arise either by the dehyroxylation of the gel or by gas formation at the metal
oxide interface. Under the action of the applied potential and during further reaction at the anode the
film self modifies and forms a series of aligned pores. The conduction path for the ions moving
between the electrodes will be along the surface of the pores. The driving force for conduction the
applied voltage will take the path of least resistance and consequently the pores will gradually align,
eventually linking up. The mechanism (Fig. 3) has been described in detail [4,5].

Figure 3. Schematic view of the growth mechanism. An anodic layer forms because ions are mobile
under the high electric field applied (a); fluorine ions generate holes (b) the oxide forms and becomes
thicker (c). Under the action of the electric field, cavities or voids would tend to become oriented
vertically to the surface of the metal, in the direction of the electric field, and to link together (d)
developing as a series of nano-tubes (e) and (f). A 3D perspective, showing the tubes as an elongated
stack of rings, is also reported (g).

26

Smart Materials

(a)
(b)
Figure 4. SEM micrographs of the (a) initial structure formed on anodisation and (b) the closely
packed array of nanotubes generated under controlled conditions.
Samples were prepared for TEM by mechanically detaching the film, supporting on carbon film
between copper grids and when necessary ion beam thinning for a short period (1-5minutes).
Subsequent examination at 200kV has demonstrated the crystalline nature of the calcined nanotubes,
with little or no grain growth taking place until sintering is found at 650OC [6]. Another feature of
interest is the development of a degree of preferred orientation in the crystals forming the tubes. The
grain boundaries were seen to be devoid of any amorphous film which suggests that any fluorine ions
have been ejected to a free surface and there is some evidence to support this.
A prototype solar cell was prepared using this technology and enhanced using N3 ruthenium organic
die as a sensitizer. The electrolyte was a tri-iodide organic capable of redox reactions and a cathode of
platinum mesh was used. It is apparent that the technology offers much in the way of aligned high
surface area TiO2 nanotubes with controlled crystal phase which can be utilised in many
photo-electric devices involving UV conversion, such as solar cells and catalytic applications.
Summary
The anodizing of titanium metal can result in the formation of layers of nanotubes on the surface with
the length of the tubes perpendicular to the surface. The diameter and wall thickness of the tubes can
be controlled. The length of the tubes is governed by the time of anodisation, the electrolyte and the
viscosity. Long times (~130h) are required to develop nanotubes in glycol based electrolytes
compared to 2h in aqueous solutions. Calcination of the oxide film results in the formation of anatase
at 200OC and at higher temperatures increasing amounts of rutile are formed until at 600OC the
conversion is complete. The structures have been investigated and the crystal morphology
characterized using TEM, which shows the tendency to preferred orientation in the nanotubes. Using
an appropriate Ruthenium organic dye sensitizer, a dye sensitized solar cell has been constructed and
shown to work.
References
[1]
[2]
[3]
[4]
[5]
[6]

Shang-Di Mo and W. Y. Ching, Phys. Rev. B Vol. 51 (1995), p. 13023.


J.-G. Li, T. Ishigaki, and X. Sun, J. Phys. Chem. C Vol. 111 (2007), p. 4969.
K.M. Gopal, K.V. Ooman, M. Paulose,K. Shankar, C.A. Grimes, Solar Energy Materials &
Solar Cells Vol. 90 (2006), p. 2011.
A. Jaroenworaluck, D. Regonini, C.R. Bowen, R. Stevens, D. Allsopp, J Mat Sci Vol. 42(2007),
p. 6729.
A. Jaroenworaluck, D. Regonini, C.R. Bowen, R. Stevens, J Mat. Res., 2008 (in press)
D. Regonini, C.R. Bowen, R. Stevens, D. Allsopp , A. Jaroenworaluck, Phys. Stat. Sol. (a) Vol.
204 (2007) p.1814.

Advanced Materials Research Vols. 55-57 (2008) pp 27-32


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.27

Magnetic Nanoparticles as Smart Heating Mediator for Hyperthermia


and Sorbent Regeneration
1

N. X. Phuc,1N. A. Tuan, 1N. C. Thuan, 2 V. A. Tuan, and 1L. V. Hong


1

Institute of Materials Science, 2Institute of Chemistry


Vietnamese Academy of Science and Technology
18 Hoang Quoc Viet, Cau Giay, Ha Noi

Keywords: Magnetic nanoparticles, Magnetic heating, hyperthermia, desorption

Abstract: This work presents the results of our recent studies on magnetic heating of several
nanomaterial systems. Nanoparticles of Fe3O4, (Mn, Zn)Fe2O4 and (La, Sr, Ca)MnO3 were
synthesized by co precipitation and mechanical milling technique. Structural characterization
showed that the prepared particles are of single phase with particle size ranging from 10 to 40 nm.
Basic magnetic characteristics such as Curie temperature Tc, coercive field Hc and saturated
magnetization Ms were determined. For studying magnetic heating effect, a set up with use of an
alternating field of strength Ho = 40 100 Oe and frequency f = 130 400 kHz; and alcoholic
thermometer or Cu-Const thermocouple was established. Basic parameters of magnetic heating
effect, such as saturated heating temperature Ts, specific loss power (SLP) were thoroughly
investigated for the fluids of manganite and magnetite suspended in water. The relationships
between the Ts and SLP parameters and Hc, Tc, Ms and/or suspension concentration C will be
presented and discussed. For the application of the heating effect to regenerate an adsorbent,
composite of spinel ferrite nanoparticles with several mesoporous materials was prepared. The
studies show that the magnetic heating desorption of m-xylene from the adsorbed composite is very
effective.
Introduction
The response of magnetic nanoparticles to an external magnetic force is their unique feature for
many applications in biomedicine as well as environmental treatment [1, 2]. When exposing to an
alternating magnetic field, the nanoparticles can absorb energy via various physical mechanisms
including the magnetic hysteresis loss, Neel relaxation loss and Brownian loss [3]. This energy is
considerably high to make the particles as the local nano-fires for the application of magnetic
hyperthermia and adsorbent regeneration [3, 4].
The first case, magnetic hyperthermia, is the most promising method in cancer treatment
because of its capability to destroy the tumor cells selectively by heating them up to a desired
temperature range (e.g. 42-46 oC) at which the healthy tissues can still survive. By now the iron
oxides are the common materials using for this application since their biocompatibility has been
proven. However, the empirical investigations often show that specific loss power (SLP) of the iron
oxide nanoparticles depends strongly not only on their microstructural properties and magnetic
behaviors, but also on the technical parameters of the alternating magnetic field (frequency and
field strength) [5]. Therefore, the heating capacity of nanoparticles synthesized by different methods
might be utilized with different factors. The highest value of SLP of 960 W/g at the field of 410
kHz and 10 kA/m was found for magnetosomes produced by magnetotactic bacteria [6].
Alternatively with utilizing SLP, controlling the heating temperature by using the smart
materials with suitable Curie temperatures is also an interesting strategy [7, 8]. Some efforts has
been put on tuning the Tc of the lanthanum perovskite manganite by changing the double exchange
interaction concentration (Mn3+/Mn4+ ratio) [7,8]. However, the Curie temperature decreased from
about 90oC to about 40oC with a gradual decrease of saturation magnetization. This resulted in a
limit of obtaining high heating capacity of the material.

28

Smart Materials

Recently, the heating effect of nanoparticles was also found having many advantages in the
application of adsorbent regeneration [4]. By using the ferrite spinel nanoparticles with a Curie
temperature of 50-350 oC as the heating mediators, the desorption process was expected to be much
more efficient than the conventional one that often bring the adsorbents into contact with a hot
steam.
In this paper, we present our investigations about the heating effect of three types of magnetic
nanoparticles: (i) the iron oxide, (ii) the lanthanum perovskite manganite nanoparticles for the
application of magnetic hyperthermia and (iii) the Mn-Zn ferrite spinel nanoparticles for the
application of adsorbent regeneration.
Experimental
2.1. Synthesizes of nanoparticles
The Fe3O4 and Mn1-xZnxFe2O4 (x = 0.0-0.5) ferrite spinel nanoparticles were fabricated by using the
co precipitation method with FeCl2, FeCl3, MnCl2 and ZnCl2 as the starting materials and NaOH or
NH3 as the precipitating agent. The precipitate from the precipitation reaction was washed several
times by distilled water, separated by a permanent magnet and dried in the air at 40 oC in 20 h. The
samples with different particle sizes could be prepared by altering some technical parameters such
as the reaction temperature and the rotation rate during the fabrication procedures. The Fe3O4
samples were denoted as M1-M6 for the saturation magnetization of 28-75 emu/g, respectively. The
ferrite spinel nanoparticles were denoted as Z0-Z50 with x = 0.0-0.5, respectively.
The La0.7Sr0.15Ca0.15MnO3 bulk sample prepared by the conventional solid-state reaction method
was subjected to a high-energy milling process using a commercial milling machine (Spex 8000D)
to create the nanoparticles. After that these nanoparticles were annealed at different temperatures
ranging from 600 to 900oC for 5 hours to make samples with different crystallite size (denoted as
S600, S700, S800 and S900, respectively).
2.2. Magnetic heating experiment
The magnetic heating experiments were performed under an alternating magnetic field with a
frequency of 219 kHz and a field strength of 40 100 Oe. The magnetic field is generated by a
seven-loop induction coil of 3 cm diameter and 11.5 cm length. The samples were dissolved in the
distilled water suspensions and thermally isolated by a vacuum layer (10-3 10-4 Torr). During the
heating experiment, the temperature of the sample was observed by using an alcoholic thermometer
(in the range of 10-100 oC) and/or a Copper-Constantan thermocouple (up to 400 oC). The SLP of
the samples were estimated by comparison of their heating curves with that of a reference resistance
heater.
2.3. VOC adsorption/desorption experiment
The adsorption equilibrium measurements were carried out by gravimetric method. The
mixtures of adsorbent (silica SBA-15) and the ferrite spinel particles were calcined at 400oC to
eliminate possible adsorbed impurities and hygroscopic moisture in particular. After at least 3h of
this activation regeneration, the samples were rapidly transferred into a desiccators containing mxylen. Adsorption was carried out at room temperature (300C) and ambient pressure until no weight
gain was observed by an analytical balance. Adsorption equilibrium was achieved around 12h.
The desorption measurements were performed by using a digital analytical balance. Samples
were elevated at the centre of the induction coil by using a glass tube. The saturated adsorbed
absorbent composite was rapidly transferred from desiccators to the coil for the desorption
experiment.
2.4. Characterization techniques
The structural and morphological investigations were taken by using an X-ray diffractometer
(XRD) and a field-emission scanning electron microscope (FESEM). The magnetic properties were
carried out by using a vibrating sample magnetometer (VSM).

Advanced Materials Research Vols. 55-57

29

Results and Discussion


3.1. Structural and magnetic properties

Fig.1. FESEM images of (a) the Fe3O4 sample


M6, (b) the manganite sample S700, and (c) the
ferrite spinel sample Z0.

c
Figure 1 shows the typical FESEM images of (a) the iron oxide (M6), (b) the perovskite manganite
(S700) and, (c) the ferrite spinel particles (Z0). It was clearly demonstrated from the results of the
magnetic measurements and structural characterizations that the magnetic properties of the particles
depend strongly on their size. There were six iron oxide samples in this paper denoted as M1-M6
for the saturation magnetization values of 28-75 emu/g, respectively. The Ms of these samples
increased proportionally to the increasing of the particle size. One can see from Fig. 1a that the M6
particles were distributed uniformly with a particle size smaller than 20 nm.
For the lanthanum perovskite manganite nanoparticle, the increasing of particles size also leads
to the considerable increase of both saturation magnetization and Curie temperature. By using the
Warren-Averbach method, it was estimated from the XRD data that the mean crystallite size of the
particles varies gradually from 24 nm to 54 nm, depending on the annealing temperature from
600oC to 900oC.
The change in composition of the ferrite spinel samples by increasing Zinc concentration leads
to a strong decrease of particle size as well as saturation magnetization and Curie temperature.
3.2. Magnetic heating of nanoparticles
The magnetic heating curves of various iron oxide samples with particle concentration of 20
mg/ml are shown in Fig. 2. After about 20 30 minutes of heating, temperature of the samples
come to saturation when the energy exchanged to the surrounding medium equals to the energy
released from the magnetic particles.

30

Smart Materials

90
120

80

70

100

60

80

SLP (W/g)

50
40
30
M1
M2
M3

20
10

500

M4
M5
M6

1000

(emu/g)
10

15

20

1T

Temperature ( C)

80

80

60
40
20
0
20

1500

30

40

Time (s)

Fig. 2. The magnetic heating curves of sample M1


M6 (particle concentration is 20 mg/ml).

50

1T

60

70

80

(emu/g)

Fig. 3. The dependences of initially heating rate on


M1T and M80.

0.3

50

0.25

45

Temperature ( C)

0.2

dT/dt ( C/s)

Sample with higher saturation magnetization demonstrates faster temperature rising rate and
higher saturation temperature. Figure 3 shows the dependences of initially heating rate on M1T and
M80 (magnetization at field strength of 1 Tesla and 80 Oe, respectively). Approximately, these
dependences obey the square function, except for sample M6 with an extra-high heating rate and a
SLP value of 107 W/g. Figure 4 shows the field strength dependence of the heating rate for sample
M5 with particle concentration of 20 mg/ml. This dependence obeys closely the square function.
Most of the researches already found that the heating power is proportional to H, where H the field
strength and = 1 3, depending on the magnetization process of the materials [7-10].
The self-controlled heating effect is demonstrated evidently through the time-dependent heating
curves of the samples with various Curie temperatures (figure 5). With the magnetic particle
concentration of 20 mg/ml, the equilibrium temperatures remain 1115oC below the Curie points.
This can be explained by the less energy absorption of the particles from alternating magnetic field
due to the progressive decline of magnetization in the vicinity of TC.

0.15
0.1

40
35

S600
S700
S800
S900

30

0.05
0

25

20

40

60

80

100

Field strength (Oe)

120

500

1000

1500

2000

Time (s)

Fig. 4. The field strength dependence of the heating Fig.


5.
Magnetic
heating
curves
of
rate for sample M5 with particle concentration of La0.7Sr0.15Ca0.15MnO3 nanoparticle suspensions (20
mg/ml) under various annealing temperatures (H =
20 mg/ml.
80 Oe, f = 219 kHz)

Advanced Materials Research Vols. 55-57

31

Figure 6 demonstrates the dependences of Curie temperature, magnetization at field strength of


2 Tesla and mean particle core size (inset) on saturation temperature of the various samples. With
the same particle concentration, it is clear that not only Curie temperature gives contribution to the
equilibrium point but also the roles of saturation magnetization and the sharpness of the
ferromagnetic paramagnetic phase transition are very important.
For further study on the self-controlled heating behavior of these La0.7Sr0.15Ca0.15MnO3
nanoparticles, the influences of particle concentration and magnetic field strength on heating
capacity of the material were also taken into account. The relationship between saturation
temperature and magnetic particle concentration in suspension is demonstrated in figure 6. By
increasing concentration from 10 mg/ml to 100 mg/ml, the difference between saturation
temperature and Curie temperature reduces from 13 degree to 9 degree. One can predict from this
trend that with very high concentration of magnetic nanoparticles, the saturation temperature will
reach closely the value of Curie temperature. The self-controlled heating characteristics also can be
found with the ferrite spinel nanoparticles. Figure 8 shows the heating curves of the various ferrite
samples with the particle concentration of 200 mg/ml.
49

65

40

55

50

45

48

30

45
42
39
36
20

30

40

48

50

60

Saturation te mperature o( C)

M 2T

M2T (emu/g)

Curie temperature ( C)

TC

Saturation temperature ( C)

60

50

20

60

47
46
45
44
43
42

M e an dia me t er ( nm)

41

36

38

40

42

44

46

48

50

Saturation tem perature (oC)

20

40

60

80

100

120

C o ncen tration (m g/m l)

Fig. 6. Dependence of Curie temperature, Fig. 7. Saturation temperature vs. particle


magnetization at field strength of 2 Tesla and mean concentration in suspension of sample S700 as
particle core size (inset) on saturation temperature exposed to the AMF of 80 Oe and 219 kHz.
of S600, S700, S800 and S900 nanoparticles

The temperature of the samples was elevated fast during several first minutes and then approach
to the saturation point. This saturation temperature decreased with increasing the Zinc
concentration.
200

120

Z0
Z10
Z20

150

120

Z30
Z40

100

60

40

10%
20%
30%
40%
50%

50

20

0
0

200

400

600

800 1000 1200 1400

t (s)

Fig. 8. Heating curves for


various ferrite samples (Z0Z40) with particle concentration
of 200 mg/ml

Z10
Z5

80

H (%)

H (%)

T ( C)

80

100

Z40
Z30
Z20

100

100

200

300

t (s)

400

500

60

40

20

600

100

200

300

400

500

600

t (s)

Fig. 9. Desorption curves for Fig. 10. Desorption curves for


various
concentrations
of ferrites with various Zn contents
magnetic nanoparticle media in in mdes/mads (%)
mdes/mads (%)

32

Smart Materials

3.3. Desorption processes


Figure 9 shows the desorption curves of the Z0 sample with different magnetic nanoparticle
concentrations (from 10 to 50 wt. %). A high desorption efficiency was achievable from 80 to 100
%. The desorption rate decreased systematically with the decrease of the magnetic concentration.
With 50 wt. %, the mean desorption rate was about 1 %/second and this remained 0.2 %/second
with 10 wt. %.
Figure 10 shows the desorption curves of the samples with various Zn content (with particle
concentration of 30 wt. %). It is clearly indicated that the desorption rate decreased for the lower TC
sample. This maybe due to the heating capability of the sample increased with decreasing the Zn
content. Therefore, the sample of high Zn content cannot elevate the heating temperature high
enough for the desorption process.
Summary
Fe3O4, La0.7Sr0.15Ca0.15 and Mn1-xZnxFe2O4 nanoparticles were successfully manufacture by a coprecipitation method and a high energy milling technique combined with the solid state reaction
method, respectively. Magnetic heating test experiments were performed by using the magnetic
nanoparticles as heating mediators that confirmed the magnetic nanoparticles are suitable for the
magnetic heating by an alternating magnetic field in the hyperthermia application as well as in the
VOC sorbent regeneration.
Acknowledgement
This work was performed under the Grant No. 4.107.06 of National Program for Natural Sciences
and the research project in magnetic nonmaterial and applications of Vietnamese Academy of
Science and Technology. A part of this work was done using the facilities of the National Key
Laboratory for Electronic Materials and Devices, Institute of Materials Science.
References
[1]
[2]

[3]
[4]
[5]
[6]
[7]
[8]

Q.A. Pankhurst, J. Connolly, S.K. Jones, and J. Dobson: J. Phys. D: Appl. Phys. Vol. 36
(2003), p. 167.
Cafer T. Yavuz, J. T. Mayo, William W. Yu, Arjun Prakash, Joshua C. Falkner, Sujin Yean,
Lili Cong, Heather J. Shipley, Amy Kan, Mason Tomson, Douglas Natelson and Vicki L.
Colvin: Science. Vol. 314 (2006), p. 964.
R. Hergt, W. Andra, C. G. dAmbly, I. Hilger, W. A. Kaiser, U. Richter, and H. Schmidt:
IEEE Trans. Magn. Vol. 34 (1998), p. 3745.
N. Kikukawa, M. Takemori, Y. Nagano, M. Sagasawa and S. Kobayashi: J. Magn. Magn.
Mater. Vol. 284 (2004), p. 206.
R. Hergt and W. Andra: Magnetism in medicine: a handbook, second edition (Willey, Berlin,
2007).
R. Hergt, R. Hiergeist, M. Zeisberger, D. Schuler, U. Heyen, I. Hilger, and W. A. Kaiser: J.
Magn. Magn. Mater. Vol. 293 (2005), p. 80.
A.A. Kuznetsov, O.A. Shlyakhtin, N.A. Brusentsov and O.A. Kuznetsov: European Cells and
Materials. Vol. 3 (2002), p. 75.
S. Mornet, S. Vasseur, F. Grasset and E. Duguet: J. Mater. Chem. Vol. 14 (2004), p. 2161.

Advanced Materials Research Vols. 55-57 (2008) pp 33-36


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.33

Defining Structure in Electrospun Polymer Fibres


G. R. Mitchell1,a, M. Belal1,b, F. J. Davis1,c, D. E. Elliott1,d,
M. Kariduraganavar2,e, S. D. Mohan1,f, R. H. Olley1,g and S. Sen1,h
1

Polymer Science Centre, University of Reading, Whiteknights, Reading RG6 6AF


2

Department of Chemistry, Karnatak University, Dharwad 580 003, India

g.r.mitchell@reading.ac.uk, bm.b.belal@reading.ac.uk, cf.j.davis@reading.ac.uk


d.e.elliott@reading.ac.uk, em.y.kariduraganavar@reading.ac.uk, fs.d.mohan@reading.ac.uk
g
r.h.olley@reading.ac.uk, hsujat.sen@reading.ac.uk

Keywords: electrospinning, SANS, WAXS, crystallization.

Abstract. We use a combination of microscopy, x-ray scattering and neutron scattering to show
how structure develops in micro and nano-size polymer fibres prepared by electrospinning. The
technique has been applied to a range of different polymers, an amorphous system (polystyrene), a
crystallisable polymer (poly--caprolactone), a composite systems (polyethylene oxide or poly vinyl
alcohol containing polypyrrole) and consider the possibility of self assembly (gelatin).
Introduction
Electrospinning is observed when a high electric field is applied to a polymer solution. The
experiment involves a polymer solution in a syringe with an electrically conducting needle and a
counter or collecting electrode [1, 2]. The application of a large electric field leads to a jet, which is
elongated, and the simultaneous process of solvent evaporation leads to the formation of fibres with
dimensions (at least in terms of fibre diameter) which range from ca. 100 nm to a few micrometers.
These dimensions are typically outside the range of fibres obtained by other methods even under
the most optimized conditions. From an experimental perspective, parameters, such as solution
viscosity, conductivity of the solution, the molecular weight distribution and many others play a part
in determining the diameter and profile of the nanofibres. Thus the systems are complex, but by
virtue of the ranges of factors involved in their formation, the dimensions are controllable. The
potential for forming fibres on this scale has clear implications in terms of the development of
structures on the nano-scale or nanotechnology. The preparation of electrospun fibres is
motivated by a range of potential applications including membranes, catalysts, medical implants,
optics and electronics [3].
The transformation from solution to solid is a complex process even for a simple film.
Electrospinning to produce micro and nano sized fibres is a highly non-linear process. In this
presentation we explore the development of structure and morphology of different types of polymer
systems. We start with polystyrene where we have conducted the first small-angle neutron
experiments of electrospun fibres to reveal both expanded polymer chain configurations and the
extent of chain anisotropy developed during the electrospinning process. We have extended the
material system to more complex examples including those involving a crystallisable polymer,
polycaprolactone, a conducting polymer composite, and a material in which an important feature of
the structure is the development of intermolecular hydrogen bonding.
Experimental
A typical electrospinning experiment was performed using a glass syringe fitted with a 22 gauge
needle of length 2.5cm and with an internal diameter of 0.71mm together with a flat aluminium
electrode placed normal to the needle at distances varying from 10 to 40cm. A High Voltage supply
was used which allowed defined voltages over the range 7.5-20kV. Electrospinning experiments

34

Smart Materials

were performed at room temperature (generally ca 20 C), in ambient conditions, except a low
velocity solvent extraction fan was employed to prevent accumulation of toxic vapors. Deuterated
polystyrene was prepared by free radical polymerization using azo-(bis)isobutryonitrile as initiator
at 55 C. Polypyrrole with a controlled particle size was prepared according to the procedure in [4].
Results and discussion
Polystyrene. We have synthesized a series of deuterated polystyrenes using a range of molecular
weights. The polymer were synthesized from d8 styrene initiated with varying concentrations of
initiator. Fibres were electrospun from solution in butanone. Small angle neutron scattering at the
ISIS facility (Oxfordshire UK) was used to provide details of the polymer chain dimensions, in
particular the radius of gyration. Typical results are shown in Figure 1. Figure 1 (a) shows the
variation of the radius of gyration for the fibres as a function of the polymer concentration used for
electrospinning. The values obtained clearly reflect more the behaviour of the polymer in the initial
solution rather than that of the bulk state. The radius of gyration of the electrospun fibres
approaches that of the bulk polymer as the concentration of the initial solution increases; there was
no obvious correlation with the final fibre diameter in these examples. Interestingly lower
molecular weight materials show less clear cut trends; at least at low concentration; we suggest that
the speed at which the polymer backbone can reorganize is crucial to the morphology of the final
product (at least in part because of chain entanglement and viscosity) but on the whole the
conformation in the solution prior to fibre formation is the predominant factor in determining the
conformation of the polymer chains in the fibres.
Figure 1 (b) shows a scattering pattern obtained for a higher molecular weight polystyrene fibre
(Mw ca. 230,000, Mn ca. 62,000), where all the fibres were oriented in the same direction. On
closer analysis it was found that there was some degree of anisotropy in the polystyrene backbone.
Our analysis indicated 2 radii of gyration parallel and perpendicular; namely 7.7 and 7.1 nm. On
the one hand this represents a substantial elongation of the polymer backbone. We have developed
a method of deconvoluting the partial misalignment of the fibres in the SANS sample and this gives
a molecular orientation parameter <P2> of ~ 0.2 Thus not-with-standing the data described above,
there is some elongation of the polymer backbone during the electrospinning process.
170

(a)

(b)

(Dilute State)

160
150

(Theta State)

140
130

Rg (angstrom)

120
110
100
90

E-spun Fibres

80
70

( Bulk State)

60
50
40
30
20
10
-10

10

20

30

40

50

60

70

Polym er Concentration (% )

80

90

100

110

M w ~ 228,701

Figure 1. Neutron scattering data obtained for electrospun polystyrene fibres (a) variation of radius
of gyration with polymer concentration (b) neutron scattering pattern for a group of fibres showing a
degree of molecular anisotropy (fibre axis vertical).
Crystallisable polymers. By virtue of its biodegradability Poly(-caprolactone) is particularly
suitable for scaffolds used in temporary tissue repair [5]. A crucial factor here is the question of
crystallisation. Crystallisation will enhance the mechanical strength of the fibres; crucial if these are
to be present in load-bearing systems, for example as scaffolds in bone regeneration. We have
investigated the crystallisation of electrospun fibres and compared these with the bulk material.

Advanced Materials Research Vols. 55-57

35

Figure 2(a) shows the wide-angle X-ray scattering pattern obtained from fibres spun from a mixture
of dimethyl formamide and dichloromethane (60: 40) their is clearly some crystallisation, but the
level is lower than for a melt crystallised system. Interesting there is a modest level of preferred
orientation of the crystals which do form. A more detailed analysis reveals some alignment of the
amorphous component. Figure 2 (b) shows optical microscopy of similar fibres. The fibres lying lop
left to bottom right, parallel to the positive direction of the mica quarter-wave plate, appear brighter,
which would be consistent with a small tendency for molecules to lie parallel to the fibre axis; those
lying bottom left to top right correspondingly appear darker. Particularly in the thicker fibres
without DBS a mottling is observed, indicative of spherulitic structure. That being said x-ray
diffraction suggests that the level of crystallisation in the fibres is somewhat lower that that for films
cast directly from solution. There are two possible explanations for this; firstly crystallisation
requires time, particularly in polymeric systems where the polymer backbone may need to be
reorganised; secondly the fact that the length scale of crystallisation may be larger than the diameter
of the fibres introduces a further complication. This latter problem becomes more obvious for
composite systems as discussed below.
(a)

(b)

Figure 2. Wide-angle x-ray scattering (fibre axis vertical) (a), and optical microscopy (50m scale)
(b), of electrospun fibres of Poly(-caprolactone) showing some (albeit slight) crystallisation.
Composites. In general conducting polymers exhibit poor solubility and it is particularly difficult to
produce solutions of sufficient viscosity to electrospin. To produce fibres with conducting materials
it is necessry to constrain the conducting material in a more suitable polymer. We have focused on
polypyrrole, although the principles will apply to other insoluble materials such as inorganic
composites and carbon-based materials such as nanotubes. A particular proplem here is the physical
dimensions of the particles to be incorporated
(a)

(b)

Figure 3. (a) SEM of polypyrrole particles with average size 50-100 nm (b) optical microscopy of
polyethylene oxide fibres; average fibre diameter ca. 10m. Bar = 50m.
It became rapidly obvious that the dimensions of polypyrrole synthesised conventionally by
oxidation of pyrrole with ferric chloride produced particles with dimensions greater than the typical
diameters of the electrospun fibres (even when the particle size was reduced using a ball mill). To

36

Smart Materials

produce smaller particles pyrrole was polymerised with ferric chloride using a microemulsion
technique using either dodecyltrimethyl ammonium bromide as a surfactant [3] or by using
dispersion polymerization of pyrrole in poly(vinylalcohol) [6]. With these smaller particles [Figure
3(a)], it was possible to generate electrospun fibres containing polypyrrole [Figure 3(b)]
Gelatin. In essence the formation of a cross-linked gel from gelatin relies on intermolecular
interactions between neighbouring molecules; on the basis of the previous paragraphs, it might be
predicted that the dynamics of electrospinning does not facilitate this. We have investigated the
gelation of (bovine) gelatin in water and a variety of solvents. It certainly is the case that spinning
fibres in aqueous solution is difficult to achieve reproducibly. However it is possible to produce
fibres in acetic acid. Water makes it difficult it is to electrospin the material due to gelation. The
fibres produced are particularly discrete [Figure 4 (a)] but x-ray scattering [Figure 4(b)] reveals that
the sort of organization present in a film cast from water (lower curve) or acetic acid (middle curve)
is not present in the electrospun fibres (upper curve).
(a)

(b)

Figure 4. Fibres electrospun from gelatin observed by SEM (a) and WAXS (b)
Summary
Electrospinning is a dynamic process in that the structures built into the fibres are not the most
thermodynamically favoured ones. Interestingly the conventional consequences of fibre formation
such as crystallization and backbone anisotropy are less marked in this process despite the enhanced
aspect ratio of the fibres. This may in some circumstances be disadvantageous on the other hand
with correct tailoring of polymers and solutions it offers the potential for the development of
materials systems with morphological features which might be difficult to obtain using conventional
processing techniques.
References
[1]

D. H. Renekera, A. L. Yarin, H. Fong, and S. Koombhongse, J. Appl. Phys. Vol. 87 (2000), p


4531.
[2] Taylor, Proc. R. Soc. London Ser. A, Vol. 280 (1964), p. 383.
[3] Z-M. Huang, Y-Z. Zhang, M. Kotaki, and S. Ramakrishna, Compos. Sci. Technol. Vol. 63
(2003), p. 2223.
[4] H.Wang. T.Lin and A.Kaynak, Synthetic Metals, Vol. 151 (2005), p. 136.
[5] H. Yoshimoto, Y.M. Shina, H. Terai, and J.P. Vacantia, Biomaterials Vol. 24 (2003), p. 2077.
[6]. S. P. Armes, J. F. Miller., and B. Vincent, J. Colloid Interface Sci. Vol. 118 (1987), p. 410.

Advanced Materials Research Vols. 55-57 (2008) pp 37-40


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.37

Sonocatalyzed Ammonothermal Preparation


of Fine Lithium Niobate Powders
A. Rujiwatra1,a, N. Thammajak2,b, Y. Chimupala1,c and P. Laoratanakul3,d
1

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200
Thailand.

National Synchrotron Research Center, PO Box 93, Nakhon Ratchasima 30000 Thailand.
3

National Metal and Materials Technology Center, Pathumthani 12120 Thailand.

apinpus@chiangmai.com, bn.thammajak@gmail.com, cyothin_33@hotmail.com,


d
pitakl@mtec.or.th

Keywords: Lithium Niobate, Chemical Synthesis, Solvothermal, Powder Technology


Abstract. The so-called sonocatalyzed ammonothermal technique has been developed for the
preparation of lithium niobate fine powders from commercially as-received niobium pentoxide and
lithium nitrate. The present work shows that the application of ultrasonic activation prior to the
ammonothermal treatment can produce a single phase lithium niobate fine powder at a relatively
low temperature of 220C. The influences of Li-precursors, ammonia solution concentration,
reaction temperature and time, as well as Li:Nb mole ratio - which is evidentially the most critical
factor promoting a single phase formation - are discussed.
Introduction
Due to the excellent pyroelectric, piezoelectric, electro-optic and photo-elastic coefficiences as well
as practical acoustic wave properties, lithium niobate (LiNbO3 or LN) can find numerous
technological applications, e.g. as acoustic wave transducers, optical modulators, dielectric
waveguides, holographic data processing devices. The performances of the fabricated devices
however can vastly differ depending particularly on phase purity and stoichiometry of the LN
powder precursors, which are still the basic problems limiting the usage. Recently, there have been
reports on the application of a solvo(hydro)thermal technique for the preparation of LN fine
powders [1-4]. The foundation of these reported techniques is remarkably alike, being based on a
freshly prepared niobic acid from the reaction of Nb2O5 with KOH and glacial acetic acid. Only
recently a success in the usage of as-received Nb2O5, the most common and cheapest commercially
available Nb-precursor, for the preparation of a single phase LN powder has been reported. This
was achieved via a simple ammonothermal reaction at 260oC [4]. Here we report the success in the
improvement of this technique by using ultrasonic activation. The influences of various synthetic
parameters are also discussed.
Experimental
White slurries of niobium pentoxide (Nb2O5, Sigma-Aldrich 99.99%) and either lithium hydroxide
hydrate (LiOH.H2O, BDH Chemicals Ltd 99%) or lithium nitrate (LiNO3, Fluka 98.0%) were
prepared using 15, 25 and 30%w/w ammonia solutions (NH3, PA-ACS 28.0-30.0%). The amount of
the starting Nb2O5 was kept constant at 0.56 moldm-3 for each experiment, whereas that of the Liprecursors was varied in order to adjust the Li:Nb mole ratio from 1:1 to 3:1. The slurries were
transferred into autoclaves (Parr Instrument) with ca. 50% filling capacity. The autoclaves were
then sealed and ultrasonic irradiated at 70C for 5 hours using a laboratory ultrasonic bath
(Bandelin Electronic RK255H, 160/320W, 35kHz), followed by ammonothermal treatments. Two
different temperatures of 200C and 220C were applied for 1-7 days under autogenous pressure.
The powders were recovered by filtration and washed with deionized water until the pH of the

38

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filtrate was ca. 7. Powder X-ray diffractometry (XRD, Siemens D500/D501, CuK, Ni filter,
=1.54 ) was used to characterize phase formation. Field emission scanning electron microscopy
(FESEM, JEOL JSM-6335F) was used to examine particle morphology, primary particle size and
aggregation, whereas laser diffraction technique (CILAS 1064, 0.04-500.00 m/100 classes) was
used to study size of the aggregates.
Results and Discussion
The experiments were at first performed using the reaction slurries prepared from the commercially
as-received Nb2O5 and either LiOH.H2O or LiNO3 with an equimolar ratio of Li:Nb. It was evident
that LiNO3 always provided a better phase formation of LN under the same preparative conditions
(Fig. 1). This is in contrast to the experiments under hydrothermal conditions where LiOH.H2O
provided better results [4], and can be accounted for by the following reactions.
2LiNO3 + Nb2O5 = 2LiNbO3 + 2NO2 + 1/2O2
5NO2 + 4NH3 = 3/2N2 + 2N2O + 2NO + 6H2O

(1)
(2)

The reaction between LiNO3 and Nb2O5 generates NO2, which will react further with NH3 under the
ammonothermal conditions [4,5]. This therefore enhances the reaction between the starting
precursors. This, however, will not be the case of LiOH.H2O due to the absence of the NO2 product.
2LiOH + Nb2O5 = 2LiNbO3 + H2O

(3)

The influence of the concentration of NH3(aq), playing an important role as mineralizer, pressure
transmitting media and reaction enhancer, is distinct. Only the highest commercially available
ammonia concentration of 30%w/w led to the formation of LN as a major phase (Fig. 1). At
15%w/w of NH3(aq), not any diffraction peak corresponding to LN appeared in the XRD pattern,
whereas some characteristic peaks of LN could be observed when 25%w/w NH3(aq) was employed.
This suggested the initiation of the LN formation, although the reaction was far from complete. A
higher temperature may be required for the completion of the reaction. The favor of a high NH3(aq)
concentration towards the formation of LN under these ammonothermal conditions can be
rationalized in the same fashion by the reactions described above.
Fig. 1 XRD patterns of the powders
obtained from the reactions performed at
200C for 3 days using (a) LiOH.H2O in
30%w/w NH3(aq), (b) LiNO3 in 15%w/w
NH3(aq), (c) LiNO3 in 25%w/w, and (d)
LiNO3 in 30%w/w, where |, and 
indicate
diffraction
peaks
of
stoichiometric and non-stoichiometric
LN, and NbxOy phases, respectively.
Regardless of reaction time (3-7 days), LN was perpetually present as a mixture of various phases
of niobium oxides and other niobium-rich LN phases, e.g. Nb2O5, Nb2O19 and Li2Nb32O81, when the
starting Li:Nb mole ratio, NH3(aq) concentration and reaction temperature were kept at 1:1,
30%w/w and 200C, respectively. There was no significant difference in the XRD patterns of the
obtained powders as exemplified in Fig. 2, although higher degrees of inter-particle fusion and
larger particle sizes were apparent with prolonged reaction times according to the FESEM images
(not shown here). The increasing of the reaction temperature to 220C on the other hand resulted in
a clearly improved phase formation. According to the results discussed thus far, LiNO3, 30%w/w

Advanced Materials Research Vols. 55-57

39

NH3(aq) and a reaction temperature of 220C were chosen for further investigations on the
influence of the Li:Nb mole ratio, which was revealed to be critical in the single phase formation.
Fig. 2 XRD patterns of the powders
obtained from the reactions using Li:Nb
of 1:1 in 30%w/w NH3(aq) at (a) 200C
for 3 days, (b) 200C for 5 days, (c)
200C for 7 days, and (d) 220C for 7
days; |, and  indicate diffraction
peaks of stoichiometric and nonstoichiometric LN, and NbxOy phases.

Fig. 3. XRD patterns of the powders


obtained from the reactions using varied
Li:Nb mole ratios of (a) 1:1, (b) 1.2:1, (c)
1.5:1, (d) 2:1 and (e) 3:1, in 30%w/w
NH3(aq) at 220C for 7 days; |, and 
indicate
diffraction
peaks
of
stoichiometric and non-stoichiometric LN,
and NbxOy phases.
Fig. 3 shows the XRD patterns of the LN powders obtained from the reactions between LiNO3 and
Nb2O5 in 30%w/w NH3(aq) at 220C for 7 days. There was no discern difference in phase purity of
the obtained LN powders when the Li:Nb mole ratio was varied from 1:1 to 1.5:1. Increasing the
Li:Nb mole ratio to 2:1 however resulted in a single phase LN powder, whereas the mole ratio of
3:1 deteriorated phase purity again. This suggests that an optimized excess of Li-precursor is
necessary to promote the completion of the reaction, and that Li:Nb of 2:1 is the optimal mole ratio
under the investigated conditions. The preparation of a single phase LN powder from Nb2O5
without any pre-treatment has therefore been successfully achieved via an ammonothermal reaction
with 5 hours of ultrasonic activation, using 30%w/w NH3(aq) at relatively low temperature of
220C. The reaction time of 7 days however was necessary for the completion of the reaction. The
duration of ultrasonic irradiation between 1 and 5 hours did not exhibit any significant difference on
phase formation of LN according to the XRD results. Comparing to the conventional
ammonothermal reactions, the ultrasonic irradiation may be regarded as a catalyzing factor driving
the reaction to complete at relatively lower temperatures. The application of the as-called
sonocatalyzed ammonothermal concept has therefore been successful.
Every diffraction peak present in the XRD pattern of the as-prepared single phase LN powder
(Fig. 3(d)), could be indexed based on a hexagonal structure in rhombohedral R3c, with refined cell
parameters a = 5.14829(2) and c = 13.8631(4) . These parameters are well consistent with those
obtained from analogous preparative routes [3,4]. The FESEM image of the single phase LN
powder (Fig. 4) revealed a poorly defined cubic morphology of the composing LN particles,
suggesting unfavorable crystal growth under this condition. It is noteworthy that although
increasing temperature and the Li:Nb mole ratio to 2:1 promoted phase formation, these parameters
seemingly worsened the particle morphology. According to the FESEM results, particle sizes of the
single phase LN powder were distributed widely between 80 nm to 2.5 m, with most of the
population distributed within a submicrometer range of 84-500 nm (Fig. 5). These LN particles are
mostly present as large aggregates of up to 18.00 m with an average aggregate size of 10.43 m

40

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based on laser diffraction results. It is essential to note that the observed particle morphology in this
case is similar to those obtained from the hydrothermal analogue [4], but altogether diverse from
those obtained under the similar ammonothermal conditions using a freshly prepared niobic acid
[3].
Fig. 4. Typical FESEM images of the powders
with corresponding XRD patterns shown in (a)
Fig. 2(c) and (b) Fig. 3(d), revealing aggregates
of poorly defined cubic particles of the latter.

Fig. 5. Size distribution of the


composing particles of the
single phase LN powder
measured from FESEM images.

Summary
The activation of the facile and basically one-pot ammonothermal reactions by ultrasonic
irradiation, or as-called sonocatalyzed ammonothermal, has been successfully applied for the
preparation of a single phase LN fine powder, from commercially available Nb2O5 at a relatively
low temperature of 220C without prior niobic acid preparation. The as-prepared LN powders are
composed mostly of large aggregates of rather poorly defined cubic particles, with the primary
particle sizes ranging from submicron to microns. The Li:Nb mole ratio of 2:1 and the NH3(aq)
concentration of 30%w/w, which is the highest concentration available commercially, are the key
factors in determining a single phase formation. Although the large aggregation of the primary
particles and the poor particle morphology are yet a hindrance for this technique, the thriving
application of the sonocatalyzed ammonothermal concept can be regarded as an example of another
unfolding possibility for real practice of this technique in the future.
Acknowledgements
The authors thank the Thailand Research Fund and the Commission for Higher Education for
financial support. Nirawat Thammajak and Yothin Chimupala thank the Young Scientist and
Technologist Program of the National Science and Technology Development Agency and the
Development and Promotion of Science and Technology Talent Project for undergraduate
scholarships.
References
[1]
[2]
[3]
[4]
[5]

C. An, K. Tang, C. Wang, G. Shen, Y. Jin and Y. Qian: Mater. Res. Bull. Vol. 37 (2002), p.
1791.
M. Liu and D. Xue: Mater. Lett. Vol. 59 (2005), p. 2908.
M. Liu, D. Xue and K. Li: J. Alloys Compd. (2006), doi: 10.1016/j.jallcom.2006.03.104.
J. Yu and X. Liu: Mater. Lett. Vol. 61 (2007), p. 355.
G. Bedford and J.H. Thomas: J. Chem. Soc., Faraday Trans. Vol. 68 (1972), p. 2163.

Advanced Materials Research Vols. 55-57 (2008) pp 41-44


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.41

Effectively Doping of Rare Earth Additives in Sol Gel Derived


PZT Ceramics
S. K. Asl1,a and S. K. Asl1,2,b
1
2

Faculty of Mechanical Eng., University of Tabriz, Daneshgah st., Tabriz, Iran

New materials group, Materials and Energy Research Center (MERC), Tehran, Iran
a

khameneh@tabrizu.ac.ir, bKhameneh@merc.ac.ir

Keywords: PZT, Piezoelectric, Microstructure, Sol-gel

Abstract. The PZT-based ceramics with a composition of Pb1.1-sRs (Zr0.53Ti0.47)O3.1+0.5s; s = 0.00


0.02, R= La, Nd, Sm were prepared by conventional mixed-oxide, and sol-gel methods, with
optimal preparation conditions. The microstructural and electrical properties were examined as a
function of the additive content and type then compared. Microstructural and compositional
analyses of the PZT-based ceramics have been carried out using SEM and XRD. Dielectric
properties of the samples were measured with an impedance analyzer. The ferroelectric properties
of the PRZT samples were measured using the frequencies. It showed that the La additive improved
both the dielectric and piezoelectric properties. Using sol gel method decreased saturation point of
PZT. The PRZT with 0.5 mol% La be in optimum condition
Introduction
Lead zirconate titanate (PZT) has the perovskite structure (general formula, AIIBIVO3) with the Asite (Pb2+) occupying the cube-octahedral interstices described by the BO6-site octahedral [1, 2].
PZT ceramic powders have been synthesized by various methods such as solid state reaction,
mechanochemical synthesis, wet chemical routs, sol gel and hydrothermal process [3]. The sol gel
process is a low temperature method to synthesize nano sized ceramic powders and films, which
offers the possibilities to control the morphology and chemical homogeneity. Hirashima,
Chakrabarty, budd synthesized PZT through sol gel techniques [4].
The other way to control the microstructure and properties is using various impurities. The
donor additives like Nb5 +, Sb3+, Nd3+ and La3 make k31 high and Qm, Curie temperature low (soft
piezoelectrics) [2]. From the crystal chemical point of view, it seems that the saturation field of
perovskite-type ferroelectrics decreases with tetragonality of the lattice giving rise. The increase in
k31 at low poling field was also reported that most of the softener additives reduced Curie
temperature. It has been reported that the cause of softening derives from the crystal structure
change toward a cubic system rather than whether the additives are donors or acceptors. As for the
decrease in Qm, it has been suggested that the pinning effect of the oxygen vacancies decreased,
This additives influence on other properties, such as dielectric constant, dielectric loss, elastic
modulus, etc [5]. Rare earth ions are donor type substitutions and are other promising way to
improve properties of PZT ceramics. i.e., Agrawal et al worked on Mechanical, piezoelectric and
dielectric properties of PZT ceramics (Pb0.98M0.02[(Zr0.535Ti0.465)0.995]O3, M=Er, Gd, Eu, Nd, La and
Bi) [6]. In other paper, Shannigrahi et al studied sol gel based PZT ceramics with 8 mol% rare earth
additives [7].In present work, PRZT was made by sol gel method. Its composition varied and the
results were compared with each others.
Experimental procedure
The starting materials were commercially available PbO, ZrO2, TiO2, La2O3, Sb2O3, Nd2O3 (all,
>99.9%, Merck) for solid state method, and trihydrated lead acetate [Pb(CH3COO)2.3H2O]
(analytical grade, nacali tesque), zirconium n-propoxide [Zr(OCH(CH3)2)4] (assay 70% in propanol,
Fluka), Rare earth acetates and tetraisopropyl titanate [Ti(OCH(CH3)2)4] (for synthesis, nacali

42

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tesque) for sol gel method, According to chemical formula Pb1.1-s(Zr0.53Ti0.47)RsO3+s/2 (R=Sm, La,
Nd) ( S= 0.0 - 0.02).
Powders were calcinated in the 550-850 C for 2 h respectively. The mixtures were pressed in to
grain pellets and sintered at 1250 C for 2 h. The ceramics were subsequently examined by room
temperature X-ray diffraction (XRD; SIEMENS D500), using CuK radiation, to identify phase
formation and crystalline parameters. The density of PRZT samples was measured by using
Archimedes method. The mean grain size was obtained from the observation of the SEM by the line
intercept method. The dielectric property of the sintered samples was measured using impedance
analyzer. The value of kp, planar coupling factor, be determined via the resonance and
antiresonance method by measuring the frequencies corresponding to the minimum and maximum
impedance of the sample, kp=(1.265(fa2-fr2)/fa2) ,where fr and fa are resonance frequency and
antiresonance frequency, respectively.
Results and discussion
The crystalline size, relative phase's intensity (internal standard), and lattice parameters of powders
that are driven from XRD patterns are given in Table 1. The sol gel powder contains of broadened
peaks, indicating reduction in crystallite size and some pyrochlore and lead oxide phases. In
conventional powder with higher calcination temperature, crystalline size and lead loss increase but
additives inhibit crystal growth. The XRD patterns of PLZT samples (sol gel) have no secondary
phase even in high content, it has extended solid solution. Phase formation occurs in low
temperature, crystalline size reduces, lead loss decreases, and additive substitutes in lattice
effectively.
Table 1. Crystallite parameters for different type and content of additives and calcination
temperature.

Sample Additive Additive Calcination Crystalline Pyrochlore


Lead
c/a
name
type
content temperature
size
phase Int. compounds
( mol%)
(C)
(nm)
(%)
Int.(%)
550
77
5
PZT
1.0181
850
>100
3
PZT
1.0188
La
0.5
550
69
5
PLZT
1.0209
850
>100
1
3
1.0217
1
550
54
4
1.0208
850
>100
1
1.0219
2
550
57
1
5
1.0212
850
>100
1
1.0231
Nd
0.5
550
76
5
P-ZT
1.0213
850
>100
1
4
1.0217
1
550
69
4
1.0221
850
>100
3
1.0229
2
550
68
2
5
1.0218
850
>100
1
2
1.0245
Sm
0.5
550
77
2
5
PSZT
1.0220
850
>100
1
4
1.0238
1
550
78
3
4
1.0238
850
>100
1
2
1.0241
2
550
73
4
4
1.0231
850
>100
3
3
1.0262

Advanced Materials Research Vols. 55-57

43

The behaviour of PNZT (N= Nd2O3) and PSZT (S=Sm2O3) samples is similar to PLZT ( with >1%
La), Substitution of these additives saturated in lower content but exchanged lattice parameters
more than PLZT case, which related to ion radius of additives [8]. By sol gel method, the distance
between ions decrease and the diffusion energy and ways to substitution are more suitable.
The relative density of sintered PRZT samples as a function of additive content is shown in Fig.
1. The sintered density increases with increasing additives initially and peaks at an optimum
content. It can be related to formation of secondary phase as seen in X-ray analyses. Extra lead and
grain size have different effect in sintering mechanism [9]. The main sintering mechanism of PZT
ceramics is lattice diffusion of vacancies that named coble's model [10]. Substituted impurities
introduce new defects to crystal and reduce grain size, so the density increases. After optimum
condition, the impurities form secondary phase, inhibit the mass transport and reduce the density. In
conventional powders, lead losses introduce defects to crystal but additives reduce it and diffusion
path and density. Substitution of La3+(1.22pm) in Pb2+(1.32pm) position done effectively and the
density increased rapidly. The PRZT (R=Sm, Nd) is much less sintering reactivity and exhibits a
much lower sintered density than that of the PLZT ceramic at each temperature and composition.

Fig. 1. A graph of the relative density against additive content and type of PRZT samples
Table 2 shows the relative dielectric constant, coupling factor and grain size of samples depending
on additives concentration and type. For the undoped PZT is about 800; it reaches to 1100 value at
0.5%La- sol gel, this composition with suitable donor ion, un deformed cell, high relative density
and limited secondary phase have the highest dielectric constant [11] For more doping
concentration (0.5-2 mol %), the dielectric constant is not changed clearly. The increases with
doping rare earth ion but its value is less than sol gel samples with the same condition. When Nd,
Sm levels increased, r increased to reach the value of 950, 920 respectively (0.5-1%). Then, the
lattice distorted and secondary phase appeared and the relative density decreased. According to
obeys rules of mixtures [12], the dielectric constant of ceramic is related to its former concentration,
i.e. Pores, piezoelectric and pyrochlore phases, so its constant decreased.
The value of kp for all additives initially increased before declined steadily for higher
concentration. The most outstanding changes caused by soft doping like lanthanides are increases in
piezoelectric coupling coefficient and increases in domain wall mobility [1]. It can be observed in
donor-doped PZT ceramics that the piezoelectric properties are very sensitive to the grain size [11].
Particularly the domain wall mobility and the configuration depend very much on the
microstructure [13]. For very small grains (in high concentration), the density of domains increases
and their mobility is reduced. The pyrochlore phase reduces coupling factor of samples, too.

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Table 2. dielectric constant (RT, 10kHz), Kp electromechanical coupling coefficient and grain
size(m) for sol gel derived PRZT with different additives.
Sample
La-550
Nd-550
Sm-550

0%
800,0.32,7.55,
800,0.32, 7.55
800,0.32,7.55

0.5%
1100,0.45,6.84
950,0.36,7.25
920,0.36,7.19

1%
1130,0.46,4.09
965,0.39, 6.79
890,0.40,6.52

2%
1150,0.46,3.85
955,0.38,6.84
875,0.38, 6.12

Summary
The PRZT ceramics were prepared by conventional and sol gel techniques. The PLZT- sol gel
ceramics exhibit better substitution of additive. Formation of single phase in low temperature, and
controlled grain size and density improved its dielectrical and piezoelectrical properties. It is also
observed that the other rare earth additives that substituted in A- site in crystal lattice increases
continuously piezoelectrical properties in low content (-2%mol). The dielectric constant (room
temperature) initially increases rapidly with additive content. The optimum additive content of sol
gel samples is lower and more effectively than conventional samples with similar condition.
Acknowledgments
The authors wish to thank: Prof. M. Hosaeni, from Mashhad University and Dr. Nemati from SUT
and the I. R. Nano Technology Research Center for their guides and financial support.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]

A.J. Moulson, J.M. Herbert: Electroceramics (Second Ed.,Wiley Press, 2003).


Andrew J. Bell: J. Eur. Ceram. Soc. Vol.28 (2008), p. 1307.
Fu Ping Wang, Yan Ju Yu, Zhao Hua Jiang, Lian Cheng Zhao: Mater. Chem. Phys. Vol. 77
(2002), p.10.
Yuan Deng, Li Liu, Yue Cheng, Ce Wen Nan, Shu Jing Zhao: Mater. Lett. Vol. 57 (2003), p.
1675.
S. Takahashi: Ferroelectrics Vol. 41 (1982), p.143.
Ajai Garg, D.C. Agrawal: Mater. Sci. Eng., B Vol.86 (2001), p.134.
S.R. Shannigrahi, F.E.H. Tay, K. Yao, R. N. P. Choudhary: J. Eur. Ceram. Soc. Vol. 24, Issue
1 (2004), p. 163.
Phanibhusan Roy-Chowdhury, Subhash B. Deshpande: J. Mater. Sci. Vol.22 (1987), p. 2209.
R. E. Newnham, K.R. Udagakumar, S. Trolier in: Chemical Processing of Advanced, edited
by L.L. Hench and J.K. West, John Wiley and Sons Inc., New York, (1992), p.379.
R.B. Atkin, R.M. Fulrath: J. Am. Ceram. Soc., Vol. 54 (5) (1971), p.265.
L. Pdungsap, N. Udomkan, S. Boonyuen, P. Winotai: Sens. Actuators, A Vol. 122 (2005),
p.250.
J.M. Herbert: Ceramic Dielectrics and Capacitors (Gordon and Breach Sci. Pub., 1985).
K.H. Hardtl: J. Am. Ceram. Soc. Vol.64 (1981), p. 283.

Advanced Materials Research Vols. 55-57 (2008) pp 45-48


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.45

Micro- and Macroscopic Observations of the Microtexture,


the Dielectric and Piezoelectric Properties in Bulk and Multilayer
Pb (Zr, Ti)O3
N. Binhayeeniyi1, a, A. Dasaesamoh1, b, J. Khakong2, c, P. Khaenamkaew3, d
and S. Muensit1,4,e
1

Department of Physics, Prince of Songkla University (PSU), Songkhla, Thailand


2

Takuapa Kerekate School, Pungnga, Phunga, Thailand

Faculty of Resources and Environment, Kasetsart University (KU), Si Racha Campus, Chonburi,
Thailand
4

NANOTEC CENTER of Excellence at Prince of Songkla University, Thailand.

nuone44@hotmail.com, bdabeding@gmail.com , cjkingkong@hotmail.com,


d

pkheanumkhaw@hotmail.com, e supasarote.m@psu.ac.th

Keywords: Sol-gel method, piezoelectric, bulk, multilayer, PZT

Abstract: The objective of the present paper is to give an insight of the fundamental properties
strongly depended on the crystallizing phase, grain size, thickness, including stoichiometry of
material. The subject of this work is the lead zirconate titanate [Pb(Zr,Ti)O3, PZT] with its
composition located at the morphotropic phase boundary (MPB) that were prepared by a solid state
method [1] and a conventional sol-gel technique [2,3]. The samples prepared by the first methods
are in a bulk form while the latter the multilayer. The physical property and the dielectric and
piezoelectric properties of the PZT samples have been discussed comparatively when the sample
size decreasing from the bulk to the thin-film scale.
Introduction
The perovskite family comprises the largest class of piezoelectric ceramics that are used in the
transducer technology. Amongst the piezoelectric ceramics, lead zirconate titanate (Pb(Zrx,Ti1-x)O3,
or PZT), has been found widespread use owing to its remarkable piezoelectric properties. The
present work has been interested in the microtexture, the dielectric and piezoelectric properties of
PZT material when its size decreased from the bulk ceramic to the thin film scale. This is to provide
an insight of the key factors controlling the desired characteristics of the PZT material, in particular
in a structure consisting of the PZT thin films, i.e. multilayer PZT which have been extensively
used mainly as actuators, generators, and micropositioners [4]. PZT thin films with homogeneous
and heterogeneous composition have been reviewed in this paper. The composition of interest to be
simultaneously discussed is the composition of x=0.52 which is located at the morphotropic phase
boundary (MPB) separating the rhombohedral and tetragonal structure. This is because large values
for the dielectric constant and the piezoelectric electromechanical coupling factor are usually
observed near this phase boundary [5]
Experimental
Regular solid state process was used for the preparation of the bulk Pb(Zr0.52Ti0.48 )O3 [1]. This is
the starting materials were PbO, ZrO2, and TiO2. Sintering of the pellets was carried out in air
atmosphere at temperatures in a range of 1200-1280 C for 1 h. The PZT film was prepared using
the sol-gel process based on the 2-methoxyethanol route and the Aldrich chemical substances of
zirconium n-propoxide, titanium isopropoxide, and lead-acetate were the starting materials [6]. The
film was elaborated on a commercial substrate from the precursor solution by a spin coater. The

46

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process of depositing the film onto (111) Pt/Ti/SiO2/Si substrate was repeated 5 times before firing
at 600 C for 30 min. Apart from the sol-gel PZT thin films with uniform Zr content, the sample
with continuously change of the Zr content along the thickness of the film were also studied [3]. To
fabricate the graded films, the solutions were spin-coated onto substrates by using the following
sequences: x= 40, x= 52 and x=60 for up-graded 40/52/60 PZT film and the sequence were reversed
for down-graded 60/52/40 PZT film. All samples were X-ray diffraction (XRD) studied to confirm
the perovskite structure. The scanning electron microscope (SEM) was used to observe the grain
size. The relative permittivity (r) measurements were carried out at room temperature in a
frequency rang of 102 to106 Hz using an impedance analyzing method. The piezoelectricity was
macroscopically observed using a Modified Michelson interferometer with a spatial resolution of
10-13 m [7] However, the observation for determining the ferroelectric and piezoelectric properties
are now nanoscale. i.e., the levels of the grain and domain structures. All films mentioned above
were then observed the surface topography using a commercial AFM and PFM measurements were
performed in a commercial setup Multimode. A sinusoidal voltage was passed between the AFM tip
and the back electrode of the PZT sample which is usually held at ground. Details of the
investigation of these films have recently been reported by Khaenamkaew et al. [8].
Results and Discussion
The sintered PZT ceramic has an XRD data confirming a perovskite tetragonal structure [1]. Only
one crystallized phase was observed indicating that the sample has a medium- or fine-grained
texture. The grain size was determined by averaging over the total number of grains in the SEM
micrograph and found to be increased from 0.18 to 0.35 m as the sintering temperature increased
from 1200 to 1280 C. The larger-grained sample however has the higher dielectric constant
(740 for 0.18 m and 830 for 0.35 m, measured at 1 kHz). This is because larger-grained sample
has lower concentration of grain boundaries [9]. A change in grain size is considered to be an
important factor to a change in the dielectric properties for the bulk. The perovskite rhombohedral
phase was observed for the 52/48 PZT thin film [2] while it is either tetragonal or rhombohedral
depending on the deposition sequence of the layers in the graded structure. From Figure 1,
columnar structure in a uniform film was changed to be successive layers in the graded films.
However, average grain size and thickness are respectively about 80-100 nm and a micrometer for
all films. The very fine grains attributed to the high dielectric constant at 1 kHz (1194) (Fig.2a) and
low dielectric loss (0.02). All films have higher dielectric constant than that of the bulk and the
maxima was found in 52/48 film. This indicated that the fine-grained films have diffusion
characteristics between adjacent layers leading to large polarization in the multilayer which in turn
contributed to good dielectric properties.

(a)

(b)

(c)

Figure 1. SEM cross sectional images of (a) uniform (52/48) film, (b) up-graded (40/52/60) film
and (c) planar texture of 52/48 PZT films.
From Fig. 2(b), the piezoelectric coefficient d33 was determined from a slope and the values for the
ceramic, uniform and up-graded films are 198.65, 117.5, and 28.6 pm.V-1, respectively. The peaking
in the d33 coefficient of the 52/48 PZT film is identical to that of the bulk PZT ceramic but the

Advanced Materials Research Vols. 55-57

47

magnitude was considerably smaller. This is due to the unrelaxed stress caused by the substrate
bending existed in the multilayer. Therefore, if the film could be free standing, the d33 value of the
film is supposed to approach to the bulk value. This was analyzed in details and recently reported
by Muensit et al. [7]
1400
uniform film
upgraded film
downgraded film
ceramic

Dieletric constant

1300

1200

1100

1000

900

800

700
102

103

104

frequency (Hz)

(a)

Displacement (pm)

2000

up graded film
uniform film
ceramic

1500

1000

500

0
0

10

12

Applied Voltage (V)

(b)
Figure 2. (a) The dielectric constant of PZT ceramic and 52/48 PZT film,
(40/52/60) and
(60/52/40) PZT films. (b) Variation of surface displacement with applied voltage for ceramic,
uniform and graded films.

(a)
(b)
(c)
(d)
(e)
Figure 3. Texture evaluation of PZT uniform films with various compositions: (a) 70/30, (b) 60/40,
(c) 52/48, (d) 40/60 and (e) 30/70.
The variation of grain size with composition ratios was also observed from the AFM topography as
shown in Fig 3. The PZT films of the other compositions were included for comparison purpose
with the MPB film. The films with higher Ti content have smaller nucleation energy as reflected in
smaller grain size. Domain walls form harder when the grains are getting smaller. The
electromechanical properties become depended on the domain size. Local ferroelectric domain in

48

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the film plane contributed to the piezoelectric response as shown in Fig. 4 [8]. Clearly, the thicker
the film is, the higher the piezoresponse observed in the film.

Figure 4. Local piezoelectric response observed from the 52/48 PZT films (black dot=single
deposition and open dot=ten depositions).
Summary
Fundamental properties of the PZT bulk, single-composition and graded films have been reviewed
comparatively in this work. The grain size of the PZT ceramic is increased with sintering
temperature. For the PZT films, grain sizes increased with increasing Zr content. The dependence
on the grain size of the dielectric constants is clearly observed in the bulk. The piezoelectric
coefficient of the bulk sample is much higher than those of the films. Find-grained PZT films have
superior dielectric properties compared to the PZT ceramics with similar composition. The PZT
films with single composition film have higher piezoelectric response than those of graded films.
This is mainly because of the complex internal stress in the multilayer. The fabrication of the
nanocrystalline thin film with homogeneous compositions and lead-free composition was addressed
in future work.
Acknowledgement
This work is financially supported by PSU Research Grant and the National Nanotechnology Center
(NANOTEC), NSTDA, Ministry of Science and Technology, Thailand, through its program of
Center of Excellence Network at Prince of Songkla University.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

J. Khakong, M.Sc. Thesis (2002) Prince of Songkla University .


P. Khaenamkaew, S. Muensit, I. K. Bdikin, and A. L. Kholkin.: Mater. Chem. Phys. Vol. 102
(2007), p. 159.
P. Khaenamkaew, I. D. Bdikin, A. L. Kholkin, and S. Muensit: J. Ceram. Int. Vol. 34 (2008),
p. 1027.
P. Khaenamkaew, I. K. Bdikin, A. L. Kholkin, and S. Muensit: Songklanakarin J. Sci. Techno.
Vol. 30(1) (2008), p. 59.
P. Muralt, M. Kohli, T. Maeder, A. Kholkin, K. Brooks, N. Setter N, and R. Luthier: Sens
Actuator A, Vol. 48 (1995), p. 157.
B.Jaffe, and R.S Roth: J. Appl. Phys. Vol. 25 (1954), p. 809.
D. S. Budd K.D, Payne D: Br. Ceram. Proc. Vol. 36 (1985), p. 107.
S. Muensit, P.Sukwisut, P. Khaenamkaew and S.B Lang: submitted to Appl. Phys. A: (2008),
in press.
L. B. Kong and J. Ma: Mater Lett, Vol. 51 (2001), p. 95.

Advanced Materials Research Vols. 55-57 (2008) pp 49-52


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.49

Effect of Annealing on the Structure and Dielectric Properties


in PZT-PCoN Ceramics
N. Vittayakorn1,5,a, N. Chaiyo1, R. Muanghlua2, A. Ruangphanit3
and W. C. Vittayakorn4
1

King Mongkuts Institute of Technology Ladkrabang Nanotechnology Research Center(NRC),


King Mongkuts Institute of Technology Ladkrabang, Bangkok, Thailand 10520

Electronics Research Center, Faculty of Engineering, King Mongkuts Institute of Technology


Ladkrabang, Bangkok Thailand 10520

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand 50200

Thai Microelectronics Center (TMEC), National Electronics and Computer Technology Center,
Nation Science and Technology Development Agency, Ministry of Science and Technology,
Chachoengsao 24000, Thailand

Materials Science Research Unit, Department of Chemistry, Faculty of Science, King Mongkuts
Institute of Technology Ladkrabang, Bangkok, Thailand 10520
a

e-mail: naratipcmu@yahoo.com

Keyword: Ferroelectric Materials, Lead Zirconate Titanate, Lead Cobolt Niobate

Abstract The solid solution between the normal ferroelectric Pb(Zr1/2Ti1/2)O3 (PZT) and relaxor
ferroelectric Pb(Co1/3Nb2/3)O3 (PCoN) was synthesized by the solid state reaction method. Sintered
PZT-PCoN ceramics were annealed at temperatures ranging from 850 to 1,100C for 4 h. X-ray
diffraction patterns revealed changes of crystalline structure after annealing, which could be
correlated to the accompanied changes in dielectric properties. Furthermore, significant
improvements in the dielectric responses were observed in this system. After annealing, a huge
increase of up to 200% occurred in the dielectric constants, especially near the temperature of
maximum dielectric constant.
Introduction
Piezoelectric lead zirconate titanate (PZT) ceramic material has been widely used for transducer
applications, due to its excellent piezoelectric properties, and was a candidate in a number of recent
investigations [1, 2]. It is well known that PZT material is almost always used with a dopent,
modifier or other chemical constituents to improve and optimize its basic properties for a particular
application [1, 3]. Lead zirconate titanate ceramics and their solid solution, along with several
complex perovskite oxides represented by Pb(BB)O3, have been investigated [4-6]. Among the
various complex ferroelectric oxide materials, several niobates with transition temperatures below
room temperature are Pb(Mg1/3Nb2/3)O3, Pb(Ni1/3Nb2/3)O3, and Pb(Co1/3Nb2/3)O3. Among them, lead
cobalt niobate [Pb(Co1/3Nb2/3)O3 (PCoN)] is also a typical ferroelectric relaxor material with a
transition temperature of -70C, as reported by Smolenskii et al. [7] in 1958 . In this compound, the
octahedral sites of the crystal are occupied randomly by Co2+ and Nb5+ ions. Recently, our previous
work has shown promise in producing phase pure perovskite PZTPCoN ceramics with the solid
state reaction method [5, 8]. A morphotropic phase boundary (MPB) between the PCoN-rich
pseudo-cubic
phase
and
the
PZT-rich
tetragonal
phase
was
reported
at
0.7Pb(Zr1/2Ti1/2)O3:0.3Pb(Co1/3Nb2/3)O3 [5].
In this study, we emphasized the effect of annealing on the crystal structure, and dielectric
properties in PZTPCoN ceramics. Based on our previous results for the PZTPCoN system, PZT
containing 30 mol% of PCoN was selected as the starting composition, which is close to the
rhombohedral MPB in this system. For annealing, the samples were heat treated at 850-1,100C for

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4 hours in a sealed Al2O3 crucible, with PbO-rich atmosphere. This paper reports evolution of the
perovskite phase, and crystal structure of the PZTPCoN ceramics. Next, the temperature and
frequency dependence of the dielectric constant are given for as-sintered and annealed samples. The
results of influence on the post-sintering annealing of these properties are shown in brief.
Experiment
The 0.7Pb(Zr1/2Ti1/2)O3-0.3Pb(Co1/3Nb2/3)O3 ceramics were prepared by conventionally mixed
oxide processing, in which stoichiometric mixtures of reagent-grade metal oxide powders of
99% + purity (PbO, CoO, TiO2, ZrO2 and Nb2O5) were used as the starting raw materials. Thermal
synthesis of blended and pressed mixture of the starting material was carried out at 900oC for a
period of 4 h. Crumbled, milled and sieved material was pressed again in the form of cylinders and
then sintered at 1,100oC for 4 h. The sintered pellets were then annealed at various temperatures
from 850 to 1,100C for 4 h. These annealing processes were performed in a double crucible, with
interior PbO + ZrO2 atmosphere, in order to maintain the established composition and, especially,
avoid the loss of PbO caused by its sublimation. The Archimedes displacement method with
distilled water was employed to evaluate sample density. The ceramic pellets were ground and
polished to make parallel surfaces, and densities were determined geometrically. After gold
sputtering onto the major faces of the pellets as electrodes, dielectric constants and losses at the
frequency decades of 10 kHz were measured, using a computer-interfaced LCR meter.
Results and Discussions
The phase development in the annealed samples was analyzed by XRD and the results are presented
in Figure 1. All samples show a single-phase powder diffraction pattern. No secondary reaction
phases such as PbO, Pb-based compounds, unreacted oxide and so on, are observed in the pattern.

Figure 1 (a) XRD patterns of 0.7PZT-0.3PZN annealed samples at various temperatures for 4 h,
(b) XRD pattern of the (1 1 1) peak, (c) XRD pattern of the (2 0 0) peak.
After annealing, a significant change in the crystal structure was observed, especially above an
annealing temperature of 1,000oC, where the crystal structure changes from pseudo-cubic to
tetragonal and rhombohedral. On the basis of XRD and dielectric experiments, we have identified
the MPB in the (1 x)PZTxPCoN system from our previous work. The MPB resides at around x ~
0.2, separating the tetragonal phase for x 0.2 from the rhombohedral phase for x 0.3. In this
study, the XRD data show that splitting of the (200) and (111) peak is not observed in ceramic

Advanced Materials Research Vols. 55-57

51

samples annealed at temperatures below 1,000oC. These results indicated that the major phase in
this ceramic sample had pseudo-cubic symmetry. Splitting of the (200) peak becomes more
pronounced as the annealing temperature approaches 1,100oC, thus indicating stabilization of the
tetragonal phase. Furthermore, the unambiguous splitting of the (111) peak indicated the
coexistence of the rhombohedral and tetragonal phase. The co-existence of the tetragonal and
rhombohedral phase is seen clearly when the XRD profile peak splits with increasing annealing
temperature. From these results, it is clear that the composition of the annealed sample has shifted
very closely to the MPB.

Figure 2 Variation of the dielectric constant (r) and loss tangent (tan ) with different annealing
temperatures at 10 kHz.

(a)

(b)

Figure 3 SEM photographs of 0.7PZT-0.3PCoN ceramics (a) as-sintered samples (b) annealing at
1,100oC.
Figure 2 shows the dielectric constant (r) at 10 kHz versus the temperature for 0.7PZT-0.3PCoN
ceramics annealed at different temperatures for 4 h. After annealing, a significant improvement in
the dielectric constant was observed, especially near the temperature of the maximum dielectric
constant (m), where the improvement was up to 200%. This change in behavior might be due to a
shift in a chemical composition close to the MPB, caused by thermal annealing. This behavior is
consistent with the conclusions of Randall et al. [9]and Leite et al. [10] in the PMNPT system.
Figure 3 shows scanning electron microscopy (SEM) images of the fractured surfaces of 0.7PZT-

52

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0.3PCoN ceramics before and after annealing at 1,100oC. There was no change in the grain size.
The density of the samples decreased from 8.120 to 8.015 g/cm3 after annealing at 1,100C for 4 h.
Obviously, the decrease in density did not lead to an improvement of electrical responses.
Summary
The dielectric properties of 0.7PZT0.3PCoN ceramics, formed via the solid state reaction, were
investigated. Thermal annealing was seen to be effective at improving the dielectric and
piezoelectric responses of PZT-based ferroelectric ceramics. The annealing time was found to have
an effect on the electrical properties. After annealing at 1,100C for 4h in a PbO-rich atmosphere,
0.7PZT0.3PCoN ceramics with m 14,400 were achieved in this study. The large improvements in
dielectric properties after annealing were attributed to a shift in the phase composition to the MPB
composition.
Acknowledgements
This work was supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), Thailand Graduate Institute of Science and Technology (TGIST), National
Research Council of Thailand (NRCT) and King Mongkuts Institute of Technology Ladkrabang
(KMITL).
References
[1]
[2]
[3]
[4]

G. H. Haertling: J. Am. Ceram. Soc. Vol. 82 (1999), p. 797.


K. Uchino: Ferroelectric Devices (Marcel Dekker,Inc., New York, 2000)
K. Uchino: Solid State Ionics Vol. 108 (1998), p. 43.
N. Vittayakorn, G. Rujijanagul, X. Tan, M. A. Marquardt and D. P. Cann: J. Appl. Phys. Vol.
96 (2004), p. 5103.
[5] N. Vittayakorn and T. Tunkasiri: Phys. Scr. Vol. T129 (2007), p. 199.
[6] N. Vittayakorn, G. Rujijanagul, X. Tan, H. He, M. A. Marquardt and D. P. Cann, J.
Electroceramic Vol. 16 (2006), p. 141.
[7] G. A. Smolenskii and A. L. Agranovskaya: Sov. Phys.-Tech. Phys. (1958), p. 1380.
[8] N. Vittayakorn, S. Wirunchit, S. Traisak, R. Yimnirun and G. Rujijanagul: Curr. Appl Phys.
Vol. 8 (2008), p. 128.
[9] C. A. Randall, A. D. Hilton, D. J. Barber and T. R. Shrout: J. Mater. Res. Vol. 8 (1993), p.
880.
[10] E. R. Leite, A. M. Scotch, A. Khan, T. Li, H. M. Chan, M. P. Harmer, S.-F. Liu and S.-E.
Park: J. Am. Ceram. Soc. Vol. 85 (2002), p. 3018.

Advanced Materials Research Vols. 55-57 (2008) pp 53-56


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.53

Phase Evolution and Physical Properties of (1-x)BZT-xBFN


Ceramic System
H. Maimon a, S. Eitssayeam b, U. Intatha a*,
T. Tunkasiri b and G. Satittada a
a
b

School of Science, Mae Fah Luang University, Chiang Rai 57000, Thailand

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
* i_uraiwan@yahoo.com

Keywords: phase formation, physical properties, lead free ferroelectric, BZT, BFN

Abstract. Phase evolution and physical properties of (1-x)BZTxBFN ceramic system were
investigated to find the optimum condition for electronic applications. (1-x)BZTxBFN powders
were prepared by solid state reaction technique varying x from 0.2 to 0.8 and various sintering
temperatures from 1350 C to 1450 C. Phase formation was investigated by X-ray diffraction
technique. The XRD analysis demonstrated that with increasing BFN content in (1x)BZTxBFN,
the structural change occurred from the tetragonal to the cubic phase at room temperature. Changes in
the physical and mechanical properties were then related to this structural transformation depending
on the BFN content.
Introduction
BaTiO3 is the most widely used ferroelectric materials. It is the most important material for multilayer
ceramic dielectric. [1] However, the relative permittivity of BT is rather low (1700) at room
temperature. [2] Many researchers have added some ions such as Fe, Ti, Zr, Nb and Mn to increase
the dielectric constant and decrease the Curie temperature of the material. [3-6] BaTiO3 is known to
have a large electromechanical coupling factor. Substitution of Ti4+ with Zr4+ exhibits several
interesting features in the dielectric behavior of BaTiO3 ceramics. When the Zr content is less than 10
mol%, the BZT ceramics show normal ferroelectric behavior and dielectric anomalies corresponding
to cubic to tetragonal (Tc), tetragonal to orthorhombic (T2), and orthorhombic to rhombohedral (T3)
phase transitions. [7, 8] The relaxor ferroelectric barium iron niobate: BaFe0.5Nb0.5O3 (BFN) was
first synthesized via solid state reaction, by Saha and Sinha [4] in 2002. They reported that the
material exhibited very high values of dielectric constant in a very wide temperature range.
In spite of the evident effect of the BFN on the BZT by solid state reaction, the phase evolution
and physical properties of dense ceramic bodies of materials obtained by the solid state reaction are
not clearly understood. Therefore, we decided to prepare (1x)BZTxBFN (x = 0.2 to 0.8) powders
and subjected the sintered ceramics to an extensive characterization and microstructure.
Experimental
(1-x)BZT-xBFN ceramics were prepared by two state mixed oxide method. Both BaFe0.5Nb0.5O3
and BaZr0.1Ti0.9O3 are separately prepared by solid state reaction from high-purity starting materials
(for BFN using BaCO3, Fe2O3, and Nb2O5 and for BZT using BaCO3, TiO2, and ZrO2). The starting
materials were weighed to give the desired stoichiometric composition, suspended in ethanol and
intimately mixed in a milling machine for 24 hours using zirconia grinding media. After drying for
2 h, the powder was ground and calcined in closed alumina crucibles. The calcination conditions
were 1200C, dwell time of 2 h with heating/cooling rate of 5C/min. Phase formation in the
samples was monitored by X-ray diffraction (XRD: XPert-pro Panalysis) with CuK radiation.
The calcinated powders of BFN and BZT were weighed and wet-mixed again using the following in
(1-x)BZT-xBFN composition with x = 0.2, 0.4, 0.6 and 0.8.The calcined powder was uniaxially

54

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pressed into15 mm dia pellets at a pressure of 287 MPa. These discs were sintered in air at different
temperature (1350, 1400 and 1450C) with a dwell time of 3 h and a heating/cooling rate of
5C/min. The densities of the sintered samples were determined using Archimedes principle and
the phases present were identified using an XRD diffractometer (XPert-pro Panalysis). The
microstructures were observed using a scanning electron microscope (LEO 1450VP). The sintered
samples were polished to obtain parallel surfaces. The hardness property was measured under the
load at 50 g, using vicker microhardness tester (Microhardness; Matsuzawa, MMT-3).
Results and Discussion
The densities of the (1-x)BZT-xBFN ceramics sintered under various temperatures are shown in Fig.
1(a) and ranging between 5.75 6.24 g/cm3. The concentration of the BFN content strongly
influences the density, the density of the (1-x)BZT-xBFN ceramics was increasing with sintering
temperature and BFN content. The maximum value of density was obtained in a sample containing
0.2BZT-0.8BFN sintered at 1450C. By comparison, the theoretical densities of BZT and BFN are
approximately 6.05 and 6.51 g/cm3. The hardness of xBFN-(1-x)BZT ceramics are shown in Fig 1(b).
Hardness of ceramics had the same trend of density. Hardness was increasing with BFN content and
increasing sintering temperature. The maximum hardness of xBFN-(1-x)BZT ceramic was 1043.52
HV in 0.2BZT-0.8BFN ceramic sintered at 1450 C).

(a)

(b)

Figure 1. (a) dependence of density in (1-x)BZT-xBFN ceramics and (b) dependence of hardness in
(1-x)BZT-xBFN ceramics with various sintering temperatures.
Figure 2 shows the X-ray diffractograms of the highest density ceramics of each composition. The
results indicated that change of crystal structure occurred as a function of (1-x)BZT-xBFN
compositions. All ceramics composition were crystallized into a perovskites structure. Mixed
tetragonal and cubic phases began to occur at x = 0.2 and completely transforms to paraelectric
cubic phase when x 0.8, as can be seen from the extended XRD patterns of (011) peaks. Similar
result was also found by Eitssayeam et al. [9] who studied the (1x)BZTxBFN. Neither BFN nor
other impurities were detected.

Advanced Materials Research Vols. 55-57

55

Figure 2. XRD patterns of (1-x)BZT-xBFN ceramics.

(a)

(b)

(c)

(d)

Figure 3. SEM micrographs of (a) 0.8BZT-0.2BFN ceramic sintered at 1450C, (b) 0.6BZT-0.4BFN
ceramic sintered at 1450C, (c) 0.4BZT-0.6BFN ceramic sintered at 1450C and (d) 0.2BZT-0.8BFN
ceramic sintered at 1400C

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Microstructure development during sintering was investigated by scanning electron microscopy


(SEM). The surface micrographs of selected (1-x)BZT-xBFN ceramics are shown in Fig. 3. The SEM
micrographs of the as-sintered ceramics show a few pores at grain boundaries, but cracks or micro
cracks were not detected. The grain size of (1-x)BZT-xBFN was increasing with BFN content. The
grain size were in a range of 0.5, 07, 1.1 and 1.4 for 0.8BZT-0.2BFN, 0.6BZT-0.4BFN,
0.4BZT-0.6BFN and 0.2BZT-0.8BFN, respectively.
Summary
The effect of BFN on the structure and dielectric of (1x)BZTxBFN system was investigated for
various chemical compositions. The (1x)BZTxBFN (when x = 0.2 to 0.8) ceramics were prepared
by the mixed oxide method. The evolution of the tetragonal phase transformed to a single peak which
indicating cubic symmetry, while optimum sintering temperature was standing at 1450C. They were
identified as a single BZT phase material with a perovskite structure having the symmetry from
tetragonal to cubic when the ratio of BFN increased. Changes in the physical and mechanical
properties were then related to them structural transformation depending on the BFN content.
Acknowledgement
The authors would like to express their sincere thanks to financial support from the Thailand
Research Fund (TRF) and Graduate school and Faculty of Science, Chiang Mai University,
THAILAND.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

Y. Masaru: Jpn. J. Appl. Phys. Vol. 9B (1995), p.5338.


T. Keitaro, H. Kou and H. Yukio: J. Solid State Chem. Vol. 154 (2000), p.591.
I.P. Raevski, S.A. Prosandeev, A.S. Bogatin, M.A. Malitskaya and L. Jastrabik: J. Appl. Phys.
Vol. 93 (2003) p.4130.
S. Saha and T.P. Sinha: J. Phys.: Condens. Matter Vol. 14 (2002), p.249.
The Inorganic Crystal Structure database (ICSD) code 43622.
N. Rama, J.B. Philipp, M. Opel, K. Chandrasekaran, V. Sankaranarayanan, R. Gross and
M.S.R. Rao: J. Appl. Phys., Vol. 95 (2004), p.7528.
D. Hennings and H. Schell: J. Am. Ceram. Soc., Vol. 65 (1982) p.235.
W. Cao, j. Xiong and J. Sun: Mater. Chem. Phys., Vol. 106 (1997) p.338.
S. Eitssayeam, U. Intatha, G. Rujijanagul, K. Pengpat and T. Tunkasiri: Appl. Phys. A., Vol. 83
(2006), p.295.

Advanced Materials Research Vols. 55-57 (2008) pp 57-60


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.57

Relationships Between Processing Parameters and Properties of


PZT Ceramics
C. Puchmark1,a and G. Rujijanagul2,b*
1

Department of Physics, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
a

kungmic2002@yahoo.com, *brujijanagul@yahoo.com

Keywords: Sintering temperature, Dielectric constants, PZT ceramics

Abstract. In present work, lead zirconate titanate (PZT) ceramics, having the composition near
morphotropic phase boundary were prepared by conventional mixed oxide method. The sintering
process was performed at various sintering temperatures ranging from 1100 to 1300 oC. Relationships
between phase and sintering temperature, and phase and structure were reported. An increase
sintering temperature affected the increase in grain size. The grain growth rate was found to have a
linear fit with the phenomenological kinetic grain growth equation. Tetragonal relative fraction
increased with increasing sintering temperature. In addition, dielectric constant at dielectric peak
increased with increasing grain size which consistent with the trend of tetragonality.
Introduction
Lead zirconate titanate (Pb(Zr1-xTix)O3) ceramic is a well known material for various sensors and
actuators because of their excellent electrical properties [1]. The high electrical properties of PZT
ceramic was found for a composition close to the morphotropic phase boundary (MPB). This MPB
is located around PbZrO3:PbTiO3 0.52:0.48 which separates a Ti-rich tetragonal from a Zr-rich
rhombohedral phase [2]. Therefore, PZT and modified PZT for electrical applications are designed
in vicinity of the MPB. It is known that the properties and phase transition of the lead-based
ferroelectric materials are strongly influenced by density, composition, phase, and microstructure
which in turn depend on the method of preparation [3-5]. In case PZT, processing conditions such
as sintering temperature, soaking time, and heating rate was also found to have effect on its
properties [6, 7]. Although the properties of PZT ceramics have been studied in the past, some
relationships between processing and the properties have not been observed. In the present work
properties of the PZT ceramics prepared at different sintering temperature were investigated. Some
relationships between phase, structure and properties of PZT were also reported.
Experimental
PZT ceramics were prepared by mixed oxide method. The starting materials of PbO, ZrO2 and TiO2
were mixed in a ball-mill pot for 24 h with ethyl alcohol and a zirconia ball and calcined at 800oC
for 2 h with heating rate of 5oC/min. The calcined PZT powder was sieved and pressed into a disc
shape and sintered at 1100, 1150, 1200, 1250, and 1300oC for 6 h with heating rate of 5oC/min.
Density of the sintered samples was measured by Archimedes method with distilled water as the
fluid medium. Phase formation of the sintered pellets was determined by X-ray diffraction (XRD).
Microstructures of the sintered samples were examined using a scanning electron microscope
(SEM). For the electrical measurement, the pellets were polished and then the silver past was
applied on both surfaces for making electrode. The dielectric constant ( r ) of the sintered samples
was measured at various temperature ranging from 30 to 425 oC with a heating rate of 3 C/min
using a LCR meter in junction with an environmental chamber.

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Results and Discussion


Fig. 1 shows XRD patterns of PZT ceramics sintered at various sintering conditions (1100 to 1200

C for 6 h with heating rate of 5oC/min). The XRD result revealed that the main phase has a
perovskite structure [8]. Small amounts of other phases were found in the samples sintered at 1250
and 1300 C, as indicated in Fig.1. An existence of other phases may be due to the PbO loss at
higher temperature which made non-stoichiometric composition.

Figure 1. XRD patterns of PZT ceramics at various Figure 2. Tetragonality (c/a) as a function of fraction
sintering temperature ( indicates second phase).
of tetragonalilty and rhombohedral phase.
To study the relation between relative fraction phase and sintering temperature, tetragonal and
rhombohedral phase was identified by an analysis of the peaks in the 2 range 4346o. However,
there was appearance of multi peaks due to the superposition of the tetragonal and rhombohedral
(200) peaks. In order to identify the phase compositions between rhombohedral and tetragonal
phase, the (200) peaks can be fitted using Gaussian equation. Relative fraction of tetragonalilty and
rhombohedral phase was determined. The percentage of relative phases was then calculated by the
following equations: [9]
(1)
and
(2)

where T and R were defined as the tetragonal and rhombohedral phases, respectively. In addition,
tetragonalilty (c/a) was calculated from the position of (200) peaks. Relative fraction of tetragonality
phase was found to increase with increasing sintering temperature. Fig.2 shows the tetragonality as a
function of T(%)/R(%). A linear increase of the tetragonality was observed, indicated that an
increase in tetragonal phase resulted in the increase in tetragonality.

Advanced Materials Research Vols. 55-57

59

Figure 3. Effect of sintering temperature on grain Figure 4. Maximum dielectric constant and sintered
density versus sintering temperature.
growth.
Grain size as a function of sintering temperature is shown in Fig.3. With increasing sintering
temperature, the grains grew and the average grain size exponentially increased. A plot log(Grain
size) as a function the reciprocal of the temperature (1/T) is also shown in Fig. 3. Linear relationship
between log(Grain size) and 1/T was observed. Although, variation in the data was found, the trend
can be well fitted by the phenomenological kinetic grain growth equation [10] expressed as
(3)
where G defines as the average grain size at the time t, k the constant, m the kinetic grain growth
exponent, E the apparent activation energy, R the gas constant, and T is the temperature in Kevin.

Figure 5. Maximum dielectric constant and sintered Figure 6. Maximum dielectric constant as a function of
density versus grain size of selected samples.
c/a.
Plots of dielectric constant versus temperature for PZT ceramics in the inset of Fig. 4, indicated that
the sintering temperature has an effect on the dielectric behavior. Fig. 4 also shows maximum
dielectric constant at dielectric peak(r,max) as a function of sintering temperature. There was an
increase in maximum dielectric constant from 14890 for the 1100 oC sintered sample to 21150 for the
1200 oC sintered sample, followed by reductions for further sintering temperatures. This result can be
well explained by the effect of density in the samples. The values of sintered density as a function of
sintering temperature are also shown in Fig4. It can be seen that the density values of samples sintered

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at 1100 - 1250 oC have not much different. Therefore, the samples sintered at these temperatures were
selected for studying the effect of grain size on some properties. Fig.5 shows a plot of maximum
dielectric constant as a function of grain size. The maximum dielectric constant was found to increase
with increasing the grain size which is consistent with the observation made by previous researchers
[11]. However, we found that the maximum dielectric constant has a relation with the tetragonality,
i.e., lower tetragonality samples gave lower maximum dielectric constant (Fig.6).

Summary
Relationships between processing, phase, microstructure, and properties in PZT ceramics were
investigated. The PZT ceramics were sintered at different sintering temperatures. At high sintering
temperature, some second phase occurred. An increase in tetragonal phase produced an increase in
the relative fraction of tetragonality phase. A plot logG as a function the reciprocal of the sintering
temperature indicated that grain growth rate matched the phenomenological kinetic grain growth
equation. Although the maximum dielectric constant was observed to increase with increasing the
grain size, we found that the maximum dielectric constant has an empirical relation with
tetragonality.

Acknowledgment
This work was supported by The Thailand Research Fund (TRF), National Metal and Materials
Technology Center (MTEC), Commission on Higher Education (CHE) Faculty of Science Chiang
Mai University, and Faculty of Science Naresuan University. The authors would like to thank Prof.
Dr. Tawee Tunkasiri for his help in many facilities.

References
A.J. Moulson and J.M. Herbert: Electroceramics: Materials, Properties, Applications, 2nd
Edition, (John Wiley & Sons Ltd, West Sussex, 2003).
[2] B. Jaffe, W.R. Cook and H. Jaffe, Piezoelectric ceramics (R.A.N. Publishers, 1971).
[3] N. Vittayakorn, G. Rujijanagul, T. Tunkasiri, X. Tan and D.P. Cann: Mater. Sci. Eng., B., Vol.
108(3) (2004), p. 258.
[4] Y. Liou: Ceram. Int., Vol.30(4) (2004), p. 567.
[5] C. Puchmark, S. Sirisomboon, G. Rujijanagul and T. Tunkasiri: Ferroelectrics Letters, Vol.31
(2004), p. 1.
[6] A. Kinsgon and J. Clark: J. Am. Ceram. Soc., Vol. 66(4) (1983), p. 256.
[7] J. Ryu, J. Choi and H. Kim: J. Am. Ceram. Soc., Vol .84(4) (2001), p. 902.
[8] Powder Diffraction File, Card No.33-0784. Joint Committee on Powder Diffraction Standards
(JCPDS) PDF-4, Internation Centre for Diffraction Data (ICDD), 2000.
[9] M. Yoon and H. Jangb: J. Appl. Phys., Vol. 77(8) (1995),p.3991.
[10] S. Zhao1, H. Wu and Q. Sun: Mater. Sci. Eng. B Vol. 123 (2005),p. 203.
[11 ] C. A. Randall, N. Kim, J. Kucera, W. Cao, and T. R. Shrout: J. Am. Ceram. Soc., Vol. 81(3)
(1998) ,p. 677.
[1]

Advanced Materials Research Vols. 55-57 (2008) pp 61-64


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.61

Synthesis of Conducting Polymer Films by


Plasma Polymerization Process
W. Bhanthumnavin*,1,a, P. Kamphiranon2 and B. Paosawatyanyong3
1
2

Organic Synthesis Research Unit, Department of Chemistry,

Program of Petrochemistry and Polymer Science, 3 Department of Physics


Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand
a

worawan.b@chula.ac.th

Keywords: microwave plasma polymerization, polythiophene

Abstract. A microwave (MW) plasma reactor for the synthesis of polythiophene (PTh) thin films as
well as in situ doping during polymerization process has been designed and assembled. Plasma
polymerization parameters were studied. A good MW power was found to be in the range of 150250W. PTh films were characterized by various spectrophotometric methods. IR analyses showed
absorption frequencies of important functional groups. PTh films exhibited UV-Vis spectra
indicative of increased conjugative systems as the MW power increased although at 300 and 380W
partial fragmentation was evident. Surface analysis by SEM revealed a uniformly deposited film
morphology. EDS results were also suggestive of partial fragmentation of the films at high MW
powers. Preliminary conductive measurements revealed that the undoped films exhibit higher
conductivity (3 to 910-5 s.cm-1) than PTh typically prepared from electrochemical methods.
Introduction
Conducting polymers were first synthesized in the 1970s as a novel generation of organic materials
which possess electrical and optical properties similar to those of metals and inorganic
semiconductors, yet display attractive properties associated with polymers. Their light weight, ease
of synthesis, processibility, and resistance against corrosion have led to applications including those
possible to replace metals or semiconductors. Consequently, development of conjugated
polyheterocycles such as polythiophene (PTh) has received more attention. PTh exhibits high
electrical conductivity upon doping and good stability, therefore, potential applications exist.
Examples include sensors, organic light emitting diodes, solar cells, applications requiring photonic
and conductive properties, and polymeric batteries. Traditionally these polymers are synthesized by
chemical or electrochemical polymerization, while an alternative is plasma polymerization.
Advantages of plasma polymerized polymer films have been characterized as high quality with a
high degree of crosslinking and branching.[1,2] Chemical structure of the deposited polymer can be
different from conventional polymers and are dependent on the polymerization parameters. Plasma
generators can be realized by several energy sources such as radio frequency (RF) and microwave
(MW). In this study MW was utilized as an energy source for the synthesis of PTh films.
Experimental and results
Plasma Polymerization. PTh films were deposited on glass substrates by microwave plasma
polymerization method. The schematic diagram of the homemade Microwave Waveguide Plasma
Reactor (MWPR) is shown in Fig.1. Major components of the system are a chamber, a MW
generator, a waveguide, tuner assemblies, and gas handling components. The chamber was made
from stainless steel in a rectangular cavity shape with gas inlet and outlet ports all around. A
domestic MW oven magnetron was utilized to generate MW at a frequency of 2.45 GHz at different
output power. The magnetron was placed inside a grounded metal box in order to prevent the stray

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MW from leaking to the surroundings. A high


high voltage
voltage controller unit, described elsewhere [3],
controller unit
was setup to supply appropriate current to the
Pressure
magnetron and hence control the output MW
Guage
power. In addition, the system also consisted of
3-Stub Turner
Magnetron
a waveguide, a 3-stub tuner, and a plunger in
order to match the impedance of the cavity to
the microwave source at the desirable
Plunger
electromagnetic resonance mode [4]. Gas
handling components comprised of a monomer
Mass
Vacuum
Flow
vessel and a cold trap which is used in
Chamber
Controller
conjunction with a rotary pump to collect
condensation produced from residue monomer.
Cold Trap
Prior to polymerization process, glass
Argon
substrates were cleaned by acetone, methanol
Monomer
and de-ionized water in an ultrasonic bath. At
Vessel
Argon
the beginning, glass substrates were placed
Rotary Pump
inside the chamber which was evacuated to the
base pressure of approximately 0.03 torr. Argon
was then introduced and the microwave was fed
Figure 1. MWPR for polymerization process
into the chamber for a 1-min plasma pretreatment. In this pre-treatment step, the flow
rate of argon (Ar), the pressure and the microwave power were fixed at 5 sccm, 0.97 torr, and 170
W respectively. After the pre-treatment, polymerization was performed using a colorless thiophene
monomer which was fed into the evacuated and pretreated chamber as a vapor by an Ar carrier gas.
PTh film, deposited on the glass substrates, became visible as a brown layer. Polymerization process
was repeated by varying electrical power (150, 250, 300, and 380W) and deposition time (1 and 2
min) while chamber pressure and monomer flow rate were maintained constant and the positions of
the glass substrates were fixed.
In addition to growing PTh films, a preliminary in situ doping by an iodine vapor with an
objective to incorporate dopant molecules into the polymer framework was also carried out for
comparison. Among dopants which exert a significant influence on the transport of electric charges
in polymer, iodine has been one of the most studied in plasma-polymerized films. Conventional
iodine doping involves a placement of the film in an I2-saturated chamber. In plasma-polymerization
method, an alternative is to perform an in situ doping. This is possible due to iodines high vapor
pressure which facilitates the introduction of its vapor in vacuum plasma reactors. This should in
principal lead to a chemically more homogeneous material. Plasma polymerization of 2iodothiophene employing MW [5] or RF [6] offer an alternative means to incorporate iodine into
the films. Conditions for in situ doping of I2 in this work are still yet to be optimized.
Film Characterization. The obtained PTh films were characterized by various spectroscopic
methods. ATR-IR absorption spectra were recorded using a Continuum infrared microscope
attached to a Nicolet 6700 FT-IR spectrophotometer. Spectra of all samples exhibit the following
characteristic peaks: aromatic =CH stretching mode around 3000-3100 cm-1; asymmetric CH
stretching of the alkyl and methylene group around 2950-2920 cm-1; symmetric methylene CH
stretching around 2850 cm-1; symmetric C=C stretching mode around 1450 cm-1; CC stretching of
the thiophene rings around 1370 cm-1. A thorough analysis showed a CH out-of-plane bending at
around 830 cm-1 in the (CH) on the thiophene ring; CH thiophene ring bending at around 780
and 700 cm-1. For comparison purposes, a spectrum of chemically synthesized PTh as well as that of
an in situ iodine-doped plasma-polymerized PTh are also included in Fig. 2. As illustrated, most of
the IR absorption characteristics of the thiophene monomer were retained during plasma

Advanced Materials Research Vols. 55-57

63

polymerization, although the peaks became


broader, which is consistent with the highly
disordered nature of plasma polymers in
general.
Surface morphology and film thickness
were investigated by Scanning Electron
Microscopy (SEM) on a JSM-6480LV
JEOL scanning electron microscope.
Micrographs representing films deposited
at 380W at various reaction times are
depicted in Fig. 3. SEM analysis revealed a
relatively uniformly distributed deposition
of the so-formed polymer films. Longer
deposition time yielded a smoother surface.
It is well documented that an increase in
the power of the plasma source would give
Figure 2. Infrared Absorption spectra of PTh.
rise to enhancement in both the
fragmentation in plasma phase and the ion bombardment on the growing film. This, apparently, can
produce more branching and bring about crosslinking reaction inside the film, producing a denser
film. This is confirmed by illustrated scanning electron micrographs. Nevertheless, the microwave
power should be optimized since at very high power fragmentation of polymeric structure may take
place (vide infra).

(a)

(b)

(c)

(d)

Figure 3. PTh film fabricated at 380W at: (a) 1 min; (b) 1.5 min; (c) 2 min; and (d) 3 min.
Energy-Dispersive X-Ray Spectroscopy (EDS) was also performed to determine elemental
composition of the polymer films. On the average, the carbon to sulfur (C:S) ratio of the deposited
films carried out at high MW power were in the range of 7:1 (300W) up to 17:1 (at 380W). It is
noteworthy that as the MW power increased, the C:S ratio is significantly higher. This is indicative
of a decrease in sulfur content from the main structure. This is highly possible since a more
energetic plasma environment may be experienced by the existing film. Moreover, C-C and C=C
bonds are stronger (290 and 720 kJ mol-1, respectively) than the C-S bond (272 kJ mol-1) [7].
The films were subjected to solid-state UV-Vis spectrophotometric analysis on a UV-2250
Shimadzu spectrophotometer to investigate their optical properties (Fig. 4). It is well known that
highly conjugated -systems usually exhibit absorption at high wavelength maxima (max).
Typically, conjugation length may be preliminarily determined by UV-Vis measurement prior to
further investigation by more sophisticated techniques. In general an increase in -electron
delocalization in wide band states with a reduction in the band gap would be experienced as the
power increased. However, too high of a power can result in fragmentation or decomposition of the
films. Spectra 1 and 2 indicated that undoped MW plasma polymerized PTh (at 150W, 2 min)
possess comparable optical properties as PTh from chemical synthesis. Apparent shifts in max
occurred as the power increased from 150W to 250 W (spectra 2 and 3). However, when the
polymerization was performed at 300W and 380W a trend in decreased wavelength maxima were

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observed (spectra 4 and 5). Apparently, these


values exceeded optimum MW power suitable
for deposition of PTh films, all else being
equal. This is in good agreement with the EDS
data which showed some decomposition of the
film at high MW power.
Preliminary
electrical
conductivity
measurement by a source-measure unit
(HP4140B) revealed that undoped MW
plasma-polymerized PTh showed conductivity
310-5 - 910-5 s.cm-1. This is two orders of
magnitude higher than typical undoped PTh
from electrochemical synthesis ( 310-7 s.cm1
). Optimization of conditions is underway and
will be further reported after thorough
investigations.

Summary

Figure 4. UV-Vis spectra of PTh films


fabricated from MW plasma polymerization in
comparison with a spectrum of material
obtained from chemical synthesis

In summary, PTh films were successfully prepared by MW plasma polymerization process. Surface
analysis indicated well defined films as observed in SEM. It has been demonstrated by UV-VIs
spectroscopic analysis that as MW power increased, films with desirable properties were better
formed. At very high MW powers, however, deterioration of the films began to take place. EDS
data are also supportive of this observation. Preliminary determination of conductivity of the soformed films gave promising indication that under optimized conditions and parameters, in situdoped PTh films will possess highly desirable properties.
Acknowledgment
This work was supported by the National Research Council of Thailand (NRCT).
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

A. Kruse, A. Baalmann, W. Budden and V.Schlett: Surf. Coat. Tech. Vol. 59 (1993), p. 359.
W. Jinggong, K.G. Neoh and E.T. Kang: Thin Solid Films Vol. 446 (2004), p. 205.
B. Paosawatyanyong, K. Honglertsakul and D.K. Reinhard: Solid State Phenom. Vol. 107
(2005), p. 75.
L.G. Meiners and D.B. Alford: Rev. Sci. Instrum. Vol. 57 (1986), p. 164.
A. Kruse, A. Baalmann, W. Budden, V. Schlett and M. Hennecke: Surf. Coatings Technol.
Vol. 59 (1993), p. 359.
M.E. Ryan, A.M. Hynes, S.H. Wheale, J.P.S. Badyal, C. Hardacre and R.M. Ormerod: Chem.
Mater. Vol. 8 (1996), p. 916.
R.C. Weast and M.J. Astle: CRC Handbook of Chemistry and Physics, 63rd ed. (CRC Press,
U.S.A. 1982).

Advanced Materials Research Vols. 55-57 (2008) pp 65-68


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.65

Chemical Synthesis and Characterization of ZnTiO3 Powder Prepared by


the Coprecipitation Oxalate Method
P. Pookmanee1,a, J. Yotasing1,b and S. Phanichphant2,3,c
1

Department of Chemistry, Faculty of Science, Maejo University, Chiang Mai, 50290, Thailand

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200,Thailand
3

NANOTEC Center Excellence at Chiang Mai University, Chiang Mai, 50200, Thailand
a

pusit@mju.ac.th, bjatupoly@yahoo.co.th, csphanichphant@yahoo.com

Keywords: Coprecipitation oxalate method, ZnTiO3

Abstract. Zinc titanate (ZnTiO3) powder was prepared by the coprecipitation oxalate method. Zinc
nitrate and titanium (IV) isopropoxide were used as the starting materials with the mole ratio of
Zn:Ti was 1:1. Oxalic acid and ammonium hydroxide were added into the mixed solution.
Precipitated powder was obtained after the final pH of solution was 5. The fined powder was
washed with deionized water, filtered, dried at 100 oC for 2h, and followed by the calcination at
500, 700 and 900 oC for 2h. The phase of ZnTiO3 powder was studied by X-ray diffraction (XRD).
The morphology was characterized by scanning electron microscopy (SEM). Hexagonal and cubic
phase of ZnTiO3 powder were obtained after calcination at 900 oC. The particle size of ZnTiO3
powder was in the range of 0.1-0.5 m with irregular in shape and agglomerated. The chemical
composition was identified by energy dispersive X-ray spectroscopy (EDXS). The elemental
composition of zinc, titanium and oxygen shows the characteristic X-ray energy values.
Introduction
Fundamental studies concerning the phase diagram and the characterization of the Zn-TiO2 system
have been continuing since 1960s [1,2]. This system is still attracting the attention of researchers
because of its importance in practical applications [3]. With the recent progress of microwave
applications, including mobile telephones and satellite communication system, high-quality
microwave dielectric resonators, capacitors and filters have been developed. Zinc titanates are
promising candidates as dielectric materials for microwave devices and more preferably for lowtemperature cofired ceramics (LTCCs) [4]. It is reported that three compounds exist in the Zn-TiO2
system, including Zn2TiO4 (cubic), ZnTiO3 (hexagonal) and Zn2Ti3O8 (cubic) [5]. Zinc titanate
(ZnTiO3) has an ordered corundum structure, lattice parameters of a- and c-axis are 5.0787 and
13.9271 , respectively [6]. ZnTiO3 powders could be prepared by the solid state method [7],
metalloorganic decomposition (MOD) method [8], a semi-chemical route combined with vigorous
microbeads milling [9] and sol-gel method [10]. But the sol-gel processes are generally complicated
and the reagents used are expensive. In wet chemical processes for preparing highly quality of
powders, better homogeneity, control morphology and smaller particle size are preferred. The
coprecipitation oxalate method was considered to be a promising way to prepare powder for the
ferroelectric materials [11]. In this research, ZnTiO3 powder was prepared by the coprecipitation
oxalate method. The phase transformation was studied by X-ray diffraction (XRD). The
morphology was characterized by the scanning electron microscopy (SEM). The chemical
composition was identified by energy dispersive X-ray spectroscopy (EDXS).
Experimental
ZnTiO3 powder was prepared by the coprecipitation oxalate method. Solution A was prepared by
dissolving Zn(NO3)2.6H2O in deionized water. Solution B was prepared by adding concentrated
NH4OH to TiO(C3H7)4 to form white precipitate Ti(OH)4 which dissolved in 6M HNO3 and 30%
H2O2 to produce TiO2(NO3)2, a reddish brown solution. Solutions A and B were mixed well

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together by using the control temperature water bath with continuous stirring at 30 oC for 10 min in
the mole ratio of Zn:Ti = 1:1. Deionized water containing H2C2O4.2H2O and NH4OH was added to
adjust the pH value of the mixed solution. The white precipitate powder was obtained after
adjusting the final of pH of the solution to 5, then washed, filtered and dried in an oven
(Gallenkamp, England) at 100 oC for 2h. The precipitated powder was calcined at 500-900 oC for
2h. The phase transformation of powder was studied by X-ray diffractometer (modified D500,
SIEMENS, Germany). The phase structure of ZnTiO3 powder was confirmed by using the Joint
Committee on Powder Diffraction Standards (JCPDS) File Card No. 30-0190 [12] and 14-0033
[13]. The morphology was characterized by scanning electron microscope (JSM5410-LV, JEOL,
Japan). The chemical composition was analyzed by the energy dispersive X-ray spectrophotometer
(ISIS300, Oxford).
Results and Discussion
Figure 1 shows the XRD patterns of ZnTiO3 powder prepared by the coprecipitation oxalate method
calined at (a) 500 C (b) 700 C and (c) 900 C for 2h. At lower calcinations temperature, 500 oC
for 2h, the XRD pattern shows a mixture multiphase of ZnO with hexagonal and ZnTiO3 with cubic
structure (Fig. 1. (a)) corresponding to the JCPDS File Card No. 05-0664 [14] and 30-0190 [12],
respectively. At calcinations temperature, 700 oC for 2h, the XRD pattern shows a mixture
multiphase of TiO2 with anatase and ZnTiO3 with cubic structure (Fig. 1. (b)) corresponding to the
JCPDS File Card No. 12-1272 [15] and 30-0190 [12], respectively. At calcinations temperature,
900 oC for 2h, the XRD pattern shows a mixture multiphase of ZnTiO3 with cubic and dominant
ZnTiO3 with hexagonal structure (Fig. 1. (c)) corresponding to the JCPDS File Card No. 30-0190
[12] and 14-0033 [13], respectively. The intensity of ZnTiO3 peaks increased with increased
calcination temperature.

Figure 1. XRD patterns of ZnTiO3 powder prepared by the coprecipitation oxalate method calined
at (a) 500 C (b) 700 C and (c) 900 C for 2h
Figure 2 shows SEM micrographs of ZnTiO3 powder prepared by the coprecipitation oxalate
method calined at (a) 500 C (b) 700 C and (c) 900 C for 2h. The particle size increased as the
calcination temperature increased. The powder consisted of small and soft agglomerate. The SEM
micrograph of powder calcined at 500 C (Fig. 2 (a)) showed the highly agglomerate and irregular

Advanced Materials Research Vols. 55-57

67

particle with 0.1 m. At 700 C, Fig. 2 (b), the particle was agglomerated and become slightly
larger in size 0.3 m. At 900 C, Fig. 2 (c), the particle was agglomerated, fused together and some
grain growth occurred with the average size of 0.5 m. The particle size of powder was smaller than
previously reported from solid state method [7].

(a)

(b)

(c)

Figure 2. SEM micrographs of ZnTiO3 powder prepared by the coprecipitation oxalate method
calined at (a) 500 C (b) 700 C and (c) 900 C for 2h
Figure 3 shows EDXS spectra of ZnTiO3 powder calcined at 900 C for 2h. It was employed to
investigate and indicate composition of powder calcined with the energy dispersive value. The
elemental composition of ZnTiO3 showed the characteristic X-ray energy value as follows: zinc of
L = 1.012 keV, K = 8.630 keV and K = 9.570 keV, titanium of K = 4.508 keV and K = 4.931
keV and oxygen of K = 0.525 keV, respectively.
Intensity

Energy (keV)
Figure 3. EDXS spectra of ZnTiO3 powder prepared by the coprecipitation oxalate method calined
at 900 C for 2h
Summary
Zinc titanate (ZnTiO3) powder was prepared by the coprecipitation oxalate method. Zinc nitrate and
titanium (IV) isopropoxide were used as the starting materials with the mole ratio of Zn:Ti was 1:1.
Hexagonal and cubic phase of ZnTiO3 powder were obtained after calcination at 900 oC. The
particle size of powder was in the range of 0.1-0.5 m with irregular in shape and agglomerate. The
elemental constituents of powder were identified by the energy dispersive value.

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Acknowledgements
The authors would like to thank the financially support from the Department of Chemistry, the
Faculty of Science, Maejo University, Chiang Mai, Thailand. The authors would like to thank Prof.
Dr. Tawee Tunkasiri and Mr. Suwich Chaisupan from Department of Physics, Chiang Mai
University, Chiang Mai, Thailand for the performance of X-ray diffractometer (XRD), Ms.
Passapan Sriwichai from Biotechnology Center, Maejo University, Chiang Mai, Thailand for
scanning electron microscope (SEM) facilities and the National Nanotechnology Center
(NANOTEC), the National Science and Technology Development Agency (NSTDA), Ministry of
Science and Technology, through its program of Center of Excellence Network, Thailand.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]

F.H. Dulin and D.E. Rase: J. Am. Ceram. Soc. Vol. 43 (1960), p. 125
S.F. Bartram and R.A. Slepetys: J. Am. Ceram. Soc. Vol. 44 (1961), p. 493
O. Yamaguchi, M. Morimi, H. Kawabata and K. Shimizu: J. Am. Ceram. Soc. Vol. 70 (1987),
p. c97
H.T. Kim, J.D. Byun and Y. Kim: Mater. Res. Bull. Vol. 33 (1998), p. 963
Y.S. Chang, Y.H. Chang, I.G. Chen, G.J. Chen, Y.L. Chai, S. Wu and T.H. Fang: J. Alloy.
Compd. Vol. 354 (2003), p. 303
H.T. Kim, S. Nahm, J.D. Byun and Y. Kim: J. Am. Ceram. Soc. Vol. 82 (1999), p. 3467
Y.S. Chang, Y.H. Chang, I.G. Chen, G.J. Chen, Y.L. Chai, T.H. Fang and S. Wu: Ceram. Int.
Vol. 30 (2004), p. 2183
Z.X. Chen, A. Derking, W. Koot and M.P. van Dijk: J. Catal. Vol. 161 (1996), p. 730
H.T. Kim, S.H. Kim, S. Nahm, J.D. Byun and Y.H. Kim: J. Am. Ceram. Soc. Vol. 82 (1999),
p. 3043
Y.S. Chang, Y.H. Chang, I.G. Chen, G.J. Chen and Y.L. Chai: J. Cryst. Growth Vol. 243
(2002), p. 319
P. Pookmanee, C. Khantha, and S. Phanichphant: Mater. Sci. Forum Vol. 561-565 (2007), p.
515
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 30-0190
Swarthmore, PA
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 14-0033
Swarthmore, PA
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 05-0664
Swarthmore, PA
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 21-1272
Swarthmore, PA

Advanced Materials Research Vols. 55-57 (2008) pp 69-72


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.69

Dielectric and Piezoelectric Properties of B2O3 and SnO2


Doped Barium Titanate Ceramics
a

N. Tawichai and G. Rujijanagul

Department of Physics, Faculty of Science, Chiang Mai University,


239 Huay Kaew Road, Suthep, Muang, Chiang Mai, Thailand
a

n_tawichai@yahoo.com, rujijanagul@yahoo.com

Keywords: Barium Stannate Titanate, Dielectric Properties, Piezoelectric Properties

Abstract. Boron oxide doped barium stannate titanate ceramics were prepared by a solid-state
reaction method. Properties of the ceramics were investigated. The experimental results showed that
most properties of the ceramics depend on the sintering temperature. The higher relative
permittivity of 13887 with tan 0.034 at 34 C was observed for the samples sintered at 1350 C.
Piezoelectric coefficient (d33) of the samples was found to be in the range of 90 - 115 pC/N.
However, the optimum d33 coefficient was observed for the sample sintered at 1250 C.
Introduction
Lead-based ceramics are widely used in electronic applications due to their superior piezoelectric
and dielectric properties [1]. However, the lead-based ceramics are not environmentally friendly for
their lead oxide toxicity [2]. Therefore, much attention has been paid for lead-free piezoelectric
ceramics for the recent years [3-10]. Barium stannate titanate (BaSnxTi1-xO3) is one of most
interesting lead free materials. The Curie temperature of BaSnxTi1-xO3 (BST) can be controlled for
various applications by varying the stannate molar fraction. BST also exhibits a diffuse phase
transition with no relexor ferroelectric behaviour [4]. It was reported that Ba(Ti0.9Sn0.1)O3; (BST01)
is a high dielectric constant near room temperature [5]. For multilayer capacitor applications,
researchers have focus on decreasing the sintering temperature by adding sintering aids. Many
sintering aids such as LiF, Bi2O3, Nb2O5, Co3O4, ZnO and B2O3 have been suggested for barium
titanate-based ceramics [6-8]. However, properties of BST ceramics doped with B2O3 have not been
studied. In the present work, B2O3-doped BST01 ceramics were fabricated. The effect of sintering
temperature on the properties of B2O3-doped BST01 ceramics was investigates.
Experimental
The present B2O3-doped BST01 samples were prepared by a conventional ceramics fabrication
processes. Commercial powders of BaCO3, SnO2, TiO2, and B2O3 were mixed in a ball-mill for 24 h
with ethylalcohol and zirconia balls. After drying and sieving, the slurry was calcined at 1300 C for
4 h using a heating rate of 5 C/min. The calcined powders were reground by ball milling with 3 wt.
% PVA as the binder. Cylindrical pellets 15 mm in diameter were isostatically pressed at 80 MPa.
The pellets were sintered at 1250 - 1450 C for 2 h using a heating rate of 5 C/min. The density of
the sintered samples was measured by the Archimedes method using distilled water as the fluid
medium. In order to study phase formation, X-ray diffraction analysis (XRD) was performed using
a diffractrometer. Microstructural evolution was examined using scanning electron microscopy
(SEM). The average grain size of the sintered samples was measured by the linear intercept method.
To study the electrical properties, both flat surfaces of the samples were polished and then
electroded with a conducting silver paint. The dielectric constant (r) and dissipation factor (tan) of
the pellet samples were measured at various temperatures ranging from 100 to 180 C with a
heating and cooling rate of 3 C/min using an LCR meter in conjunction with a temperature

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chamber. The piezoelectric coefficient (d33) was measured with a d33 meter (Model PM-3001 d33
Meter) on poled slices.
Results and Discussion

Fig. 1. XRD patterns of B2O3 doped BST01 ceramics.


XRD patterns of 1 wt. % B2O3 doped BST01 ceramics sintered at various sintering temperatures are
shown in Fig. 1. All samples exhibited a pure perovskite structure. All peaks are well matched with
the perovskite structure [9]. The secondary phase was not observed for all samples. The similar
result was reported in ref. 10.

Fig. 2. Density as a function of sintering temperature for B2O3 doped BST01 ceramics.
The values of sintered density as a function of sintering temperature are shown in Fig. 2. The
density increased with increasing sintering temperature up to 1300 C and then decreased for
further sintering temperatures. It is expected that the presence of a B2O3 liquid phase assists
densification during sintering. However, high evaporation of B2O3 at high temperature may result in
a lower final density. SEM micrographs of the ceramics are illustrated in Fig. 3. The porosity levels
in SEM micrographs of the pellet surfaces were consistent with trends in measured density values.
The microstructural analysis revealed that the increase of the sintering temperature enhances the
grain size. Average values of grain size, as measured by the linear intercept method, increased from
26 m for the sample sintered at 1250 C to 30 m for the sample sintered at 1450 C.

Advanced Materials Research Vols. 55-57

(a)

(b)

71

(c)

Fig. 3. SEM photographs of B2O3 doped BST sintered at: (a) 1250 C, (b) 1350 C, (c) 1450 C.

Fig. 4. Dielectric constant and dielectric loss versus temperature for B2O3 doped BST01ceramics.
Fig. 4 shows the dielectric constant (r) as a function of temperature for the samples sintered at
various temperatures. The results revealed that sintering temperature has an effect on the dielectric
properties. There was an increase in peak dielectric constant from 6477 for the sample sintered at
1250 C to 13887 for the sample sintered at 1350 C, followed by reductions for the sample sintered
at 1350 C (Table 1). This trend matches that of the sintered densities, i.e., the higher density
samples gave higher measured dielectric constants. Fig.4 also shows the variation of dielectric loss
as a function of temperature. The dielectric loss of our ceramics was less than 0.02. It was observed
that the transition temperature of the samples is in the range of 34 - 36 C. Although, sintering
temperature has a significant effect on the grain size, but this factor has not influenced on the
transition temperature (Table 1). Change in the piezoelectric constant (d33) values as a function of
the sintering temperature is shown in Table 1. The d33 coefficient was found to be in the range of
90 - 115 pC/N. However, the better d33 coefficient of 115 pC/N was observed for the sample
sintered at 1250 C.
Summary
In the present work, 1 wt.% B2O3-doped BST01 ceramics were fabricated at various sintering
temperatures. Because of the high dielectric peak board and exceptional d33 value, the sintering

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temperature of 1350 C is selected as the sintering condition which has an optimum property of this
system.
Table 1 Electrical properties of B2O3 doped BST01ceramics
Sintering
Tc max
temperature
[C]
[C]

r max

tan

d33
[pC/N]

1250

35.21

6477

0.0134

115

1350

34.15

13887

0.0345

107

1450

36.29

8281

0.0193

90

Acknowledgements
This work was supported by The Thailand Research Fund (TRF), National Metal and Materials
Technology Center (MTEC), Faculty of Science and Graduate School Chiang Mai University, and
Commission on Higher Education (CHE-Ph.D.-SW) Thailand. The authors would like to thank
Prof. Dr. Tawee Tunkasiri for his help in many facilities.
References
[1]

A. J. Moulson and J.M. Herbert: Electroceramics: Materials, Properties, Applications,


(Chapman and Hall, New York 1990).
[2] K. Pengpat, S. Hanphimol, S. Eitssayeam, U. Intatha, G. Rujijanagul and T. Tunkasiri: J.
Electroceram. Vol. 16 (2006), p. 301.
[3] K. Pengpat, P. Jarupoom, P. Kantha, S. Eitssayeam, U. Intatha, G. Rujijanagul and T.
Tunkasiri: Curr. Appl. Phys. Vol. 8 (2008), p. 241.
[4] M. Valant and D. Suvorov: J. Am. Ceram. Soc. Vol. 87 (2004), p. 1222.
[5] Y. L. Tu, J. M. Herbert and S. J. Milne: J. Mater. Sci. Vol. 29 (1994), p. 4152.
[6] C. Ma, X.H. Wang, R.Z. Chen, L.T. Li and Z.L. Gui: Key Eng. Mater. Vol. 336-338 (2007),
p. 83.
[7] D. Prakash, B. P. Sharma, T. R. R. Mohan, and P. Gopalan: J. Solid State Chem. Vol. 155
(2000), p. 86.
[8] S. M. Rhim, S. Hong, H. Bak, and O. K. Kim: J. Am. Ceram. Soc. Vol. 83 (2000), p. 1145.
[9] X. Wei and X. Yao: Mater. Sci. Eng., B Vol. 137 (2007), p.184.
[10] J. Q. Qi, Z. Qing, W. Yongli, W. Yajing, and L. Longtu: Solid State Commun. Vol. 120
(2001), p. 505.

Advanced Materials Research Vols. 55-57 (2008) pp 73-76


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.73

Ferroelectricity of (1-x)(Bi0.5Na0.5)TiO3 xBa(Ti0.95Zr0.05)O3 Solid Solution


Ceramics
N. Sawangwan1,a, J. Tontrakoon2,b, S. Sirisoonthorn3,c and T. Tunkasiri4,d
1,2,4

Department of Physics, Faculty of Science, Chiang Mai University


Chiang Mai, 50200 THAILAND

Nation Metal and Materials Technology Center, 114 Paholyothin Road, Klong 1, Klong Luang,
Pathumthani, 12120 THAILAND
a

netima_s@hotmail.com, bjerapongton@gmail.com, csomnuk@hotmail.com


d
tawee@chiangmai.ac.th

Keyword: (Bi0.5Na0.5TiO3Ba(Ti0.95Zr0.05)O3, Morphotropic phase boundary, Relative permittivity


and Piezoelectric constant

Abstract: (1-x)(Bi0.5Na0.5TiO3)-xBa(Ti0.95Zr0.05)O3 ceramics were prepared by the mixed oxide


technique and their dielectric, piezoelectric and ferroelectric properties determined in detail in the
range x = 0.06 to 0.09. At x = 0.07 the maximum relative permittivity of 1338 and piezoelectric
constant of 167 pC/N were obtained. It was concluded that 0.93(Bi0.5Na0.5TiO3)0.07Ba(Ti0.95Zr0.05)O3 is the morphotropic phase boundary region for this system.
Introduction
The bismuth sodium titanate (BNT)-barium zirconate titanate (BZT) system is possible lead-free
ferroelectric material. The mixture of BNT and BZT was made in order to minimize their individual
disadvantages. BNT is a ferroelectric at room temperature. Above the first phase transition
temperature (Tp = 220o C), the ferroelectric phase changes to the antiferroelectric phase. BNT
ceramics show the strong ferroelectric properties such as a large remanent polarization (Pr = 38
C/cm2). [1-2], but they have two main problems. Firstly, they are not easily poled because of their
high conductivity and thus a high coercive field (Ec = 73 kV/cm) is required [2]. The second
problem is that BNT ceramics are not easily sintered [2]. By contrast, barium zirconate titanate
(BZT) ceramics have no problems associated with poling and are good relaxors with a broad phase
transition [3]. However, BZT ceramics have other drawbacks as they require a high sintering
temperature (1327-1577o C ) and have low Curie temperatures Tc values (about 120o C) which limit
their applications [3-4]. Therefore, it is hoped that a combination of the two compounds, focused
on the morphotropic phase boundary (MPB) region, may improve their properties.
Takenaka et al. [5] studied the ferroelectric properties of (Bi0.5Na0.5TiO3 BaxTiO3 (BNT-BT),
and reported that the MPB composition, showing a superior piezoelectric constant (d33 = 125 pC/N)
and high electromechanical coupling factor (k31 = 19.2% and k33 = 55%) occurred at x = 0.06. In the
BNT-BZT system, Peng et al. [6] studied (1-x)(Bi0.5Na0.5TiO3 xBa(Ti0.945Zr0.058)O3 solid solutions
in the range x = 0.03, 0.06, 0.09 and 0.12 and reported the MPB region occurs at x = 0.09, with a
maximum piezoelectric constant (d33 = 147 pC/N) and highest room-temperature relative
permittivity (r = 881.4). In this work we reexamine the MPB of the (1-x)BNT-xBZT system with a
detailed investigation of the range x = 0.06 to 0.09. Phase analysis, dielectric and piezoelectric
properties of the system are presented in this work.
Experimental
In this study, the raw materials were reagent grade barium carbonate (BaCO3), zirconium oxide
(ZrO2), titanium oxide (TiO2), bismuth oxide (Bi2O3) and sodium carbonate (Na2CO3). The BZT
and BNT powders were prepared separately. The mixed powders were ball milled with zirconia
balls in ethyl alcohol for 24 h and dried in an oven (at about 1000 C). Both mixtures were calcined at

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12000 C for 4 h. and 8500 C for 3 h. in air to form BZT and BNT powders, respectively. The two
resulting powders were weighed in appropriate proportions on the basis of the formula (1-x) BNTxBZT where x = 0.06, 0.07, 0.08 and 0.09. The samples were ball milled again in alcohol for 24 h.
and dried. Disc shaped green compacts were produced by uniaxial cold pressing the powder at 60
MPa and sintered at 11800 C for 3 h. in air at the heating rate of 50 C/min. The sintered samples
were analyzed by x-ray diffraction (XRD). Silver paste was applied on both faces of the samples for
electrical measurements. Evolution of the relative permittivity (r) and dissipation factor (tan) as a
function of temperature was measured up to 4000 C using an LCZ meter (Hewlett Packard 4276A)
operated at 1 kHz. The piezoelectric constants (d33) of the samples were measured using a
Piezoelectric D33 meter (4562114 KCF Technologies) samples after polarization in silicone oil at
80o C at 35 kV/cm for 30 min.
Results and discussion
The XRD patterns of ceramic samples are presented in Fig. 1. All the peaks can be attributed to
BZT (tetragonal) and BNT (rhombohedral) phases and their mixtures. It can be seen that the peaks
of BNT and BZT are clearly separated, which is not the case in solid solutions of (1-x)BNT-xBZT
ceramics. The XRD patterns of the samples where x = 0.00, 0.06, 0.07 0.08, 0.09 and 1.00 are
denoted as BNT, BNT-BZT6, BNT-BZT7, BNT-BZT8, BNT-BZT9 and BZT respectively. All the
patterns (x = 0.06-0.09) show splitting of the {200} reflection at 2 = 45o to 47o, indicating that
BZT additions of to 6 mol% lead to splitting of the (200) and (002) peaks.

Fig. 1 X-ray diffraction patterns of


(1-x)BNT-xBZT ceramics, where x
varies from 0.00, 0.06, 0.07, 0.08,
0.09 and 1.00 mol

Fig. 2 Relative permittivity as a function


of temperature for (1-x)BNT-xBZT
where x varies from 0.06-0.09 mol

The relative permittivity as a function of temperature of BNT-BZT6 to BNT-BZT9, is shown in


Fig. 2, indicating that the relative permittivity curves of BNT-BZT6 and BNT-BZT7 show a more
diffuse phase transition than the others. This is caused by a disordered ionic arrangement with
unstable positions of Na+ and Bi3+ that affect the ionic mobility of the A site [7]. This directly
affects the first phase transition (Tp) and Curie temperatures (Tc) of samples BNT-BZT6 and BNTBZT7. Furthermore, a high content of BZT tends to increase Tp and slightly lowers Tc (Table 1), as
expected. Similarly Herabut and Safari [8] showed that the Tc of BNT ceramics decreases with

Advanced Materials Research Vols. 55-57

75

increased content of La2CO3. Inspection of the phase transition temperature and the humps on the
relative permittivity curves suggest that the latter may arise from A site disorder, giving a broad
peak of relative permittivity and making it difficult to identify the Tc point. The values of these are
shown in Table 1 and 2.

Fig. 3 The relationship between relative permittivity and piezoelectric constant of (1-x)BNT-xBZT
ceramics where x = 0.06-0.09 mol
Fig. 3 presents the piezoelectric constants (d33) and relative permittivities (r) at room temperature
of (1-x)BNT-xBZT ceramics plotted as a function of BZT content. The maximum value of d33 (167
pC/N) was found in BNT-BZT7, while the r values showed a similar trend with a corresponding
maximum value of 1338. These results are shown in Table 2. Furthermore, an increase in BZT
content of more than 7 mol% decreases both d33 and r, suggesting that the MPB in the BNT-BZT
system may be around BNT-BZT7.

Table 1. Comparison of the dielectric properties of (1-x)(Bi0.5Na0.5)TiO3-xBa(Ti0.95Zr0.05)O3 and


(Bi0.5Na0.5)(1-1.5x)LaxTiO3 ceramics at Curie temperature.
conditions
BNT-BZT6
BNT-BZT7
BNT-BZT8
BNT-BZT9
BNLT [8]
BNLT2 [8]

Tp (o C)
112
107
130
151
-

Tc (o C)
270
270
259
252
345
335

r
5568
7285
7242
7928
550
495

tan (%)
1.10
0.90
0.81
0.97
4.00
3.30

Table 2. Comparison of the dielectric and piezoelectric properties of (1-x)(Bi0.5Na0.5)TiO3xBa(Ti0.95Zr0.05)O3 and (Bi0.5Na0.5)(1-1.5x)LaxTiO3 ceramics at room temperature (250 C).
conditions
BNT-BZT6
BNT-BZT7
BNT-BZT8
BNT-BZT9
BNLT [8]
BNLT2 [8]

r
672
1338
1123
1098
~ 750
-

tan (%)
6.77
6.83
7.05
7.28
~ 5.50
-

d33 (pC/N)
145
167
163
154
91
89

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Summary
The addition of BZT strongly affects the dielectric, piezoelectric, ferroelectric properties and
microstructure of BNT-based ceramics. The diffuse phase of the BZT-BNT system can reduce the
external electric field required for poling from 73 kV/cm to 35 kV/cm. A BZT content greater than
7 mol% was found to decrease the Curie temperature Tc, the relative permittivity at room
temperature and the piezoelectric constants, but increases the first phase transition temperature Tp.
Moreover, the maximum values of relative permittivity at room temperature, the piezoelectric
constant (1338 and 167 pC/N, respectively) were obtained in the BNT-BZT7 composition. These
results suggest that the MPB region could be at about the BNT-BZT7 composition.
Acknowledgement
The authors would like to express their sincere thanks to Financial support from the Thailand
Research Fund through the Royal Golden Jubilee Ph.D. Program to students initial and advisors
initial, Ministry of University Affairs, Graduate school and Faculty of Science, Chiang Mai
University, THAILAND and National Metal and Materials Technology Center, THAILAND.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

H. Nagata and T. Takenaka: J. Eu. Ceram. Soc. Vol. 21 (2001), p. 1299.


S. Kuharuangrong: J. Mater. Sci. Vol. 36 (2001), p. 1727.
C. Hofer, R. Meyer, U. Bttger and R. Waser: J. Eu. Ceram. Soc. Vol. 24 (2004), p. 1473.
Z. Yu, R. Guo and A.S. Bhalla: J. Appl. Phys. Vol. 88 (2000), p. 410.
T. Takenaka, K.I. Maruyama and E. otsuki: Jpn. J. Appl. Phys. Vol. 30 (1991), p. 2236.
C. Peng, J.F. Li and W. Gong: Mater. Lett. Vol. 59 (2005), p. 1576.
S. Kuharuangrong and W. Schulze: J. Am. Ceram. Soc. Vol. 79 (1996), p. 1273.
A. Herabut and A. Safari: J. Am. Ceram. Soc. Vol. 80 (1997), p. 2954.

Advanced Materials Research Vols. 55-57 (2008) pp 77-80


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.77

Effect of Calcination Temperature on Phase and Morphology of Sol-gel


Derived PZTN Powders
C. Sangsubuna, A. Watcharapasornb and S. Jiansirisomboonc
Department of physics, Faculty of science, Chiang Mai University, Chiang Mai 50200, Thailand
a

csangsubun@hotmail.com, banucha@stanfordalumni.org, csukanda@chiangmai.ac.th

Keywords: PZT, triol-sol-gel, dopant, phase, powder morphology

Abstract. Niobium doped PZT (PZTN) powder was prepared by a triol-sol-gel method from a
mixture of lead (II) acetate trihydrate, 1,1,1-tris (hydroxymethyl), acetylacetone, titanium (IV)
isopropoxide, zirconium (IV) propoxide and niobium (V) ethoxide and calcined at temperature
ranging from 300-600oC for 2 h and 600oC for 4 h with a heating/cooling rate of 5oC/min. Thermal
characteristics of the PZTN powders were studied using thermogravimetric/differential thermal
analyses (TG/DTA). Phase formation in the powder was determined using X-ray diffraction
analysis (XRD). Morphology of the PZTN powder was investigated by a scanning electron
microscopy (SEM) and transmission electron microscopy (TEM). High purity perovskite structure
of PZTN powder with a rhombohedral structure and a crystallite size 38 nm was obtained at the
temperature of 600oC for 4 h dwell time. Well separated particles with uniform particle size
distribution within 10-50 nm were also observed by TEM.
Introduction
Lead zirconate titanate (Pb(Zr0.52Ti0.48)O3) is a piezoelectric ceramic widely used in transducers,
ferroelectric memories and actuators. The ferroelectric PZT has interesting physical properties when
its composition is close to the morphotropic phase boundary (MPB), i.e. between the tetragonal and
rhombohedral regions of the phase diagram, and in this region the material also exhibits outstanding
electromechanical properties [1]. In addition, the structural and electrical properties of PZT can be
modified by a substitution of various dopants, such as Bi, La, Nd, Ta, Nb, Sb etc. Nb is one of the
most importanting dopants which can alter properties of PZT ceramics. A significant increase in
dielectric constant and piezoelectric coefficients was observed in PZT with small amount of Nb
content (~2 wt%) [2, 3]. Jaffe et al. [4] have also reported that 1 wt% Nb-doped PZT caused an
abrupt increase in dielectric constant from 730 to 1700 and the piezoelectric coefficient from 223 to
374 pC/N.
Recently, PZT ceramics and thin films fabricated by sol-gel processes have attracted wide
interest because of high purity and precise compositional control. Moreover, sol-gel method can
produce rather reactive PZT nano-powders at low temperature (600C) which then give rise to the
ceramics with good compositional and structural homogeneity [5]. The most common method for
sol-gel synthesis involves hydrolysis and condensation of metal alkoxides with different modifiers
including methoxylethanol [6], acetic acid [7], and acetlyacetone [8]. Milne et al [9] devised a solgel process in which , -dihydroxyalkanes (diol) were introduced into the solution. Subsequently,
a triol route was introduced by Milne et al. [10] in which 1,1,1-trishydroxymethl (triol) was used as
a solvent. It has been reported that the triol route offered a number of processing advantages over
the diol route. In this research, Pb0.99(Zr0.52Ti0.48)0.98Nb0.02O3 powder was prepared by a triol solgel
route. Preliminary studies on phase formation and transition temperature of as-synthesized powder
were carried out. Microstructure, phase development and thermal behavior of PZTN powders
calcined at different temperatures were reported and discussed.

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Experimental
Firstly, Pb0.99(Zr0.52Ti0.48)0.98Nb0.02O3 (PZTN) sol was prepared using a triol sol-gel route. The
starting materials were zirconium (IV) propoxide (70%, Aldrich), niobium (V) ethoxide (99.95%,
Aldrich), and acetylacetone (99%, Fluka) in a dry nitrogen atmosphere. The mixture was refluxed in
an oil bath at 90C for 2 h. The solution was then cooled down to room temperature before adding
titanium (IV) isopropoxide (99%, Aldrich), lead (II) acetate trihydrate (99%, Riedel) and 1,1,1- tris
(hydroxymethyl) ethane (99%, Aldrich) into the solution. The mixture was subsequently heated at
70C for 4 h. The final product was a viscous golden solution, so called a sol. After the resulting sol
was dried at 120C for 24 h, the powders were formed and then were subjected to a calcination
process at various temperatures between 300-600C for 2 h and 600oC for 4 h with a
heating/cooling rate of 5oC/min. Thermal characteristics of powders were studied using TG and
DTA. Phase formation was determined using XRD (Phillip Model X-pert) with CuK radiation.
Microstructure and particle size of the PZT powders was investigated using SEM (JEOL JSM6335F) and TEM (JEOL JSM-2010).
Results and discussion
Figure 1 shows TG and DTA curves of as-synthesized PZTN powder. The DTA curve shows an
exothermic peak at ~120C due to a removal of water and/or organic species within micropores of
the gel powder. The exothermic peak at ~380oC was likely caused by decomposition of organic
groups including the C-H-O bonds as reported earlier [11, 12] which resulted in corresponding
weight loss observed in the TG curve. An exothermic peak at 500C correlated to the reaction phase
transition of PZTN, corresponding to the starting point of flat region in TG curve. The result of
XRD patterns of as-synthesized and calcined PZTN powders are shown in Fig. 2, at temperature up
to 300C, the powder comprised only amorphous structure which was indicated by the broadened
XRD peak. The amorphous pyroclore phase undergone crystallization at 2 ~ 29 as calcination
temperature increased to 400C. The crystalline perovskite-type structure of rhombohedral PZT
started to form together with the small pyroclore phase when the powder being calcined at 500C
and the reaction seemed complete at 600C. However, increasing the calcination dwell time to 4 h,
the amount of pyroclore phase disappeared, resulting in a single phase perovskite PZTN powder
corresponding to a rhombohedral structure. The crystallite size of PZTN powder calcined at 600C
for 4 h determined from X-ray (d110) line broadening studies using Scherers equation [13] was
found to be ~38 nm.

Figure 1. TG/DTA diagrams of as-synthesized


PZTN powder.

Figure 2. XRD patterns of as-synthesized and


calcined PZTN powders.

Advanced Materials Research Vols. 55-57

79

TEM images and selected area electron diffraction (SAED) patterns of PZTN powders calcined at
400C, 500C for 2 h, and 600C for 4 h are shown in Fig. 3. At calcination temperature of 400C,
the powders seemed to agglomerate which was typical for the amorphous pyrochlore phase. The
corresponding SAED pattern in Fig. 3(a) shows diffuse ring patterns indicating the occurrence of
amorphous pyrochlore phase as reported earlier [14]. This is also in good agreement with the results
of TG/DTA and XRD shown in Fig. 1 and Fig. 2, respectively. TEM micrograph in Fig. 3(b)
showed more separated agglomerates and small particles in the powder after being calcined at
500C, corresponding to SAED shown in Fig. 3(b), which suggested a presence of polycrystalline
particles of PZTN as observed by TG/DTA and XRD. This seemed to indicate a complete
decomposition of residual organic species with well-developed perovskite structure in agreement
with the results reported by Chen et al. [12]. At the calcination temperature of 600C, an increase in
calcination dwell time from 2 h to 4 h showed that the particle partially aggregated into large
agglomerates with irregular shape (Fig. 3(c)). The SAED pattern of this powder indicated discrete
polycrystalline ring pattern. TEM observation in a particular area of the powder calcined at 600C
for 4 h clearly showed individually uniform particles distributed around a large agglomerate. These
small individual particles had average size in the range of 10-50 nm (Fig. 3 (d)). The set of selected
area diffraction patterns shown in Fig. 3(d) also indicated polycrystalline ring patterns
corresponding to a perovskite-type structure of rhombohedral PZT (JCPDS file no.73-2022). The
indexed planes corresponded to those planes detected in XRD pattern.

(b)

a)

(d)

(c)

110
111
121
220

Figure 3. TEM micrographs and selected area diffraction patterns of PZTN powders calcined at
different temperatures; (a) 400C, (b) 500C for 2 h, (c) and (d) 600C for 4 h.

80

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Summary
PZTN nanopowder has been synthesized by a triol solgel route. According to the results of XRD
patterns, the crystallization of the pyroclore phase started to occur in the powder at calcination
temperature of 400C. Increasing the calcination temperature to 500C, crystallization of
rhombohedral PZTN began with a presence of very small amount of pyrochlore phase. However,
increasing the calcination time of 4 h at 600C could produce single phase of perovskite-type
PZTN. Phase formation observed by XRD corresponded well with the results of TG/DTA analysis.
TEM micrographs showed that the uniform particle size in the range 10-50 nm was obtained at
calcination temperature of 600C for 4 h. This research indicated that both a calcination temperature
and dwell time affected phase formation of PZTN powder with optimum calcination condition
reported.
Acknowledgements
This work is supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), the National Nanotechnology Center (NANOTEC) through its program of Center
of Excellence Network and the Faculty of Science, Chiang Mai University. CS would also like to
acknowledge the Graduate School, Chiang Mai University and financial support from the CHE
through Thaksin University, Thailand.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

G. H. Haertling and C. E. Land: J. Am. Ceram. Soc. Vol. 54 (1971), p. 1.


K. Miura and M. Tanaka: J. Appl. Phys. Vol. 36 (1997), p. 226.
D. Dims, R. W. Schwartz and S. J. Lockwood: J. Am. Ceram. Soc. Vol. 77 (1994), p. 3000.
B. Jaffe, W. Cook and H. Jaffe: Piezoelectric Ceramics (Academic Press, London, U.K.
1971).
Z. J. Xu, R. Q. Chu, G. R. Li, X. Shao and Q. R. Yin, Mat. Sci. Eng. B. Vol. 117 (2004), p.
113.
K. D. Budd, S. K. Dey and D. A. Payne: Proc. Brit. Ceram. Soc. Vol. 36 (1985), p. 107.
G. Yi and M. Sayer: J. Sol-Gel. Sci. Tech. Vol. 6 (1996), p. 65.
Y.L. Tu, M.L. Calzada, N. J. Phillips and S. J. Milne: J. Am. Ceram. Soc. Vol. 79 (1996), p.
441.
N. J. Philips, M. L. Calzada and S. J. Milne: J. Non-Cryst. Solids. Vol. 147 (1992), p. 285.
S. J. Milne, R. Kurchania, J. D. Kenedy, M. Naksata, S. Arscott, D. Kaewchinda, N. Sriprang
and R. Miles: Ceram. Trans. Vol. 95 (1999), p. 95.
L. Wu, B. H. Chen, T. Y. Chang, J. L. Huang and C. L. Huag: Jpn. J. Appl. Phys. Vol. 41
(2002), p. 6962.
Y. Z. Chen, J. Ma, L. B. Kong and R. F. Zhang: Mater. Chem. Phys. Vol. 75 (2002), p. 225.
M. P. Klug and L. E. Alexander: X-ray Diffraction Procedure for Polycrystalline and
Amorphous Materials (Wiley, New York. Vol. 635, 1974).
C. K. Kwok and S. B. Desu: Appl. Phys. Lett. Vol. 60(12) (1992), p. 1430.

Advanced Materials Research Vols. 55-57 (2008) pp 81-84


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.81

BaMnTiO3 Synthesized by the Oxalate and Impregnation Methods


P. Pookmanee1,a, P. Ketwong1,b and S. Phanichphant2,3,c
1

Department of Chemistry, Faculty of Science, Maejo University, Chiang Mai, 50290, Thailand
2

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai, 50200,
Thailand
3

NANOTEC Center Excellence at Chiang Mai University, Chiang Mai, 50200, Thailand
a

pusit@mju.ac.th, bpradudnetk@yahoo.co.th, csphanichphant@yahoo.com

Keywords: Oxalate method, impregnation method, BaTiO3, Ba(Mn0.33Ti0.67)O2.84

Abstract. Barium titanate (BaTiO3) was synthesized by the oxalate method with the starting
precursors as barium chloride and potassium titanium oxalate with mole ratio of 1:1. Precipitate was
obtained after adding oxalic acid until the pH of the final solution was 4. The precipitate was milled
and calcined at 700 oC for 2h. Mn-doped barium titanate (BaMnTiO3) was prepared by the
impregnation method. Barium titanate calcined at 700 oC was mixed with 2 and 4 mole % of Mn
from manganese chloride. The mixed powder was calcined at temperatures of 800 oC and 900 oC
for 2h. The phase of BaMnTiO3 was studied by X-ray diffraction (XRD). Hexagonal structure of
Ba(Mn0.33Ti0.67)O2.84 was obtained after calcination at 900 oC for 2h with 2 and 4 mole % of Mn.
The morphology and chemical composition were investigated by scanning electron microscopy
(SEM) and energy dispersive spectroscopy (EDS). The particle size of Ba(Mn0.33Ti0.67)O2.84 powder
was in the range of 50-60 nm with irregular in shape. The elemental composition of barium,
manganese, titanium and oxygen showed the characteristic X-ray energy values.
Introduction
Barium titanate (BaTiO3) has been widely used because of its attractive dielectric and ferroelectric
characteristics. Due to its high dielectric constant and low losses, BaTiO3 represents the basis for
the preparation of multi-layer ceramic capacitors (MLCCs), embedded capacitance in printed circuit
boards (PCB) and thermistors with positive temperature coefficient of resistivity. In recent years,
MLCCs have become smaller in size. To be able to achieve high capacitance in a small size, the
dielectric layer thickness has to be lowered while the total number of active layers increased in the
device [1]. To meet with this demand, BaTiO3 powders with well-crystallized, smaller and more
uniform particle size are required. Several recent methods, such as catecholate [2], sol-gel [3]
hydrothermal [4], and oxalate methods were studied [5]. However, the development of softchemistry routes are a promising alternative for the synthesis of perovskite materials, because they
can be better controlled from the molecular precursor to the final material to give highly pure and
homogeneous materials and allow low reaction temperatures to be used, the size and morphology of
the particles to be controlled. However, during calcination large number of ionized oxygen
vacancies is created. Doping with manganese is one of several ways to reduce the oxygen vacancies
and has been reported to exhibit good photoluminescence properties [6]. Mn-doped BaTiO3
ceramics are mainly used for capacitors and PTCR devices where Mn influences both the electrical
properties and the microstructure [7]. Therefore, doping with Mn into BaTiO3 would reduce the
conductance of BaTiO3 and change the crystallographic structure to the hexagonal phase with the
stabilizing effect from Mn. In this work, it reveals with the preparation of BaMnTiO3 by the oxalate
and impregnation methods. The phase of BaMnTiO3 powder was studied by X-ray diffraction. The
morphology and chemical composition were investigated by scanning electron microscopy (SEM)
and energy dipersive spectrometry (EDS).

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Experimental
Barium titanate (BaTiO3) powder was synthesized by the modified oxalate method. Barium chloride
dihydrate [BaCl2.2H2O], potassium titanium oxalate dihydrate [K2C4O9Ti.2H2O] and oxalic acid
dihydrate [(COOH)2.2H2O] were used as the starting precursors. BaCl2.2H2O solution was added to
K2C4O9Ti.2H2O solution with mole ratio of 1:1. Deionized water containing (COOH)2.2H2O was
added to adjust the pH value of the solution. The white precipitate powder was obtained by
adjusting the final pH of solution to 4, then filtered, washed and dried in an oven (Gallenkamp,
England) at 80 oC for 12h. The milled precipitate was calcined in the muffle furnace (Inter Kilns,
Thailand) at 700 oC for 2h. Mn doped barium titanate (BaMnTiO3) was prepared with 2 and 4 mole
% of Mn using manganese chloride tetrahydrate [MnCl2.4H2O]. The ground-mixed powder was
calcined at temperatures of 800 oC and 900 oC for 2h. The phase of BaMnTiO3 powder was studied
by X-ray diffractometer (modified D-500, SIEMENS, Germany) using the Ni-filtered
monochromatic CuK radiation. The detection range was 1060o with the step size of 0.10o (2/s/s).
The structure of BaMnTiO3 powder was confirmed with the Joint Committee on Powder Diffraction
Standards Card File No. 15-0239 [8]. The fine powder were dispersed with absolute ethanol
[C2H5OH] medium in an ultrasonic bath (Model 5880, Cole-Parmer, USA) for 10 min, and goldcoated by the fine coater (JSC1200, JEOL, Japan). The morphology of powder was investigated by
scanning electron microscope (JSM5410-LV, JEOL, Japan) with the tungsten (W) filament K type,
accelerate voltage 25 kV. The chemical composition was analyzed by energy dispersive
spectrophotometer (ISIS300, Oxford, UK).
Results and Discussion
Figure 1 shows the XRD patterns of BaMnTiO3 powder after calcined at temperatures of 800 oC
and 900 oC for 2h with 0, 2 and 4 mol % Mn. At 800 oC with 0 to 4 mol % of Mn, Fig. 1 (a-c), a
single phase of BaTiO3 with tetragonal structure was obtained corresponding to the JCPDS File
Card No. 83-1880 [9]. At 900 oC with 2 and 4 mol % of Mn, Fig. 1 (e,f), a single phase of
Ba(Mn0.33Ti0.67)O2.84 with hexagonal structure at 2 = 41.989 was obtained corresponding to the
JCPDS Card File No. 15-0239 [8]. The intensity of Ba(Mn0.33Ti0.67)O2.84 peaks increased with
increased calcination temperature.

Figure 1. XRD patterns of BaMnTiO3 powder calined at 800 C with mole % of Mn as (a) 0, (b) 2
and (c) 4 and 900 C with mole % of Mn as (d) 0, (e) 2 and (f) 4

Advanced Materials Research Vols. 55-57

83

Figure 2 shows the SEM micrograph of BaMnTiO3 powder after calcination at 900 oC for 2h with
0, 2 and 4 mol % Mn. The average of particle size of BaTiO3 powder was 100 nm with highly
agglomerate and irregular in shape as shown in Fig.3 (a). The range of particle size of
Ba(Mn0.33Ti0.67)O2.84 powder with 2 and 4 mol % Mn, (Fig. 2 (b) and (c)), were 60 nm and 50 nm,
respectively, with irregular in shape.

(a)

(b)

(c)
Figure 2. SEM micrographs of BaMnTiO3 powder calined at 900 C with mole % of Mn as (a) 0,
(b) 2 and (c) 4
Intensity

Energy (keV)
Figure 3. EDS spectra of BaMnTiO3 powder calined at 900 C with mole % of Mn as 4

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Figure 3 shows EDS spectra of BaMnTiO3 powder with 4 mol % Mn after calcination at 900 oC for
2h. Energy dispersive spectrophotometry was employed to investigate and indicate the composition
of powder calcined with the energy dispersive values. The characteristic X-ray radiation of each
element has different energy value; barium of L1 4.465, L 4.827 and L2 5.156 keV, manganese of
K 5.894 keV, titanium of K 4.508 keV and oxygen of K 0.525 keV, respectively.
Summary
Tetragonal structure of BaTiO3 powder was prepared from the oxalate and the impregnation
methods after calcination at 800 oC for 2h with 0-4 mol % Mn and 900 oC for 2h with 0 mol % Mn.
Hexagonal structure of Ba(Mn0.33Ti0.67)O2.84 powder was obtained after calcination at 900 oC for 2h
with 2-4 mol % Mn. The particle size of Ba(Mn0.33Ti0.67)O2.84 powder was 60 and 50 nm for 2 and 4
mol % Mn, respectively, with irregular in shape. The elemental constituents of the powder were
identified by the energy dispersive values.
Acknowledgements
The authors would like to thank the financially support from the Department of Chemistry, the
Faculty of Science, Maejo University, Chiang Mai, Thailand. The authors would like to thank Prof.
Dr. Tawee Tunkasiri and Mr. Suwich Chaisupan from Department of Physics, Chiang Mai
University, Chiang Mai, Thailand for X-ray diffractometer (XRD), Ms. Passapan Sriwichai from
Biotechnology Center, Maejo University, Chiang Mai, Thailand for scanning electron microscope
(SEM) facilities and the National Nanotechnology Center (NANOTEC), the National Science and
Technology Development Agency (NSTDA), Ministry of Science and Technology, through its
program of Center of Excellence Network, Thailand.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

M. Xu, Y.-N. Lu, Y.-F. Liu, S.-Z. Shi, T.-S. Qian and D.-Y. Lu: Powder Technol. Vol. 161
(2006), p. 185.
W. Maison, R. Kleeberg, R.B. Heimann and S. Phanichphant: J. Eur. Ceram. Soc. Vol. 23
(2003), p. 127.
M.H. Frey and D.A. Payne: Phys. Rev. B. Vol. 54 (1996), p. 3158.
S.W. Lu, B.I. Lee, Z.L. Wang and W.D. Samuels: J. Cryst. Growth. Vol. 219 (2000), p. 269.
P. Pookmanee, C. Khantha and S. Phanichphant: Mater. Sci. Forum. Vol. 561-565 (2007), p.
515.
T. Sahoo, G.K. Pradhan, M.K. Rath, B. Pandey, H.C. Verma, S. Nandy, K.K. Chattopadhyay
and S. Anand: Mater. Lett. Vol. 61 (2007), p. 4821.
H.T. Langhammer, T. Mller, A. Polity, K.-H Felgner and H.-P. Abicht: Mater. Lett. Vol. 26
(1996), p. 205.
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 150239 Swarthmore, PA
Joint Committee on Powder Diffraction Standards. Powder Diffraction File, Card No. 831880 Swarthmore, PA

Advanced Materials Research Vols. 55-57 (2008) pp 85-88


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.85

Ammonothermal Preparation of Barium Zirconate Fine Powders


S. Wannapaiboon1,a and A. Rujiwatra1,2,b
1

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
2

Center of Excellence NANOTEC, Chiang Mai University (A Member of National Science and
Technology Development Agency), Chiang Mai 50200, Thailand
a

sutti_beernb@hotmail.com, bapinpus@gmail.com

Keywords: Barium Zirconate, Solvothermal, Ammonothermal, Chemical Synthesis

Abstract. Barium zirconate fine powders of pure cubic phase were readily prepared from the
reactions between BaCl22H2O and ZrOCl28H2O under ammonothermal conditions at a very low
temperature of 130oC as the lowest. KOH concentration was important in determining phase
formation and particle morphology. Reaction temperature and time showed influences on the
evolution of particle morphology and aggregation formation, respectively. Sizes of the primary
particles critically depended on the BaII:ZrIV mole ratio. Phase formation mechanism is suggested.
Introduction
Due to distinctively high melting point and chemical inertness, barium zirconate (BaZrO3 or BZ) is
one of the most widely utilized perovskite materials, e.g. as an inert crucible [1] and a promising
candidate for sensor applications at high temperatures [2]. Different applications however require
different BZ powder characteristics, which can be drastically diverse depending on preparative
routes and conditions. Recently, various alternative solution-based techniques have been developed
including a simple and environmentally benign hydrothermal technique [3-4]. Further development
of the technique is, nonetheless, still by far a challenge for synthetic chemists. Herein, the
achievement of cubic phase-pure BZ powders via ammonothermal reactions conducted at
considerably low temperature is reported. The influences of KOH mineralizer concentration,
reaction temperature and time, and BaII:ZrIV mole ratio on the powder characteristics are discussed.
Experimental
White slurries of BaCl22H2O (J.T. Baker 99%) and ZrOCl28H2O (BDH Chemicals Ltd. 96%) were
prepared in ammonia solution (NH3(aq), PA-ACS 28.0-30.0%). To examine the influences of the
KOH concentration, reaction temperature and time, the concentration of each precursor was kept
equal at 1.16 moldm-3. Pellets of KOH (Merck 85%) were then gradually added to the reaction
slurries while being stirred vigorously, to the pre-calculated concentrations varied in a range of
0.00-4.80 moldm-3. The slurries were transferred into 50 cm3 Teflon-lined hydrothermal reactors
(Parr Instrument) with ca. 70% filling capacity. The reactions were carried out under autogenous
pressure at 110-200oC for 3-72 hours. To investigate the influence of BaII:ZrIV mole ratio, the
concentration of ZrOCl28H2O was kept at 1.16 moldm-3, while that of BaCl22H2O was varied to
adjust the BaII:ZrIV mole ratio from 1.0:1.0 to 2.0:1.0. Powder X-ray diffraction data (XRD,
Siemens D500/D501, CuK, Ni filter, =1.54 ) were used to follow phase formation of the
crystalline solids. A field emission scanning electron microscope (FESEM, JEOL JSM-6335F)
equipped with the energy dispersive X-ray (EDX) microanalyzer was used for the investigation of
the composing particle morphology and size, aggregation formation and elemental composition.
Laser diffraction technique (CLAS 1064 ranging from 0.04 to 500.00 um/100 classes) was used to
examine particle/aggregate size distribution.

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Results and Discussion


The influence of the KOH concentration was studied from the reactions using stoichiometric
BaII:ZrIV, conducted at 180oC for 24 hours. Fig. 1 shows the XRD patterns of the obtained powders,
revealing the minimal KOH concentration of 3.50 moldm-3 was necessary in providing the phasepure BZ powders under these conditions. At lower KOH concentrations, poorly crystalline
tetragonal zirconium oxide could be presumed from the XRD and EDS results [5]. The increasing
of the KOH concentration up to 4.80 moldm-3 resulted in better crystallinity of the obtained
powders. Every peak present in Fig. 1(d) to Fig. 1(g) could be readily indexed based on a cubic BZ,
with similar refined cell parameter a = 4.184(4)-4.201(4) . There was no apparent correlation
however between the KOH concentration and the refined cell parameters, whereas the effect on the
growth of the composing particles was discernible. According to the SEM photographs as shown in
Fig. 2, the KOH concentration of 4.80 moldm-3 provided the best defined particle morphology of
truncated rhombic dodecahedra (Fig. 2(c)). The lower KOH concentrations led to the formation of
aggregates of poorly defined BZ particles with distinguishing necks between the particles (Fig. 2(a)
and Fig. 2(b)). The incomplete particle growth could be implied. Sizes of the obtained truncated
rhombic dodecahedral BZ particles measured from the SEM photographs were distributed in a wide
range of ca. 0.47-3.42 m with an average size of ca. 1.77 m. These particles were commonly
existed also as large aggregates with an average size scaling up to ca. 16 m, based on the laser
diffraction results. It was therefore deducible here that the increasing of KOH concentration from
3.50 to 4.80 moldm-3 favored a better phase formation and crystal growth of BZ.
Fig. 1 XRD patterns of the powders obtained from the
reactions conducted at 180C for 24 hours using the KOH
concentration of (a) 0.00 (b) 2.00 (c) 3.00 (d) 3.50 (e) 4.00
(f) 4.50 and (g) 4.80 mol dm-3. The solid and dotted lines
indicate the indexed diffraction peaks of cubic BZ and
tetragonal zirconium oxide, respectively.

Fig. 2 The SEM photographs showing the evolution of particle morphology obtained from the
reactions at 180oC using the KOH concentration of (a) 4.00 moldm-3 and (b) 4.50 moldm-3,
compared with those obtained from the reactions conducted using the KOH concentration of 4.80
moldm-3 at (c) 180oC (d) 150oC and (e) 130oC.
Fig. 3(a) to Fig. 3(c) show the XRD patterns of the powders obtained from the reactions using the
KOH concentration of 4.80 moldm-3 conducted at three different temperatures for 24 hours. It was
apparent that the phase-pure cubic BZ could be achieved at as low temperature as 130oC, which was
relatively lower than that required for the hydrothermal analogue [3-4], in only 24 hours. This could
be partially due to a better pressure transmitting ability of ammonia compared to water and hence a
higher vapor pressure in the system. In addition, NH4OH(aq) in the system could promote the
formation of a reactive hydrous zirconium oxide from the hydrolysis of the ZrOCl28H2O precursor
[6,7]. The SEM photographs of the powders with the corresponding XRD patterns shown in Fig.
3(a) to Fig. 3(c) revealed the evolution of the particle morphology from mostly spherical when the

Advanced Materials Research Vols. 55-57

87

reaction temperature was 130oC (Fig. 2(e)), to truncated rhombic dodecahedral when the reaction
temperature was 180oC (Fig. 2(c)).
It was also intriguingly observed that the higher
reaction temperatures led to better particle dispersion
and therefore smaller average sizes of the aggregates,
i.e. 19.54, 18.97 and 16.32 m for the 130oC, 150oC
and 180oC cases, respectively, based on the laser
diffraction results. Fig. 3(d) to Fig. 3(h) show the XRD
patterns of the powders obtained from the reactions
performed at varied temperatures from 110oC to 200oC
for 72 hours. Regardless of the reaction temperature, the
prolonged reaction time of 72 hours always led to the
formation of other crystalline phase, denoted by
Fig. 3 The XRD patterns of the powders asterisks in Fig. 3. These diffraction peaks could not be
obtained from the reactions using the indexed without any dubiety, due to deficiency in
[KOH] of 4.80 mol dm-3, conducted at diffraction peak numbers. Fig. 4 exemplifies the XRD
prepared from the reactions
(a) 110oC (b) 130oC and (c) 150oC, for patterns of the powders
o
24 hours compared with those of the conducted at 180 C for 3-48 hours. It was apparent that
reactions conducted at (d) 110oC (e) the phase-pure cubic BZ could be obtained in only 6
130oC (f) 150 oC (g) 180 oC and (h) hours at this temperature with similar refined cell
200oC, for 72 hours. The asterisks parameters a = 4.183(2)-4.215(6) , showing also no
correlation with reaction time. According to the SEM
indicate unidentified peaks.
and laser diffraction results, although the prolonged
reaction time revealed no influence on size distribution
of the primary BZ particles, i.e. 0.47-3.42 m, those of
the aggregates on the other hand differed significantly.
Fig. 5 shows size distribution ranges and mean
diameters of the aggregates, revealing the tendency of
the distribution toward smaller size region of less than
10 m when the reaction times were 36 hours. The
abruptly decrease of the mean diameter of the
aggregates to ca. 2.83 m, which was closer to that
observed in the primary particle sizes, when the
reaction was carried out for 36 hours should be
noteworthy. The morphology of the BZ particles,
obtained from the reactions using the same KOH
Fig. 4 The XRD patterns of the powders concentration and conducted at the same reaction
prepared from the reactions using the temperature however showed no variation with reaction
KOH concentration of 4.80 mol dm-3, time. These results suggested the KOH concentration
conducted at 180oC for (a) 3 (b) 6 (c) and reaction temperature to be the prime factors
12(d) 18 (e) 24 (f) 36 and (g) 48 hours; determining particle morphology, whereas the reaction
where the asterisks indicate unidentified time as a prominent factor in affecting the aggregation
peaks.
formation.
The influences of the starting BaII:ZrIV mole ratio on phase formation and characteristics of the
composing BZ particles were also studied. Sizes of the composing BZ particles were withal reduced
discernibly with increasing BaII:ZrIV mole ratio. Fig. 6(a) shows variation of size distribution and
mean diameter of the BZ particles with BaII:ZrIV mole ratio. The smallest mean particle sizes of ca.
0.40-0.60 m were obtained when the employed BaII:ZrIV was at least 1.50:1.00. The abrupt
reduction in the primary particle sizes was consistent with the line broadening effect observed in the
diffraction peaks as exemplified by the (110) peak shown in Fig. 6(b). This implied the importance
of BaII ion in nucleation process. Based on the solid phase diffusion mechanism [8], the reaction

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may presumably occurs via the diffusion of the dissolved BaII ions into the hydrated zirconium
oxide framework. The increase in relative amount of BaII can therefore promote the possibility and
number of nucleation rather than crystal growth, which then results in smaller particle sizes and
poorly defined morphology.
Fig. 5 Size distribution of the aggregates based on the
laser diffraction results, measured from the powders with
the corresponding XRD patterns shown in Fig. 4(b) to Fig.
4(g), where the horizontal bar and the indicate the
distribution margin and mean value, respectively.
Fig. 6 (a) Primary particle size
distributions and the average
values measured from the SEM
photographs of the powders
obtained from the reactions
conducted at 150C for 24 hours,
and (b) line broadening observed
in the (110) diffraction peak. The
horizontal bar and the indicate
the distribution margin and mean
value, respectively.
Summary
The cubic phase-pure BZ powder could be successfully prepared at very low temperature. It was
evident that the concentration of KOH mineralizer was critical in both determining the purity of the
powders and the well-define morphology of the primary particles. Reaction temperature was the
prime factor determining the complete particle growth, whereas reaction time was critical in
affecting the formation of aggregation. The influences of the investigated preparative parameters
could lead to an assumption for the phase formation mechanism to occur via the diffusion of BaII
ions into the transformed zirconium oxide framework.
Acknowledgement
The authors thank to the Thailand Research Fund and the Committee for Higher Education for
financial support. Suttipong Wannapaiboon thanks the Development and Promotion of Science and
Technology Talent Project and Junior Science Talent Project for undergraduate scholarship.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

A. Erb, E. Walker and R. Flukiger: J. Physica Vol. C258 (1995), p. 9.


H. Iwahara, T. Yajima, T. Hibino, K. Ozaki and H. Suzuki: Solid State Ionics Vol. 61 (1993),
p. 65.
A. Dias and V.S.T. Ciminelli: Chem. Mater. Vol.15 (2003), p. 1344.
Z. Lu, Y. Tang, L. Chen and Y. Li: J. Cryst. Growth Vol. 266 (2004), p. 539.
J. Liang, X. Jiang, G. Liu, Z. Deng, J. Zhuang, F. Li and Y. Li: Mater. Res. Bull. Vol. 38
(2003), p. 161.
S.Wang, X. Li, Y. Zhai and K. Wang: Powder Technology Vol. 168 (2006), p. 53.
K. Matsui and M. Ohgai: J. Am. Ceram. Soc. Vol. 80 (1997), p. 1949.
A. Rujiwatra, N.Thammajak, T. Sarakonsri, R.Wongmaneerung and S. Ananta: J. Cryst.
Growth Vol. 289 (2006), p. 224.

Advanced Materials Research Vols. 55-57 (2008) pp 89-92


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.89

Effect of Al2O3 Addition on Dielectric, Piezoelectric and Ferroelectric


Properties of 0.2Pb(Zn1/3Nb2/3)O30.8Pb(Zr1/2Ti1/2)O3 Ceramics
A. Ngamjarurojana*, S. Ananta and R. Yimnirun
Department of Physics, Faculty of Science, Chiang Mai University, 50200, Thailand.
*Corresponding author. Tel.: +66-53-941921 ext 445; fax: +66-53-943445.
E-mail address: Ngamjarurojana@yahoo.com
Keywords: Dielectric properties, Piezoelectric properties, Ferroelectric properties and Hard doping

Abstract. The structure and electrical properties of Al2O3-doped 0.2Pb(Zn1/3Nb2/3)O30.8Pb(Zr1/2Ti1/2)O3 ceramic, which is the morphotropic phase boundary composition of the PZNPZT system, were investigated. The addition of Al2O3 content transformed the crystal structure
from coexisting with rhombohedral to purely tetragonal structure. Furthermore, addition of Al2O3
decreased r, d33 and kp, but increased Curie temperature and enhanced the mechanical quality factor.
Finally, the PE and s-E loops demonstrated decreased Pr, Ec and strain level with addition of Al2O3.
Introduction
Lead zirconate titanate, Pb(Zr,Ti)O3 or PZT, is a well known piezoelectric that has been widely
employed in a large number of sensing and actuating devices. PZT ceramics have very high Curie
temperature (~ 390 oC). Lead zinc niobate, Pb(Zn1/3Nb2/3)O3 or PZN, which exhibits a perovskite
structure and a Curie temperature of ~140 oC, is one of the most important relaxor ferroelectric
materials with a high dielectric constant and large electrostrictive coefficient. They have excellent
dielectric, piezoelectric and elastic properties suitable for wide range of practical applications [1-3].
Though the PZN-PZT based ceramics have excellent electrical properties, poor mechanical
properties such as fracture strength and toughness have been reported [4]. In some applications at
high power and high stress, mechanical properties of this material become critically important.
Recently, it is reported that the mechanical properties of structural ceramics can be improved by an
addition of second phase nanoparticles such as SiC and Al2O3 [5]. It is therefore of interest to
explore the possibility of using Al2O3 as both electrical properties modification with possible
mechanical properties benefit.
Thus, in this study 0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3 ceramics were prepared and the
influences of Al2O3 addition on structure, and electrical properties of the ceramics were
investigated, which are especially important from the viewpoint of the development of practical
piezoelectric materials.
Experimental
The specimens studies were fabricated according to the formula: 0.2Pb(Zn1/3Nb2/3)O30.8Pb(Zr1/2Ti1/2)O3+x wt% Al2O3, where x = 0.1, 0.3, 0.5, 0.7 and 0.9. Raw materials of PbO, ZrO2,
TiO2, ZnO, Nb2O5 and Al2O3 with >99% purity were used to prepare samples by a conventional
mixed oxide process. The starting powders were mixed by zirconia ball media with isopropanal as a
medium in a polyethylene jar for 30 min via vibro-milling technique. The mixed slurry was dried
and calcined at 900 oC for 2 h. The calcined powders were ball-milled again with additives and
consolidated into disks of 12.5 mm diameter using isostatic pressing about 150 MPa. PbO-rich
atmosphere sintering of the ceramics was performed in a high-purity alumina crucible at 1200 C
for 2 h. The crystal structure and symmetry of the sintered bodies were examined by X-ray
diffraction (XRD) and densities were measured by Archimedes method. Surface morphologies of
sintered ceramics were directly imaged, using scanning electron microscopy (SEM; JEOL JSM840A). Grain size was determined from SEM micrographs by a linear intercept method.

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For electrical properties characterizations, silver electrode (Dupont, QS 171) was printed on the
lapped surfaces. The electrode was fired at 850 oC for 45 min. The specimens were poled in
silicone oil at 150 oC by applying a DC field of 3 kV/mm for 30 min. The dielectric properties of the
sintered ceramics were studied as functions of both temperature and frequency with an automated
dielectric measurement system. The computer-controlled dielectric measurement system consists of
a precision LCR-meter (Hewlett Packard, model 4284A), a temperature chamber, and a computer
system. The capacitance and the dielectric loss tangent are determined over the temperature range
of 50 and 450 C with the frequency ranging from 100 Hz to 100 kHz. The Curie temperature (Tc)
was determined by the temperature dependence of the dielectric constant at 1 kHz. The
piezoelectric constant (d33) was measured using a quasi-static piezoelectric d33 meter (Model ZJ-3d,
Institute of Acoustics Academic Sinica, China). The planar coupling coefficient (kp) and the
mechanical quality factor (Qm) were determined by the resonance and anti-resonance technique [6]
using an impedance analyzer (Model HP4294A, Hewlett-Packard). Ferroelectric switching
measurements were made using a modified Sawyer-Tower circuit with a linear variable differential
transducer (LVDT) for strain measurement, DSP lock-in amplifier (SR830, Stanford Research),
high voltage power supply (TREK 609C-6, Trek), and computerized control and data acquisition.
Results and Discussion
Figure 1 shows the XRD patterns of Al2O3-doped 0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3 ceramics
sintered at 1200 C for 2 h. In these patterns, the crystal structure of the specimens is modified by
the addition of Al2O3, as revealed by the evolution of (200) and (002) peaks. The perovskite
structure appears to change from coexisting with rhombohedral to purely tetragonal structure. Slight
shift in diffraction angle by doping Al3+ ions indicates their substitution (solid solution) into the
lattice of PZN-PZT. Al3+ions are expected to substitute B-sites of the perovskite structure because
ionic radius of Al3+ is closer to that of Zr4+ , Ti4+ , Zn2+ and Nb5+ than that of Pb2+ [7].

(a) undoped (b) 0.1 wt% (c) 0.3 wt%


(d) 0.5 wt% (e) 0.7 wt% (f) 0.9 wt%
Figure 1. XRD patterns of Al2O3-doped
PZN-PZT ceramics sintered at 1200 C for 2 h.

Figure 2. SEM photographs of the surfaces of


Al2O3-doped PZN-PZT ceramics

Figure 2 shows SEM photographs of the surfaces of 0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3


ceramics doped with 0.10.9 wt% Al2O3. As shown in Fig. 2, the grain sizes of ceramics are
slightly increased with increasing amount of Al2O3 addition. However, the SEM micrographs in
Fig. 2(e-f) show that a higher porosity level is observed when the amount of Al2O3 is increased,
which indicates that the specimens are not sintered effectively. The above results are obviously
consistent with the change in the bulk density with Al2O3 content for Al2O3-doped
0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3 ceramics. It can be seen from Fig. 2 that Al ions are mainly

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91

accumulated at the grain boundaries [8]. Atkim et al. [9] reported that dopant ions were
concentrated at grain boundaries and took excess impurities by diffusion when grain boundaries
moved, which in turn reduced grain boundary mobility and size. These inferences are obviously
consistent with the changes mentioned above in the microstructures. The micrographs also show
that the grain size of the ceramics varies considerably.
The temperature dependences of the dielectric constant (r) at 1 kHz for 0.2PZN0.8PZT + x
wt% Al2O3, x = 0, 0.1, 0.3, 0.5, 0.7 and 0.9 are plotted in Fig. 3. The observed broadening of the
dielectric peaks may be caused from decreasing of density of ceramics and higher porosity. The
variation of the Curie temperature (Tc) as a function of composition x is displayed, which shows an
increase in Tc with increasing Al2O3 content. Thus, the Curie temperature of 0.2PZN0.8PZT + x
wt% Al2O3 system can be varied over a range of 340 and 360C by controlling the content of Al2O3
addition in the system.

Figure 3. The temperature dependences of


the dielectric constant (r) at1 kHz

Figure 4. , dielectric constant rpiezoelectric


constant (d33), electromechanical coupling factor
(kp) and the mechanical quality factor (Qm)

Figure 4 shows the changes in density, dielectric constant rpiezoelectric constant (d33),
electromechanical coupling factor (kp) and the mechanical quality factor (Qm) as a function of the
amount of Al2O3 addition. With addition of Al2O3, the density, r kp and d33 rapidly decrease. It is
well known that the substitutions of acceptor dopant Al ions will lead to the creation of oxygen
vacancies, which pin the movement of the ferroelectric domain walls and result in a decrease of r
kp and d33. On the other hand, Qm rapidly increases with increasing Al2O3 content. These
observations are in good agreement with previous work by Kulascar et al. [10], which reported that
in the case of substitution of 3+ ions for B-sites of the perovskite structure, oxygen vacancies
produced by charge neutrality beyond solid solution limit lead to decrease in electromechanical
coupling factor, dielectric constant and electrical resistivity, and to increase in mechanical quality
factor. Hence, these results clearly indicate that increased Al2O3 would degrade piezoelectric
properties due to exceeding the solution limit of lattices [11].
The polarization-field (PE) hysteresis loops of 0.2PZN0.8PZT + x wt% Al2O3 ceramics are
shown in Fig. 6. The well-developed and fairly symmetric hysteresis loops with the field are
observed for all compositions. To further assess ferroelectric characteristics in Al2O3modified
PZN-PZT ceramics, the ferroelectric parameters, i.e. the remnant polarization (Pr) and the coercive
field (Ec), have been extracted from the experimental data and given in Table III. It can be seen
clearly that Pr, Ps and Ec decrease with an addition of Al2O3 into the PZNPZT composition [12].
Strain of specimens as function of the electric filed is shown in Fig. 7. Decreasing in strain and
coercive field with increasing Al2O3 content is clearly observed. Finally, the decrease in Pr, Ec, and
strain level with Al2O3 addition suggests the reduction of the polarization and strain that are
achieved during an electric field cycle. These quantities depend directly on the extent of domain
boundary motion [9].

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Figure 5. PE hysteresis loops of


0.2PZN0.8PZT + x wt% Al2O3 ceramics

Figure 6. Strain loops of 0.2PZN0.8PZT


+ x wt% Al2O3 ceramics

Summary
The structure and electrical properties of Al2O3-doped 0.2Pb(Zn1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3
ceramic, which is the morphotropic phase boundary composition of the PZN-PZT system, are
investigated. The addition of Al2O3 transformed the crystal structure from coexisting with
rhombohedral to purely tetragonal structure. Furthermore, added Al2O3 decreases r, d33 and kp, but
increases Curie temperature and enhances the mechanical quality factor. The PE and s-E loops
demonstrate decreased Pr, strain level, and Ec when addition of Al2O3 in PZN-PZT ceramic
systems.
Acknowledgment
This work was jointly supported by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), and the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of
Science and Technology, Thailand, through its program of Center of Excellent Network, Faculty of
Science, Chiang Mai University. Thanks are also extended to Kenji Uchino, ICAT, Penn State
University for helpful discussion and use of facility.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]

Xu Y.: Ferroelectric Materials and Their Applications (Elsevier Science Publishers,


Amsterdam, The Netherlands, 1991).
Uchino K. and. Giniewicz J. R: Micromechatronics (Marcel Dekker, New York, 2003).
Moulson A.J. and Herbert J.M.: Electroceramics (2nd ed., Wiley, New York, 2003).
Tajima K., Hwang H., Sando M. and Niihara K.: J. Eur. Ceram. Soc. Vol. 19 (1999), p. 1179.
Sternitzke M.: J. Eur. Ceram. Soc. Vol. 17 (1997), p.1061.
IEEE Standard on Piezoelectricity: IEEE Standard 1761978. Institute of Electrical and
Electronic Engineers, New York, 1978.
Shannon R. D.: Acta Crystal. A. Vol. 32 (1976), p. 751.
Fang J.X. and Yin Z. W.: Physics of Dielectric (Science Press, Beijing, 1989)
Atkin R. B., and Fularath R. M.: J. Am. Ceram. Soc.Vol. 54 (1971), p. 265.
Kulascar F.: J. Am. Ceram. Soc. Vol. 42 (1959), p. 343.
Kim Y.-M., Kim J.-C., Ur S.-C. and Kim H.-H.: J. Electroceram. Vol. 16 (2006), p. 347.
Iijima T., HeG., Wang Z., Isuboi H., Hiyama K. and Okada M.: Jpn. J. Appl. Phys. Vol. 39
(2000), p. 5426.
Yimnirun R, Ananta, S Ngamjarurojana A, and Wongsaenmai S.: Appl. Phys. A. Vol. 81
(2005), p. 1227.

Advanced Materials Research Vols. 55-57 (2008) pp 93-96


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.93

Microstuctural Study and Properties of 0.8PZT-0.2BT Ceramics


using a Two-stage Sintering Procedure
W. C. Vittayakorn
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand
wanwilai_chaisan@yahoo.com
Keywords: Microstructure, Sintering, PZT, BT

Abstract. Lead zirconate titanate-barium titanate (0.8PZT-0.2BT) ceramic was prepared by


conventional mixed-oxide method combined with a two-stage sintering procedure. A sintering time
of 2 h at 1000 C followed by a second step in the temperature range of 1000-1200 C for 2 h was
employed to the samples and compared to the one-step sintering process. Phase formation,
densification and microstructure of all ceramics were examined via X-ray diffraction (XRD),
Archimedes method and scanning electron microscope (SEM). The results lead to the conclusion
that the pure perovskite phase and high densification of 0.8PZT-0.2BT ceramics with small grain
can be successfully achieved under suitable two-stage sintering conditions.
Introduction
Nowadays, lead-based ferroelectric ceramics are widely applied in multilayer capacitors,
transducers and sensors because of their excellent electrical properties [1]. Many of these
applications require materials with superior electrical properties. Both PZT and BT are among the
most common ferroelectric ceramics and have been studied extensively since the late 1940s [2, 3].
These two ceramics have distinct characteristics that make each ceramic suitable for different
applications. The PZT ceramic has great piezoelectric properties which can be applied in transducer
applications. Furthermore, it has a high TC of 390 C which allows electronic devices to be
operated at high temperatures. BT ceramic is a normal ferroelectric material which exhibits a high
dielectric constant, a lower TC (~120 C) and better mechanical properties [1-3]. However,
sintering temperature of BT is higher than PZT. Thus, mixing PZT with BT is expected to decrease
the sintering temperature of BT-based ceramics, a desirable move towards electrode of lower cost
[4]. Moreover, since PZT-BT is not a pure-lead system, it is easier to prepare single phase ceramics
with significantly lower amount of undesirable pyrochlore phases, usually associated with leadbased system [5, 6]. With their complimentary characteristics, it is expected that excellent electrical
properties with preparation ease can be obtained from ceramics in PZT-BT system.
The electrical properties of ferroelectric ceramics depend strongly on microstructure as well as
chemical compositions [1, 7]. It was reported earlier that the high value of dielectric constant can
be revealed if polycrystalline ferroelectric ceramics of fine grain size is achieved [8, 9]. Thus, a
fine grain is essential to attain optimum dielectric properties. In the literatures, it is well known that
the microstructure of most ferroelectric ceramics can be normally controlled by two approaches.
Utilizing additives to prohibit the grain growth is one approach [10-12]. Another approach uses
novel processing technique to modify the microstructure. Numerous studies on the sintering
process of ferroelectric ceramics have been reported in previous works [9, 13, 14]. Recently, a twostage sintering method has been proposed by Chen and Wang to achieve the densification of
ceramic bodies without significant grain growth [15]. Moreover, Kim and Han [9] found that
intermediate dense and fine grain size BT ceramic was achieved from the two-stage sintering
technique and showed much greater dielectric constant than that of the normal sintering technique.
However, there is no systematic study about two-stage sintering on lead-based ferroelectric
ceramics. Therefore, in this work a two-stage sintering method, which is a low-cost technique and
simple ceramic fabrication to obtain highly dense ceramics, has been adopted to produce the fine

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grain PZT-BT ceramic. The influence of two-stage sintering on densification and microstructure of
the ceramics is investigated with comparison to the normal sintering scheme.
Experimental
0.8Pb(Zr0.52Ti0.48)O3-0.2BaTiO3 powders used in this study were prepared by a simple mixed oxide
synthetic route. Commercially available powders of PbO, ZrO2, BaCO3 and TiO2, (Fluka, >99%
purity) were used as starting materials. PZT and BT powders were first form in order to avoid
unwanted pyrochlore phases. The 0.8PZT0.2BT powders were then formulated from the PZT and
BT components by employing the mixed-oxide procedure. The mixing process was carried out by
ball-milled a mixture of raw materials for 24 h with corundum media in ethanol. After wet-milling,
the slurry was dried at 120 C and calcined in a closed alumina crucible, with the optimum
calcination condition (1200 C for 2 h). Ceramic fabrication was achieved by adding 1 wt%
polyvinyl alcohol (PVA) binder, prior to pressing as pellets (15 mm of diameter and 1.0 mm of
thickness) in an uniaxial die press at 100 MPa. Each pellet was placed in an alumina crucible
together with atmosphere powders of identical chemical composition. In the so-called two-stage
sintering process, the first sintering temperature (T1) was assigned for 1000 C and variation of the
second sintering temperature (T2) between 1000 C and 1200 C was carried out (Fig. 1). For
comparison, normal sintering process was also carried out at the firing temperature between 1150
and 1350 C for 2 h. The two sintering schemes also included the binder burn out process at 500 C
for 1 h. Phase formation of all ceramics was examined via X-ray diffraction (XRD). Densities of
the final sintered products were determined by using the Archimedes principle. Microstructural
development was characterized using a JEOL JSM-840A scanning electron microscopy (SEM).

Fig. 1. A two-stage sintering procedure.

Results and Discussion


The XRD patterns of two-stage sintered 0.8PZT-0.2BT ceramic compared with normal sintered
ceramic were illustrated in Fig. 2. The XRD graphs for both ceramics show almost the same. From
Fig. 2, it can be indicated that the single phase of 0.8PZT-0.2BT (yield of 100% within the
limitations of the XRD technique) was found in both samples. The ceramics were identified as
perovskite structure having tetragonal symmetry and the diffraction peaks shifted towards to XRD
pattern of tetragonal PZT which can be matched with the JCPDS file no. 33-0784. The cell
parameter of each ceramic can be calculated using nonlinear least-square method. The cell
parameters a = 0.4013 nm, c = 0.4071 nm can be achieved for normal sintered ceramics and a =
0.3994 nm, c = 0.4056 nm for two-stage sintered ceramic.
The microstructure of 0.8PZT-0.2BT ceramics with the highest density was revealed by SEM.
Micrographs of samples sintered with different schemes are shown in Fig. 3. As shown in Fig. 3,
SEM micrographs reveal that the both ceramics exhibit good densification and homogenous grain

Advanced Materials Research Vols. 55-57

95

size. For the normal sintered ceramic, the grain size varies greatly from 0.5 to 10 m. However, it
can be noticed that the microstructure of the two-stage sintered ceramics (Fig. 3b) is slightly
different from that of the normal sintered PZT-BT samples (Fig. 3a). The two-stage sintered
ceramic contains smaller average grain size (~ 2.0 m) and some degree of porosity is clearly seen.
In the two-stage sintering process, the first sintering temperature was fixed at 1000 C, for constant
dwell time of 2 h and heating/cooling rates of 10 C/min, while the second sintering temperature
was varied from 1000 C to 1200 C. It is found that the relative density of the two-stage sintered
ceramics increased significantly from 69 to 82 % with increasing sintering temperature, while grain
size changed only slightly (about 1-5 m). However, in normal sintering process, while the highest
relative density is about 99 %, but the highest grain size is about 10 m. From this observation, it
can be said that the advantage of the two-stage sintering technique in producing small grain size of
0.8PZT-0.2BT ceramic is clearly signified. Although the average grain size of 0.8PZT-0.2BT
ceramic prepared by two-stage sintering is small but the highest densification is not so effective
(82%), this is the result of volatile PbO loss due to double firing at moderate temperature.
However, the highest densification can be improved by designing the proper sintering temperature.

Fig. 2. XRD patterns of 0.8PZT-0.2BT ceramics prepared by normal and two-stage sintering.

(a)

(b)

Fig. 3. SEM micrographs of 0.8PZT-0.2BT ceramics (a) normal sintered at 1300 C and (b) twostage sintered at 1000/1200 C.

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Even though exact mechanism of the microstructure observed here is not well established, but it
should be noted that the various features of microstructure in PZT-BT ceramics are dependent on
the grain growth rate in the different planes [16]. However, the sintering process and growth
environment also play an important role in the formation [17]. More importantly, it can be assumed
that the two-stage sintering process could suppress the grain growth mechanism efficiently whereas
the relative density of both normal- and two-stage sintered ceramics is in high value. This can be
explained that the feasibility of densification without grain growth, which is believed to occur in
two-stage sintered ceramic, relies on the suppression of grain boundary migration while keeping
grain boundary diffusion active. The kinetic and the driving force for grain growth behavior in the
second-step sintering were previously discussed by Chen and Wang [15]. Their work suggested
that the suppression of the final stage grain growth was achieved by exploiting the difference in
kinetics between grain-boundary diffusion and grain-boundary migration.
Summary
Even though the simple mixed-oxide method employing a conventional ball-milling was used, this
work demonstrated that it was possible to obtain smaller grain size ferroelectric PZT-BT ceramics
with high densification by the two-stage sintering technique. It has been shown that, under suitable
condition, two-stage sintering can effectively suppress the grain growth in 0.8PZT-0.2BT, leading
to small-grained microstructure.
Acknowledgements
This work was supported by the Thailand Research Fund (TRF), Commission on Higher Education
(CHE) and Faculty of Science of Chiang Mai University. I would also like to grateful to Assoc.
Prof. Dr. Supon Ananta and Asst. Prof. Dr. Rattikorn Yimnirun from Department of Physics,
Faculty of Science, CMU and Mr. Rangsan Muanghlua from Electronic Research Center, KMITL
for all support.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]

A. J. Moulson and J. M. Herbert: Electroceramics: Materials, Properties, Applications (John


Wiley & Sons Ltd., Chichester, 2003).
G. H. Haertling: J. Am. Ceram. Soc. Vol. 82 (1999), p. 797.
B. Jaffe, W. R. Cook and H. Jaffe: Piezoelectric Ceramics (Academic Press, London, 1971).
J. Chen, Z. Shen, F. Liu, X. Liu and J. Yun: Scripta Mater. Vol. 49 (2003), p. 509.
W. Chaisan, S. Ananta and T. Tunkasiri: Cur. Appl. Phys. Vol. 4 (2004), p. 182.
B. K. Gan, J. M. Xue, D. M. Wan and J. Wang: Appl. Phys. A Vol. 69 (1999), p. 433.
Y. Xu: Ferroelectric Materials and Their Applications (Elsevier Science Publishers B.V.,
1991).
K. Kinoshita and A. Yamaji: J. Appl. Phys. Vol. 47 (1976), p. 371.
H. T. Kim and Y. H. Han: Ceram. Int. Vol. 30 (2004), p. 1719.
A. Yamaji, Y. Enomoto, K. Kinoshita and T. Murakami: J. Am. Ceram. Soc. Vol. 60 (1977),
p. 97.
M. Kahn: J. Am. Ceram. Soc. Vol. 54 (1971), p. 452.
V. S. Tiwari, N. Singh and D. Pandey: J. Am. Ceram. Soc. Vol. 77 (1994), p. 1813.
J. S. Choi and H. G. Kim: J. Mater. Sci. Vol. 27 (1992), p. 1285.
J. K. Lee, K. S. Hong and J. W. Jang: J. Am. Ceram. Soc. Vol. 84 (2001), p. 2001.
I. W. Chen and X. H. Wang: Nature Vol. 404 (2000), p. 168.
M. H. Lin, J. F. Chou and H. Y. Lu: J. Eur. Ceram. Soc. Vol. 20 (2000), p. 517.
R. M. German: Sintering Theory and Practice (Wiley, New York, 1996).

Advanced Materials Research Vols. 55-57 (2008) pp 97-100


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.97

Effects of Manganese Addition on Phase Formation, Microstructure and


Electrical Properties of Barium Titanate Ceramics
J. Tangsritrakul1,a, M. Unruan1, P. Ketsuwan1 and R. Yimnirun1
1

Department of Physics, Faculty of Science, Chiangmai University Chiang Mai 50200, Thailand.
a

tang_ji@yahoo.com

Keywords: Mn-doped BaTiO3; Hexagonal; Dielectric properties; Ferroelectric properties

Abstract. In this study, the influence of Mn addition on phase formation, microstructure and
electrical properties of Ba(Ti1-xMnx)O3 where x = 0.01 to 0.2 was investigated. The XRD patterns
showed that the crystal structure of Ba(Ti1-xMnx)O3 at room temperature changed from tetragonal to
hexagonal as Mn concentration increased, which also caused the room temperature dielectric
constant decrease from 1143 to 47. The microstructure of Ba(Ti1-xMnx)O3 ceramics at low
concentration revealed a bimodal microstructure. As the x value increased, the well grown grains
decreased with the extent of fine-grained increased. Ferroelectric hysteresis (P-E) loop was not
clearly observed as Mn concentration increased because of the formation of paraelectric hexagonal
phase.
Introduction
Barium titanate, BaTiO3, based materials are well known electroceramics that find applications as
dielectric materials in capacitors and as positive temperature coefficient of resistance (PTCR)
thermistors.1-3 At temperature above 130C, barium titanate has a paraelectric cubic phase. In the
temperature range of 130 to 0 C the ferroelectric tetragonal phase with a c/a ratio of ~ 1.01 is
stable. The spontaneous polarization is along one of the [001] directions in the original cubic
structure. Between 0 C and -90 C, the ferroelectric orthorhombic phase is stable with the
polarization along one of the [110] directions in the original cubic structure. On decreasing the
temperature below -90 C the phase transition from the orthorhombic to ferroelectric rhombohedral
phase leads to polarization along one of the [111] cubic directions. Most research to date has
focused on materials based on the ferroelectric tetragonal polymorph, t-BaTiO3, due to its high
permittivity and because its electrical properties can be tailored to exhibit the PTCR effect. On
contrary, the high temperature hexagonal polymorph has not been widely investigated. The
hexagonal polymorph was first reported by Bourgeois in 1883 and crystallises in the space group
P63/mmc with lattice parameters a=5.7238 and c=13.9649 .4,6,8 Undoped 6H-BaTiO3 is
reported to be thermodynamically stable above 1460 C , 1 but can be kinetically stabilized at room
temperature by doping with various transition metal ions on the Ti-sites, e.g. Fe, Mn, Co, Ni that
can also lead to the formation of the hexagonal polymorph at room temperature.1, 4, 7 In this study,
the influences of Mn addition on phase formation, microstructure and electrical properties of
Ba(Ti1-xMnx)O3 ceramics were investigated.
Experimental
Ba(Ti1-xMnx)O3 powders with x = 0.01 to 0.2 were prepared by a conventional mixed-oxide
method. Raw materials BaCO3 (Fluka,99.0% purity), TiO2 (Riedel-de Han, 99.0% purity) and
MnO2 (Sigma-ALDRICH, Inc., 99.999%) were mixed and vibro-milled in ethyl alcohol for 1 hour
and then oven dried overnight at 120 C. After drying, the powders were calcined at 1250 C for 2
hours with 5 C/min heating and cooling rates.8 The calcined powders were pressed into disk-shape
by uniaxial hydraulic press at pressure of 0.5 tons to form the green pellet of 1 cm diameter. The
green pellets were placed on the alumina powder inside an alumina crucible then heat treated at
500 C for 1 hour to eliminate the PVA, followed by sintering at temperatures 1450 C for 2 hours

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with 5 C/min heating and cooling rates. Phase identification of Ba(Ti1-xMnx)O3 powder and
ceramics was performed by X-ray diffraction (XRD). The densities of the sintered ceramics were
measured by Archimedes method.9 Microstructural characterization was examined by scanning
electron microscopy (SEM). For electrical properties measurement, the sintered pellets were
polished to obtain parallel faces, and the faces were then coated with silver paint as electrodes. The
dielectric properties were measured through the LCR-meter at frequency of 100 kHz. Ferroelectric
hysteresis (P-E) loops were observed by a modified Sawyer-Tower circuit at room temperature. The
frequency of the measurement was fixed at 50 Hz.
Results and Discussion
The XRD patterns of Ba(Ti1-xMnx)O3 powder and ceramics at different Mn concentrations are
shown in Fig. 1(a) and 1(b), respectively. For the undoped and Ba(Ti0.99Mn0.01)O3, the powders
were characterized as tetragonal phase (t-BaTiO3). The small amount of hexagonal phase is also
present with increasing Mn substitutution with a complete transformation to hexagonal phase when
x reaches 10 mol%, as shown in Fig. 1(a). This observation contradicts somewhat with the results of
Langhammer et al.2 and Wang et al.5 which reported that the formation of pure hexagonal phase
was observed as Mn concentration in Ba(Ti1-xMnx)O3 exceeded 18 and 15 mol%, respectively. This
is possibly due to use of different milling methods. In those eariler works, a conventional ballmilling was employed, while the vibro-milling used in this present work results in finer powder
with apparently more reactivity, hence the pure hexagonal phase is formed more easily. However,
in this work the presence of Ba2Ti5O12 was also observed in Ba(Ti1-xMnx)O3 powders. For Ba(Ti1xMnx)O3 ceramics, the XRD patterns show that the crystal structure at room temperature also
changes from tetragonal to hexagonal as Mn concentration increases. The sample with x = 0 shows
the tetragonal phase, while x = 0.01, the amount of hexagonal phase and small amount of Ba2Ti5O12
occurs. When x increases from 0.02 to 0.2, it is found that Ba2Ti5O12 disappears and the extent of
hexagonal phase increases with increasing Mn substitution with a complete hexagonal phase when
x reaches 0.1, as shown in Fig.1(b).
The lattice constants for different x values of h-Ba(Ti1-xMnx)O3 ceramics (x=0.1 to 0.2),
according to the XRD results in Fig. 1(b), were calculated. The lattice constants of hBa(Ti0.9Mn0.1)O3 are a 5.709 and c 13.957 , which are comparable to those of h-BaTiO3
(a=5.7238 and c=13.9649 ) prepared in the reducing atmosphere at temperatures above 1430
C.1,6 As the Mn concentration increases, both the a and c constants reduce with a 5.705, 5.699
and c 13.947, 13.921 for x=0.15 and 0.2, respectively, as shown in Fig. 2. The smaller ionic
radius of Mn4+ ion (0.530 ) compared with that of the Ti4+ ion (0.605 ) leads to the reductions in
lattice constants.5

Figure 1. XRD patterns of Ba(Ti1-xMnx)O3 with x = 0 to 0.2 (a) powders, (b) ceramics

Advanced Materials Research Vols. 55-57

Figure 2. The lattice constants of


h-Ba(Ti1-xMnx)O3 ceramics (x=0.1 to 0.2)

99

Figure 3. SEM micrographs of


Ba(Ti1-xMnx)O3 ceramics (x=0.01 and 0.20)

For Ba(Ti1-xMnx)O3 ceramics with x<0.10, the SEM micrographs reveal that a bimodal
microstructure consisting of well-grown plate like grains larger than 100 m with low aspect ratios
embedded in a fine-grained (about 35 m) matrix. The extensive grain growth suggests the
occurrence of a liquid phase assisted sintering process accompanied by a secondary
recrystallization, at which some grains grow rapidly at the expense of smaller ones by a mechanism
similar to Ostwald ripening. These growth mechanisms are the same type that described by
Langhammer et al.1 and Wang et al.5,6 As x increases, the well grown grains decreases with the
extent of fine-grained increases. The bimodal microstructure with distinct sizes vanishes as the x
value exceeds 0.1, and the microstructure becomes more homogeneous with an average grain size
of 1-3 m as shown in Fig. 3.
The room temperature dielectric constant of Ba(Ti1-xMnx)O3 ceramics measured at 100 kHz
decreases from 1143 to 47 and loss decreases from 0.0477 to 0.0287 as Mn concentration increases,
as shown in Fig. 4. Similar observation has also been reported by Wang et al.5 and Li et al.15
However, there is no observable change in dielectric constant of Ba(Ti1-xMnx)O3 with hexagonal
structure (x 0.1). It was also observed that dielectric constant decreases with an increase in the
measured frequency. For comparison with the same Mn concentration of x = 0.05, the dielectric
constant observed in this study is similar to that reported by Wang et al.5 The decrease of the
dielectric properties as Mn concentration increases can be explained in terms of the change in
crystalline structure from ferroelectric tetragonal to paraelectric hexagonal phase, as shown in Fig.1.

Fig.4 The room temperature dielectric


constant of Ba(Ti1-xMnx)O3 ceramics
measured at 100 kHz

Fig.5 P-E loop of Ba(Ti1-xMnx)O3 ceramics

100

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Ferroelectric hysteresis (P-E) loops of Ba(Ti1-xMnx)O3 ceramics were observed by modified


Sawyer-Tower circuit carried out at the frequency of 50 Hz. It is found that at an applied electric
field of 15 kV/cm undoped BT ceramic exhibits remanant polarizations (Pr) of 6.87 C/cm2,
saturated polarizations (Ps) of 13.09 C/cm2 and coercive electric fields (Ec) of 2.87 kV/cm. As the
Mn concentration increases, the loop area and polarizations of Ba(Ti1-xMnx)O3 ceramics decrease
noticeably and the P-E loops cannot be clearly observed, as shown in Fig.5, and for different Mn
concentrations there is no observable change in the P-E loops. It can be said that the loop area and
polarization decrease because of the existent of paraelectric hexagonal phase.
Summary
Addition of Mn into BaTiO3 can stabilize hexagonal polymorph at room temperature. The XRD
patterns showed that the crystal structure of Ba(Ti1-xMnx)O3 at room temperature changed from
tetragonal to hexagonal as Mn concentration increased, which caused the dielectric constant and
loss decrease. The microstructure of Ba(Ti1-xMnx)O3 ceramics at low concentration revealed a
bimodal microstructure consisting of well-grown plate like grains larger than 100 m with low
aspect ratios embedded in a fine-grained (about 35 m) matrix. As the x value increased, the well
grown grains decreased with the extent of fine-grained increased. Ferroelectric hysteresis (P-E) loop
measurements indicated that Mn doped BaTiO3 with the hexagonal structure seemed to be in
paraelectric phase.
Acknowledgement
This work was supported by the National Synchrotron Research Centre (NSRC), Thailand under
grant contract No. 2550/02 and PS042550.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]

H.T. Langhammer, T. Muller, K.H. Felgner and H.P. Abicht: J. Am. Ceram. Soc. Vol.
83(2000), p. 605.
H.T. Langhammer, T. Muller, A. Polity, K.H. Felgner and H.P. Abicht: Mater. Lett. Vol. 26
(1996), p. 205.
D.K. Lee, H.I. Yoo, K.D. Becker: Solid State Ionics. (2002), p. 189.
G.M. Keith, M.J. Ramplinga, K. Sarma, N. Mc. Alford and D.C. Sinclair: J. Eur. Ceram. Soc.
Vol. 24 (2004), p. 1721.
S.F. Wang, Y.C. Hsu, J.P. Chu and C.H. Wu: Applied Physics Letters. Vol. 88 (2006), p.
042909-1.
S.F. Wang, Y.C. Wu, Y.C. Hsu, J.P. Chu and C.H. Wu: Jpn. J. Appl. Phys. Vol. 46 (2007), p.
2978.
H.T. Langhammer, T. Muller, R. Bottcher, V. Mueller and H.-P. Abicht: J. Eur. Ceram. Soc.
Vol. 24 (2004), p. 1489.
N. Phoosit, T. Tunkasiri, J. Tontrakoon and S. Phanichphant: Journal of Microscopy Society
of Thailand.Vol. 20 (2006), p. 64.
ASTM Designation C37388 (reapproved 1999), p. 119.
X. Wang, M. Gu, B. yang, S. Zhu and W. Cao: Microelectron. Eng. Vol.66 (2003), p. 855.
I. BURN: J. Mater. Sci. Vol. 14 (1979), p. 2453.
M.H. Lin and H.Y. Lu: Philosophical Magazine A. Vol. 81 (2001), p.181.
R.D. Burbank and H.T. Evans: Acta Cryst. Vol. 1 (1948), p. 330.
R.M. Glaister and H.F. Kay: Proc. Phys. Soc. Vol. 76 (1960), p. 763.
T. Li, L. Li, J. Zhao and Z. Gui: Mater. Lett. Vol. 44 (2000), p. 1.

Advanced Materials Research Vols. 55-57 (2008) pp 101-104


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.101

Induced Internal Bubble Shapes Affected Piezoelectric Behaviors of


PVDF Films
D. Suwansumpan1,a, H. Manuspiya 2,a*, P. Laoratanakul b
and A. S. Bhalla c
a

Polymer Processing and Polymer Nanomaterials Research Unit, The Petroleum and
Petrochemical College, Chulalongkorn University, Bangkok, Thailand
b
c

National Metal and Materials Technology Center, Pathumthani, Thailand

Material Research Institute, Pennsylvania State University, University park, U.S.A.


2,a*

hathaikarn@chula.ac.th

Keywords: Poly (vinylidene fluoride), Piezoelectric, Dielectric constant, Microporous PVDF films,
Bubble shapes.

Abstract. In this research, the effect of induced internal bubble shapes on dielectric behavior and
piezoelectric properties in polyvinylidene fluoride (PVDF) was studied. The bubbles were created
inside PVDF films by thermal phase inversion and AZDC blowing agent techniques. Subsequently,
PVDF films with internal bubble were stretched to change the spherical to ellipsoidal. The dielectric
constant and the loss tangent of porous PVDF films were measured as a function of frequency
range, 1 kHz-10 MHz, at room temperature by an impedance/gain-phase analyzer in different %
porosities, sizes, structures, and shapes of bubbles. It was found that at high frequency the ellipsoid
bubble shape showed more promising data, including a higher dielectric constant, less relaxation
with frequency, and lower dielectric loss than spherical shaped. Also, the measured dielectric
constant is fitted well with the Yamada model indicating 0-3 connectivity of PVDF/air bubble
composites. Moreover, the ellipsoid shape can enhance the piezoelectric properties higher than
those of spherical shape in PVDF films. Consequently, the PVDF with internal bubbles can be
proposed as another candidate to use instead of ceramic-filled PVDF in lightweight piezoelectric
applications
Introduction
In recent years, cellular and porous polymers are interested by researchers. Therefore, a novel
concept of creating internal bubbles is introduced by the charge accumulate in bulk of non-polar
polymer. However, Poly(vinylidenefluoride) (PVDF) is a well known polar-polymer materials for
acoustic transducers such as air-bone, water-bone for sound applications and underwater
hydrophone devices because of their wide bandwidth, high sensitivity, good electromechanical
properties, low power requirements, high generation force, chemical resistance, flexibility, and
toughness. In the case of underwater hydrophone device, PVDF films need to add bubbles inside for
light weight applications, low acoustic (close acoustic match of water) and mechanical impedance
[1]. A novel concept of creating internal bubble is introducing cellular or porous polymer films
which contain partial discharges inside in order to produce gas bubbles to achieve improved
electrical properties of non-polar polymer such as PP [2]. The concept is very interesting and has
not been used in investigating the space-charge in the cellular PVDF in order to improve the
drawback of PVDF film before.
In this research, the effect of internal bubble shapes on dielectric and piezoelectric behavior was
studied. The dielectric constant and the loss tangent of porous PVDF films were measured as a
function of frequency range of 1 kHz-10 MHz at room temperature by impedance/gain-phase
analyzer in different % porosity, structure, and bubbles shapes.

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Experimental: Preparation of microporous PVDF films


A. Materials
The poly(vinylidene fluoride) (PVDF) powder(#1008) material was kindly supported by Solvay
(Thailand) Limited;. Azo-dicabonamide (blowing agent) was provided by Usaco (Thailand)
Limited. The solvents used were ,-Dimetyl acetamide (DMAc, 99.5%), ,-Dimetyl formamide
(DMF, 99.8%) were purchased from Lab Scan Co., Ltd. and Triethylphosphate (TEP, 98%) was
obtained from Fluka Co., Ltd. All chemicals are used without further purification.
B. Preparation of Porous PVDF Films
Porous PVDF films are prepared by two methods; First, isothermal immersion-precipitation
method. The preparation started by dissolving in solvent at 120 oC. Polymer solutions are dispersed
uniformly on a Teflon plate. After that, immersed immediately into a distill water bath to induce
phase separation at room T. The formed membrane will wash in a series of nonsolvents and then
dried under vacuum at 120 C for annealing. Second, the blowing agent as azodicabonamide
(AZDC) with dried PVDF powder by brabender which rotor speed 50 rpm and temperature 190 oC
in 30 min Finally, a mixed powder was put on the mold and placed in compression molding
machine.[3-5]
Results and Discussion
A. Morphology Analysis of Porous PVDF Films

Figure 1 (Left) The photograph of porous PVDF produced by phase inversion method, (Right) The
photograph of porous PVDF can be obtained by AZDC compression molding.
The characterization of porous PVDF films by phase inversion process (Fig.1), these films have
thickness in range 0.1564-0.1298 mm, opaque, and smooth surface. Also, the compression molding
technique has a thickness 0.569-0.684 mm which shows a non-cellular structure (Fig 3). Although,
the photographs of films seem to be the same but the SEM micrograph reveals that 3 different
methods can yield different morphology of porous inside PVDF film that show in Figure 2.

(a)

(b)

(c)

(d)

Figure 2 The SEM micrograph of porous PVDF film by phase inversion (a,c) and OM micrograph
of porous PVDF film by AZDC compression molding technique (b,d).

Advanced Materials Research Vols. 55-57

103

The effect of bubbles shapes on dielectric behavior in porous PVDF films was studied in this work;
the films were stretching (1:1) by UTM machine in heat chamber at 90C. Thus, the bubbles in
spherical and ellipsoidal shapes were confirmed.
B. Density measurement
The apparent densities of porous PVDF films were approximately 0.89-0.92 g/cc which obtained by
Ultrapycnometer 1000. As expected, the density of the porous film is lower than that of non-porous
film (1.8894 g/cc) [6] due to the penetration of air inside the films which is suitable for lightweight
applications such as air bone and water bone.
C. Dielectric Behavior of Porous PVDF Films
Spherical
Ellipsoidal

12

(a)
(b)

Spherical
Ellipsoidal

0.20

(a)
(b)

0.18

Dielectric Loss

Dielectric Constant

(a)

0.16

10

(b)

0.12
0.10

(b)

0.08
0.06

(a)

0.14

0.04
0.02
2
1000

10000

100000

1000000

0.00
1000

1E7

10000

100000

1000000

1E7

Frequency (Hz)

Frequency (Hz)

Figure 3 Frequency dependent (a) dielectric constant and (b) dielectric loss of porous PVDF films
with different shape between spherical and ellipsoidal shape.
The dielectric properties of the PVDF films with various air fractions were measured as a function
of frequency range of 100 Hz -10 MHz. For spherical shape, their dielectric constant values
dropped rapidly at high frequency (> 1 MHz) and loss tangent increased abruptly. This phenomenon
was due to the spherical occurred more dipolar relaxation than ellipsoidal shape. The comparison of
dielectric constant in spherical and ellipsoidal shapes is shown in Fig 3. The dielectric constants of
spherical bubbles PVDF films are lower than those of ellipsoid for all bubbles PVDF films
compositions. This is related to the electric displacement generated in the ellipsoidal shape and also,
higher charge density than spherical shape [7].
D. Ferroelectric Properties
6

Polarization(C/cm )

Polarization(C/cm )

3
2
1
0
-1
-2

3
2
1
0
-1
-2

-3

-3

-4

-4

-5

-5
-6

-6
-80

-60

-40

-20

20

40

Electric field(kV/cm)

60

80

-60

-40

-20

20

40

60

Electric field(kV/cm)

Figure 4 Comparative hysteresis loop between (left) spherical and (right) ellipsoidal bubble shapes
in PVDF matrix by blowing agent methods.

104

Smart Materials

The hysteresis loop (Fig.4) can be suggested that this material have ferroelectric properties and can
be classified in soft ferroelectric material when compare with others polymer [8]. The remanent
polarization (Pr) and Pmax of ellipsoidal bubble shape in porous PVDF films were higher than those
of spherical shapes which provide higher piezoelectricity.
E. Piezoelectric Properties
The highest piezoelectric coefficient up to 7 pC/N for particular poling conditions (nearly
breakdown 50 kV/mm at 90C) is reached when the mechanical deformation provides ellipsoid
shape in porous PVDF film.
Summary
The Air/PVDF 0-3 connectivity was produced by phase inversion and azodicabonamide (AZDC)
chemical blowing agent technique. From TG-DTA result, it was found that internal bubble has no
effect on a decomposition temperature and a stretching PVDF film (ellipsoidal shape) has no effect
on melting temperature but slightly affects on -phase crystallinity of PVDF film confirmed by
XRD diffraction. However, dielectric properties of non-cellular were slightly different to those of
the cellular structure (from phase inversion) and considerably lower when compared with the pure
PVDF films (non-porous). As expected, an ellipsoidal bubble shape can enhance dielectric
properties than spherical shape in porous PVDF films. The reason is the ellipsoidal shape created
the electric displacement in bubbles and their lower air gap increasing dipole density inside PVDF
films. These ellipsoidal shapes also have stable loss tangent in the frequency range of 1 kHz to 10
MHz which indicated the low relaxation behavior. Moreover, Yamada model could fit the measured
dielectric constant well for all composites indicating 0-3 connectivity of air/PVDF composites.
Finally, the ellipsoid shape can be enhanced d33 up to 7 pC/N, because of ideally charge at the
interface between the two electrets (air-PVDF). Piezoelectricity arises because the charges are
displaced relative to the electrode under mechanical stress.
References
[1]

[2]
[3]
[4]
[5]
[6]

[7]
[8]

Lines M. E. and Glass A. M., in: Principles and Applications of Ferroelectrics and Related
Materials (Oxford Classic Text in the Physical Sciences, Edited by Lines M E and Glass A M,
Clarendon, 1997).
Neugschwandtner G. S., Schwdiauer R., Bauer-Gogonea S., Bauer S., Paajanen M., Lekkala
J.: J. Appl. Polym. Sci, (2001), p.89.
Minghao G., Jun Z., Xiaolin W., Haijun T. and Litian G.: Desalination, Vol 192 (2006), p.160.
E. Quartarone, P. Mustarelli and A. Magistris: J. Phy. Chem B Vol 106 (2001), p. 10828.
Park, C.P., in: Handbook of Polymeric Foams and Foams Technology (Edited by Hanser
Publisher, Munich, 1991)
Kohpaiboon, K.,and Manuspiya, H in : 0-3 Connectivity of PVDF/BST Piezoelectric
Composites, (M.S. thesis, The petroleum and petrochemical college, chulalongkorn university,
Thailand, 2007).
Dias, C.J. and Das-Gupta, D.K: IEEE Trans. on Dielectric and Material Insul Vol. 3. (1996),
p.706.
G. S. Neugschwandtner and R. Schwodiauer: Appl. Phys. Lett, (2001).

Advanced Materials Research Vols. 55-57 (2008) pp 105-108


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.105

Dielectric Properties Enhancement in Polybenzoxazine Composite at


Multi-Frequency Range
N. Krueson1, H. Manuspiya1, *, P. Laoratanakul2 and H. Ishida3
1

The Petroleum and Petrochemical College, Chulalongkorn University, Bangkok, Thailand


2
3

National Metal and Materials Technology Center, Pathumthani, Thailand

Department of Macromolecular Science, Case Western Reserve University, USA


1,*

hathaikarn.m@chula.ac.th

Keywords: Polybenzoxazine-barium strontium titanate composite, surface modification, dielectric


properties

Abstract. This research proposed a novel nano barium strontium titanate (BST) powderpolybenzoxazine composite as a new dielectric material. In this work, the dielectric properties of a
surface-treated BST powder-polybenzoxazine composite were studied. The surface of the BST
powders were modified by using three different chemicals: 3-aminopropyl-trimethoxysilane,
benzoxazine monomer and phthalocyanine. The distribution of the BST powders in the
polybenzoxazine matrix was observed by SEM. The dielectric constants of the composites with a
function of frequency (1 kHz10 MHz) were investigated. It was found that the composites with
modified BST powders showed good distribution in the polybenzoxazine matrix, and the dielectric
constants were also much enhanced than those with untreated BST powders. In comparisons among
the three modification methods, the composite with the silane coupling modified BST powder
showed significantly in dielectric constant improvement while the composite with the benzoxazine
and phthalocyanine modified BST powders displayed lower dielectric loss due to the modified
powder dispersed well in the polybenzoxazine matrix.
Introduction
Polymer-ceramic composites are candidate dielectric material in embedded capacitor application
because they combine the processability of polymers with high dielectric constant of ceramics,
resulting in low processing temperature and operating cost [1]. Previous study was proposed a novel
Polybenzoxazine (PBZ)-BST with 0-3 connectivity as a new dielectric material. The results from this
work show that the dielectric constant of the composite can be enhanced much higher than that of pure
polybenzoxazine. But the composite still has high dielectric loss for using at high frequency [2].
However, it was reported that the uniform distribution of ceramic filler is one of the important factors
that strongly affect the dielectric properties in 0-3 polymer-ceramic composites [3]. Thus the surface
modification of ceramic fillers was interested as the method to improve the dielectric properties in
PBZ-BST composites in this research.
Experimental
A. Preparation of Benzoxazine Monomer
The synthesis of aniline based benzoxazine monomer (BA-a) is based on the reaction of bisphenol A,
paraformaldehyde, and aniline at the molar ratio of 1:4:2 by solventless method. The starting
materials were mixed together without solvent at temperature of 100C for 30 min. Then the product
with high yellow viscous liquid was obtained. This viscous product was dissolved in chloroform and
washed sequentially with 0.1 N NaOH and water dried over Na2SO4. The chloroform was then
removed and the solid products were washed by cool methyl alcohol to obtain white powder
benzoxazine monomer.

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B. Preparation of Barium Strontium Titante by Sol-Gel Process


Barium strontium titante (Ba0.3Sr0.7TiO3) was prepared by dissolving 0.3 mole of barium acetate and
0.7 mole of strontium acetate separately in acetic acid, followed by the addition of methanol to each
one. Then an equimolar amount of titanium (iv) n-butoxide was added into this mixture under
vigorous stirring. When the solution became a gel, it was calcined by using 2-step thermal
decomposition to decompose the solvent and crystallize Ba0.3Sr0.7TiO3 powders.
C. Surface Modification of BST powders by Silane Coupling, Benzoxazine Monomer, and
Phthalocyanine
3-aminopropyl-trimethoxysilane (1 g) was dissolved in water/ethanol (5ml/95ml) and the solution
was then mixed with BST powders (40 g). The treated suspension was centrifuged and subsequently
washed by ethanol and dried in a vacuum oven at 50C. Finally, the coupling agent modified BST
particles were obtained. For surface treatment by benzoxazine monomer, the benzoxazine solution
concentration at 5wt% in THF was slowly added dropwise to stirring BST particle/THF slurry. Then
the mixture was stirred for 1 hr and evaporated THF out at about 70 C. For the last treatment, 0.1 wt%
of phthalocyanine powder was dissolved in DMAc solvent then added the solution into stirring BST
particle/DMAc slurry. The mixture was then stirred for 1 hr and evaporated DMAc out at 200C.
After that the residual solvent was removed again by drying in a vacuum oven overnight.
D. Composite Preparation
The monomer and BST powder with 30wt%, 50wt% and 80wt% were firstly mixed together by melt
mixing method to prevent the separation between two phases after fabrication step. Then the mixtures
were fabricated as the composite specimens with the thickness of 1.5 mm and 15 mm in diameter by
compression molding.
Results and Discussion
A. Composite with Unmodified BST Powders
1.) BST Powders Distribution

Figure 1 SEM micrographs of the composites with (a) 30 wt%, (b) 50 wt%, and (c) 80 wt% of BST
Figure 1 (a)-(c) shows the cross-section of the composites with different BST loadings. The white and
gray colors represent the filler and the polybenzoxazine matrix, respectively. From the micrographs, it
reveals that the BST powders distribution was not uniform even in the lowest content of BST fillers
(30 wt %) and the agglomeration and pores (represent by black color) tended to form when the filler
loading volume increased. However, the agglomeration of BST is formed by the high surface energy
of the sol-gel BST nanoparticles.
2.) Dielectric Properties
From Figure 2, it can be seen that at the same frequency, dielectric constants of the composites
increased with the volume fraction of the BST ceramic powders. Because at higher ceramic filler

Advanced Materials Research Vols. 55-57

107

loading volume, the ceramics come closer then the dipole-dipole interaction increase and contribute
to higher dielectric constant [4]. However, the loss tangents of all composites are greater than pure
polybenzoxazine and tend to increase at higher ceramic content. The increasing of the loss tangent
value was attributed to the formation of porosity in the specimens.
0.20

60
Room temperature

PBZ
30 wt% BST
50 wt% BST
80 wt% BST

Dielectric constant

50
45
40

0.18
0.16

Dielectric loss

55

35
30
25
20
15

0.12
0.10
0.08
0.06
0.04

10

0.02

5
0
3
10

0.14

Room temperature

PBZ
30 wt% BST
50 wt% BST
80 wt% BST

10

10

10

10

0.00
3
10

Frequency (Hz)

10

10

10

10

Frequency (Hz)

Figure 2 Frequency dependence of dielectric constant and dielectric loss for the composites at
various BST contents.
B. Composite with Modified BST Powders
1.) Effect of Surface Modification on BST Distribution
To study the effect of surface modification on BST dispersion, the composite with 50wt% BST was
investigated in this work. Figure 3 (a)-(c) show SEM micrographs of the composites with modified
BST powders by silane coupling agent, BA-a monomer and phthalocyanine, respectively. The
micrographs reveal that the dispersion of modified BST powders was improved when compare with
the composites with unmodified BST powders (Figure 1 (b)). In comparison among silane coupling
agent, BA-a monomer and phthalocyanine modification of BST, it was observed that the composites
with phthalocyanine and benzoxazine monomer modification showed better in the ceramic dispersion
improvement than the silane coupling method. Because the molecules of phthalocyanine and
benzoxazine monomer are composed of the aromatic rings which are bulky group inhibiting the
agglomeration of BST particles.

Figure 3 SEM micrographs of the composites with 50 wt% BST modified with (a) silane coupling
agent, (b) BZ monomer and (c) phthalocyanine.
2.) Effect of Surface Modification on Dielectric Properties of Composite
Figure 4 illustrate the comparisons of dielectric constant and dielectric loss of the composites with
different BST surface modification method at 50wt% BST. It was found that the silane coupling
modification can improve in the dielectric constant of the composite higher than those in
phthalocyanine and the benzoxazine monomer modification. Because silane coupling agent can form
chemical bonds on the surface of BST powders due to this way the polarizability in the system could
be enhanced, resulting in the increasing of the dielectric constant [5]. In the case of dielectric loss of
the composites it can be seen that all three methods of surface modification could obviously lower the

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dielectric loss of the composites at high frequencies compared with the untreated BST composites. In
comparison among the three surface modification methods, it was found that the phthalocyanine and
benzoxazine monomer could lower the loss tangent of the composites than the silane coupling
method. The lower in dielectric loss was due to the BST dispersion enhancement of the
phthalocyanine and benzoxazine monomer, consequent in the lower of porosity in the composites.
Because it was reported that porosity is the important factor that mainly increases the loss in the
composite system [6]. The porosity could be generated from the segregation of different surfaces
between polymer matrix and ceramic particles and will be large when composite was pressed by
mechanical loading.
0 .1 6

14

0 .1 2

10

Dielectric loss

Dielectric constant

50
50
50
50

0 .1 4

12

8
6
4

50 w t% BS T
50 w t% treated silane

50 w t% treated BZ
50 w t% treated Pc

0
3
10

w t%
w t%
w t%
w t%

BST
tre a ted sila ne
tre a ted B Z
tre a ted P c

Room tem perature

0 .1 0
0 .0 8
0 .0 6
0 .0 4
0 .0 2

Room tem perature


0 .0 0

10

10

Frequency (H z)

10

10

10

10

10

10

10

Frequ en cy (H z)

Figure 4 Frequency dependence of dielectric constant and dielectric loss for the composites at 50
wt% BST with different surface modification methods.
Summary
The higher amount of BST powders can increase dielectric constant of the composite and also
increased the agglomeration of the powders at the same time. However this problem can improve by
the surface modification of BST before mixing in polymer matrix. It was found that phthalocyanine
and BZ monomer modification showed lower in dielectric loss due to the BST dispersion
enhancement. Silane coupling agent not only lowers the loss tangent, it also increase the dielectric
constant of the composite due to the chemical bond formed on the BST surface.
Acknowledgment
The research fund was granted by the Government Research Budget (GRB_47_50_63_04) and
partially fund from the National Excellence Center for Petroleum, Petrochemicals, and Advanced
Materials, Thailand. The dielectric measurement was supported by MTEC, Thailand.
References
[1]
[2]

[3]
[4]
[5]
[6]

Y. Rao, S. Ogitani, P. Kohl and C.P. Wong: Appl. Pol. Sci. Vol. 83 (2006), p. 1084.
G. Panomsuwan, S. Kaewwata, H. Manuspiya and H. Ishida in: Proceedings of the 2nd IEEE
International Conference on Nano/Micro Engineered and Molecular Systems, Bangkok,
Thailand (2007), p. 497.
L. Ramajo, M. Reboredo and M. Castro: Compos Part A. Vol. 36 (2005), p. 1267.
D.H. Kuo, C.C. Chang, T.Y. Su, W.W. Wang and B.Y. Lin: J. Eur. Ceram. Soc. Vol. 21 (2004),
p.1171.
M.G. Todda and F.G. Shi: J. Appl. Phys. Vol. 93(7) (2003), p. 4551.
S.D. Cho, J.Y. Lee and K.W. Paik: Mater. Sci. Eng. B. Adv. Technol. 110 (2004), p. 233.

Advanced Materials Research Vols. 55-57 (2008) pp 109-112


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.109

Effect of Thermal Treatment on Dielectric Properties of


0.8Pb(Zr1/2Ti1/2)O3 - 0.2Pb(Co1/3Nb2/3)O3 Ceramics
A. Prasatkhetragarn1,a, S. Ananta1,b, R. Yimnirun1,c and D. P. Cann2,d
1

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand

Materials Science, Department of Mechanical Engineering, Oregon State University, Corvallis, OR


97331, U.S.A.
a

Prasatkhetragarn@yahoo.com, bSupon@chiangmai.ac.th, cRattikornyimnirun@yahoo.com,


d
Cann@engr.orst.edu

Keywords: PCNPZT, MPB, Dielectric properties, Thermal treatment

Abstract. A combination between piezoelectric (Pb(Zr1/2Ti1/2)O3; PZT) and relaxor ferroelectric


(Pb(Co1/3Nb2/3)O3; PCN) materials with a formula of 0.8Pb(Zr1/2Ti1/2)O3 - 0.2Pb(Co1/3Nb2/3)O3 has
been prepared with solid-state reaction (the columbite-wolframite precursor method). This specific
composition was selected for investigation because it is close to a morphotropic phase boundary
(MPB) between the tetragonal and pseudo cubic phases. The phase formation behavior and
microstructure were studied using x-ray diffraction (XRD) and scanning electron microscopy
(SEM), respectively. The dielectric properties of the compound were measured and discussed. The
ceramics were also heat-treated at 800 oC. The results showed that the dielectric properties of the
compound depended significantly on the heat treatment conditions. Most importantly, this study
showed that the addition of PCN can improve the dielectric characteristics in PZT ceramics.
Introduction
Lead-based perovskite-type solid solutions consisting of ferroelectric and relaxor materials have
attracted great interest because of their excellent dielectric, piezoelectric, and electrostrictive
properties, which are useful in actuating and sensing applications [1]. Of the lead-based complex
perovskites, lead zirconate titanate [Pb(Zr0.52Ti0.48)O3 or PZT] ceramics have been investigated
from both fundamental and applied viewpoints [2]. A solid solution between PZ and PT of
Pb(Zr1xTix)O3 (PZT) was found to host exceptionally high value for dielectric and piezoelectric
properties for compositions close to the morphotropic phase boundary (MPB). This MPB is located
at a PbZrO3:PbTiO3 of 0.52:0.48 and separates the Ti-rich tetragonal phase from the Zr-rich
rhombohedral phase [2]. Furthermore, it has a high TC of 390 oC, which allows piezoelectric
devices to be operated at relatively high temperatures. Most commercial PZT ceramics are designed
in the vicinity of the MPB with various doping methods in order to achieve high properties.
Lead cobalt niobate Pb(Co1/3Nb2/3)O3 is a perovskite ferroelectric exhibiting the diffuse phase
transition at -30 oC. The structure is cubic at room temperature. In this compound, the octahedral
sites of the crystal are randomly occupied by Co2+ and Nb5+ ions [3]. On the basis of this approach,
solid solutions of PZT and PCN are expected to synergistically combine the properties of both the
normal ferroelectric PZT and relaxor ferroelectric PCN, which could exhibit piezoelectric and
dielectric properties that are better than those of the single-phase PZT and PCN [3,4].
Thermal annealing was observed to be effective on microstructure and dielectric properties of
materials. Normally, thermal annealing can be used to improve grain size and reduce oxygen
vacancy of ceramics during lead volatilization in calcinations and sintering process [5].
Improvement of dielectric and ferroelectric properties of ceramics was also observed in PZT-PZN
after thermal annealing [5]. In this study, effect of annealing on microstructure and dielectric
properties of specific formula is 0.8Pb(Zr1/2Ti1/2)O3 - 0.2Pb(Co1/3Nb2/3)O3 ceramics has been
investigated and discussed.

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Experimental
The specific composition ceramics as a formula 0.8Pb(Zr1/2Ti1/2)O3 - 0.2Pb(Co1/3Nb2/3)O3 was
selected for investigation because it is close to a morphotropic phase boundary (MPB) between the
tetragonal and pseudo cubic phases as reported earlier [6]. Reagent-grade oxides of PbO (99.9%),
CoO (99.9%), Nb2O5 (99.9%), ZrO2 (99.9%) and TiO2 (anatase-structure) (99.9%) were used as
raw materials. The columbite CoNb2O6 and wolframite ZrTiO4 precursors were weighed and
introduced into the batch calculations. CoNb2O6 and ZrTiO4 powders were prepared at calcination
temperatures of 1100 and 1450 oC for 2 h, respectively [7]. In the present work, 0.8Pb(Zr1/2Ti1/2)O3
- 0.2Pb(Co1/3Nb2/3)O3 sample was prepared from ZrTiO4, CoNb2O6, and PbO powders. PCN-PZT
powders were synthesized using the solid-state reaction of these raw materials and mixed by a
vibratory-milling technique in ethanol for 6 h. After drying, the product was calcined in an alumina
crucible at a temperature of 950 oC. The calcined powders were uniaxially cold-pressed at 5000 psi
into disc-shaped pellets with a diameter of 12.7 mm and a thickness of 1 mm, with 3 wt% poly
(vinyl alcohol) (PVA) added as a binder. Following binder burnout at 500C, the pellets were
sintered at 1200 oC for 2 h at a heating/cooling rate of 5 oC/min. To determine the effect of thermal
annealing, the high-density samples were thermally annealed at 800 oC for 24 hours. The phase
structure of the powders was analyzed via X-ray diffraction (XRD; Bruker-AXS D8). The
microstructures of the sintered samples were examined using scanning electron microscopy (SEM;
JEOL JSM-840A). The dielectric properties of the samples were measured using an automated
measurement system. An Agilent 4284A LCR meter was used to measure the dielectric properties
over a wide temperature range using a NorECS ProboStat high temperature measurement cell.
Results and Discussion
The XRD patterns of 0.8PZT-0.2PCN ceramics are shown in Fig. 1(a). It can be seen that a
complete crystalline solution of the perovskite structure is formed throughout the specific
compositional without the presence of pyrochlore or unwanted phases. The XRD patterns of the
0.8PZT-0.2PCN composition show a range in symmetry between the tetragonal and pseudo cubic
perovskite types [6]. It is well known that in the pseudo cubic phase, the (200) profile shows a
single narrow peak, while in the tetragonal phase, the (200) profile splits into two peaks [6] as
shown in Fig. 1(b). This observation is obviously associated with the composition showing the
coexistence of two symmetries, which in this case are the tetragonal and pseudo cubic phases. The
electrical data described later on will further support this assumption.
The SEM images in Fig. 2 reveal that annealing resulted in significant changes in the
microstructure of the 0.8PZT-0.2PCN ceramics. Fig. 2(a) has shown the sintered ceramics without
annealing, most grains are observed to have regular shapes. For annealing ceramics as shown in
Fig. 2(b), melted grains are observed. Thermal absorption in annealed ceramics has imposed
significant changes on grains of ceramics. Interestingly, the thermal annealing has not only affected
on microstructure, but also affected on electrical properties that will be described later.

(a)
(b)
o
o
Figure 1. XRD patterns of sintered (1200 C) and annealed (800 C for 24 h) ceramics
in 0.2PCN-0.8PZT system.

Advanced Materials Research Vols. 55-57

(a)

111

(b)

Figure 2. SEM micrographs of sintered and annealed ceramics in 0.2PCN-0.8PZT system.

The temperature dependence of the dielectric constant measured at 1 kHz for the (1-x)PZT-(x)PCN
samples with x = 0.1 - 0.5 is shown in Fig. 3. The compositions of the (1-x)PZT-(x)PCN system
show broad dielectric peaks with an increase in the concentration of PCN, which indicates a diffuse
phase transition. It should be noted that the formation of MPB could be clearly seen by the crystal
structure analysis as described earlier. As is well known, the value of the dielectric and ferroelectric
properties of a solid solution with MPB usually maximize approximately at the MPB. An anomaly
at the MPB has been observed by our group in solid solution (x)PZT-(1-x)PNN [8]. In addition,
here the argument that the MPB composition should be at x = 0.2 in (1-x)PZT-(x)PCN is supported
by all the XRD and electrical data.
Temperature dependent dielectric constant (r) of both sintered and annealed 0.8PZT-0.2PCN
ceramics is shown in Fig. 4. The results show significant influence of thermal annealing on
dielectric properties of ceramics in PZT-PCN system. Thermal annealing was observed to be
effective on microstructure and dielectric properties of materials. Normally, thermal annealing can
be used to improve grain size and reduce oxygen vacancy of ceramics [5]. Improvement of
dielectric and ferroelectric properties of ceramics was also observed in PZT-PZN after thermal
annealing [5]. Here the results show that the maximum dielectric constant of annealed ceramics
(30,000 at Tc ~ 300) is lower than that of sintered ceramics (64500 at Tc ~ 310) as shown in Fig. 4.
Therefore, after annealing at 800 oC, dielectric properties of 0.8PZT-0.2PCN ceramics are different
from earlier reported [5] possibly due to the structure of the annealed ceramics is changed from
tetragonal to pseudo cubic, melting in annealed ceramics and shifting of MPB.
70000

70000
x = 0.1
x = 0.2
x = 0.3
x = 0.4
x = 0.5

50000

60000

Relative Permittivity (r)

Relative Permittivity (r)

60000

40000

30000

20000

Unannealed
Annealed 24 h

50000
40000
30000
20000
10000

10000

0
100

200

300

400

500

Temperature (oC)

Figure 3. Dielectric constant of (x)PCN (1x)PZT


samples with x = 0.1 - 0.5 measured at 1 kHz.

100

200

300

400

500

Temperature (oC)

Figure 4. Dielectric constant of sintered and


annealed ceramics in 0.2PCN-0.8PZT system.

Summary
The microstructure and dielectric properties of specific 0.8PZT-0.2PCN ceramics formed via the
precursor process were investigated. Thermal annealing was observed to influence on

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microstructure and dielectric properties of PZT-based ferroelectric ceramics. After annealing at


800 C for 24 hours, the results show that the maximum dielectric constant of annealed (30,000 at
Tc ~ 300) is lower than that of sintered ceramics (64500 at Tc ~ 310). This is probably due to the
structure of ceramics change from tetragonal to pseudo cubic, melting in annealed ceramics and
shifting of MPB.
Acknowledgement
This work was supported jointly by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science
and Technology, Thailand, through its program of Center of Excellent Network, Graduate School
and Faculty of Science, Chiang Mai University.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

A.J. Moulson and J.M. Herbert: Electroceramics: Materials, Properties, Applications, (Wiley
Publications, United Kingdom 2003).
S.-E. Park and T.R. Shrout: IEEE Trans. Ultrason. Ferroelectr. Freq. Control Vol. 44 (1997),
p. 1140.
T. Hachiga, S. Fujimoto and N. Yasuda: J. Phys. D Vol. 20 (1987), p. 1291.
R. Yimnirun, S. Ananta and P. Laoratanakul: Mater. Sci. Eng. B Vol. 112 (2004), p. 79.
N. Vittayakorn, G. Rujijanagul and D. P. Cann: J. Alloy and Compounds. Vol. 440 (2007), p.
259.
A. Prasatkhetragarn, N. Vittayakorn, S. Ananta, R. Yimnirun and D. P. Cann: Jpn. J. Appl.
Phys. Vol. 47 (2008), p. 998.
A. Prasatkhetragarn, R. Yimnirun and S. Ananta: Ferroelectrics Vol. 356 (2007), p. 203.
N. Vittayakorn, G. Rujijanagul, X. Tan, M. A. Marquardt and D. P. Cann: J. Appl. Phys. Vol.
96 (2004), p. 5103.

Advanced Materials Research Vols. 55-57 (2008) pp 113-116


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.113

Influence of Fabrication Processing on Perovskite Phase Formation of


KNN-BZT
M. Sutapun1, R. Muanghlua2, C-C Huang3, D. P. Cann3, W. C. Vittayakorn4
and N. Vittayakorn1,a
1

Materials Science Research Unit, Department of Chemistry, Faculty of Science, King Mongkuts
Institute of Technology Ladkrabang, Bangkok, Thailand 10520
2

Electronics Research Center, Faculty of Engineering, King Mongkuts Institute of Technology


Ladkrabang, Bangkok Thailand 10520

Materials Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon


State University Corvallis, Oregon, 97331, USA

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand 50200
a

e-mail: naratipcmu@yahoo.com

Keywords: Lead-free piezoelectric ceramics; Dielectric properties; perovskites; (K0.5Na0.5)NbO3;


Bi(Zn0.5Ti0.5)O3

Abstract The binary system of (1-x)(K1/2Na1/2)NbO3xBi(Zn1/2Ti1/2)O3; x = 0.0-0.30 ceramics was


fabricated by conventionally mixed oxide and two-stage mixed oxide methods. Phase development
of calcined powders and the crystal structure of sintered ceramics were analyzed by X-ray
diffraction (XRD). The microstructure analyses were undertaken by scanning electron microscopy
(SEM). In the conventional method, the perovskite phases were obtained for compositions
containing only 10 mol % KNN. For compositions above this amount, a complex mixture of phases
was observed. However, the complete solid solution of perovskite phase, prepared by twostage
mixed oxide, was retained up to 20 mole % BZT content. The experiments in this study suggest that
the two-stage mixed oxide method helps to stabilize the perovskite phase better, when compared
with the conventional method.
Introduction
Piezoelectric materials based on Pb(Zr1-xTix)O3 (PZT) ceramics have been widely used, due to their
excellent piezoelectric and dielectric properties at the morphotropic phase boundary(MPB) [1].
However, the use of lead-based ceramics has caused serious environmental problems because of the
high toxicity of lead oxide [2]. Alkali niobate K0.5Na0.5NbO3 (KNN), a solid solution of
ferroelectric KNbO3 and antiferroelectric NaNbO3, is thought to be a promising candidate for leadfree piezoelectric ceramics because of its high Curie temperature (420 C) and large
electromechanical coupling factors [2]. Bi(Zn1/2Ti1/2)O3 (BZT) is a ferroelectric, which has a Zn2+
and Ti4+ complex on the B-site of ABO3 perovskite structure, with a tetragonal symmetry [4, 5].
The BZT exhibits a high Tc and tetragonality enhanced through solid solution with PbTiO3[4].
However, BZT is unstable in pure form and can only be stabilized under high pressures or in solid
solutions with other perovskite end members [3, 4]. In order to develop lead-free piezoelectric
materials, KNN was used for this research to stabilize the BZT perovskite phases in a solid solution.
Both the conventionally mixed oxide and two-stage mixed oxide methods have been used in
synthesizing the KNN-BZT ceramic. Finally, a comparison of the important dielectric properties
was made to identify the optimum processing conditions.
Experimental
The (1-x)(K1/2Na1/2)NbO3xBi(Zn1/2Ti1/2)O3; x = 0.0-0.30 lead-free ceramics were prepared by the
conventionally mixed oxide and two-stage mixed oxide methods. Both methods used high purity

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AR grade K2CO3 (99.0%), Na2CO3 (99.5%), Bi2O3 (99.5%), Nb2O5 (99.9%), ZnO (99.0%) and
TiO2 (99.0%). Alkali carbonates were used as a starting material, which had been treated carefully
by a special drying process before use. These powders were placed in an oven at 230C for 2 days
and then stored in a moisture-free vessel. For the conventionally mixed oxide method, KNN-BZT
ceramics were prepared by mixing starting reagent powders in the desieved stoichiometry and ballmilling in polyethylene, with ethanol and stabilized zirconia (YTZ) media, for 18 h After drying,
the mixture was calcined at 850oC for 4 h. For the two-stage mixed oxide method, (K0.5Na0.5)NbO3
(KNN) powders were prepared first, followed by a reaction with Bi2O3, Nb2O5 and TiO2 to form the
KNN-BZT solid solution. Uncalcined powders were weighed according to the following chemical
reaction equation and characterized by TG-DTA (Perkin Elmer). The microstructure analyses were
undertaken by scanning electron microscopy (SEM, Leo 1455VP). The calcined powders, with
polyvinyl alcohol (PVA) added as binder, were pressed into pellets of 15 mm diameter and ~ 2 mm
thickness, and sintered at 1,000C in KNN-atmosphere for 2 h in a closed alumina crucible. For
dielectric measurement, sample surfaces were polished and painted with silver paste. Dielectric
properties were measured using an LCR meter (HP-4284, HewlettPackard Inc.).
Results and Discussion
TG-DTA curves are given in Figure 1(a) and (b) for the conventional method (K2CO3, Na2CO3,
Bi2O3, Nb2O5, ZnO and TiO2) and two-stage method (KNN, Bi2O3, ZnO and TiO2), respectively.
The TGA curve, showing overall weight loss, was equal to 32.5% for the conventional method and
~24.5% for the two-stage method. The DTA curve showed an endothermic peak positioned at
around 114-197oC and 115-179oC for the conventional method and two-stage method, respectively,
which associated with the decomposition of water molecules. Furthermore, the TGA curve showed
a 4.37 % and 3.51% weight loss at between 400C and 600C for the conventional method, which
associated with the decarbonation of K2CO3 and Na2CO3, respectively. However weight loss was
not observed at all in the same temperature for the two-stage method. The endothermic peaks,
appearing at 850oC for both methods, should be correlated to the phase transition of perovskite
structure because there was no weight loss on the TGA curves. These data were used to define the
calcined temperature of the perovskite phase.

Figure 1 TG-DTA curves for the powder mixture of the starting reagent for (a) the conventionally
mixed oxide method and (b) the twostage mixed oxide method.
XRD patterns of the sintered (1-x) KNN xBZT ceramics for both methods are shown in Figure
2(a) and (b). In the conventional method, the perovskite phases were obtained for compositions
containing only 10 mol % KNN. For compositions above this amount, a complex mixture of phases
was observed. However the complete solid solution of perovskite phase prepared by two stages was
retained up to 20 mole% BZT content. The experiments in this study suggest that the two-stage
method helps to stabilize the perovskite phase better, when compared to the conventional method.

Advanced Materials Research Vols. 55-57

115

Figure 2 XRD patterns of the (1-x)KNN xBZT powders calcined at 850 oC for 4 h, obtained by
(a) the conventional mixed oxide method and (b) the two-stage mixed oxide method.

G.S. ~ 0.4 m

G.S. ~ 0.9 m

G.S. ~ 0.3 m

G.S. ~ 0.5 m

Figure 3 SEM micrographs of the (1-x)KNN xBZT powders calcined at 850 oC for 4 h, obtained
by the conventional mixed oxide method with (a) x = 0.1, (b) x = 0.2, and two-stage mixed oxide
method with (c) x = 0.1 and (d) x = 0.2.
Figure 3 (a), (b), (c) and (d) show SEM micrographs of KNN-BZT powders for both methods, in
which the average particle size was seen to increase with increasing BZT. However, there were no
significant changes in grain size in the different preparation methods. Dielectric constant (r) and
loss tangent (tan () at room temperature in both methods are shown in Figure 4. When compared to
the conventional method, the two-stage method produces a slightly higher dielectric constant as
well as a lower loss tangent. This may be attributed to the heterogeneous composition of ceramics
synthesized by the conventional method. These results indicated that the two-stage method helps to

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stabilize the perovskite phase and produces ceramics with better dielectric properties when
compared to the conventional method.

Figure 4 Dielectric constant (r) and loss tangent (tan ()) of (1-x)KNNxBZT ceramics at room
temperature.
Summary
The properties of (1-x)KNN-xBZT; x = 0.0-0.3 ceramics prepared by conventional and twostage
methods were investigated. Perovskite phase formation behavior and dielectric properties were
found to depend on the the methods of preparation. In the conventional method, the perovskite
phases were obtained for compositions containing only 10 mol % KNN. For compositions above
this amount, a complex mixture of phases was observed. However the complete solid solution of
perovskite phase prepared by twostage mixed oxide was retained up to 20 mole % BZT content. A
better dielectric property was found for the ceramics synthesized by the two-stage method. The
higher chemical homogeneity in ceramics synthesized by the two-stage method is the main reason for the
higher dielectric constant.

Acknowledgements
This work was supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), National Research Council of Thailand (NRCT) and King Mongkuts Institute of
Technology Ladkrabang (KMITL).
References
[1]
[2]
[3]
[4]

G. H. Haertling: J. Am. Ceram. Soc. Vol. 82 (1999), p. 797.


T. Takenaka and H. Nagata: J. Eur. Ceram. Soc. Vol. 25 (2005), p. 2693.
M. R. Suchomel and P. K. Davids: Appl. Phys. Lett. Vol. 86 (2005), p. 262905.
M. R. Suchomel, A. M. Fogg, M. Allix, H. Niu, J. B. Claridge and M. J. Rosseinsky: Chem.
Mater. Vol.18 (2006), p. 4987.

Advanced Materials Research Vols. 55-57 (2008) pp 117-120


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.117

Effect of Lead Nickel Niobate Substitution on Phase Transitions of Lead


Zirconate Ceramics Prepared by the Solid State Reaction Method
S. Wirunchit1, P. Laoratanakul2 and N. Vittayakorn1,a
1

Materials Science Research Unit, Department of Chemistry, Faculty of Science, King Mongkuts
Institute of Technology Ladkrabang, Bangkok, Thailand 10520
2

National Metal and Materials Technology Center (MTEC), Pathumthani 12120, Thailand
a

naratipcmu@yahoo.com

Keyword: Antiferroelectric Materials, Ferroelectric, Lead Zirconate

Abstract The solid solution between the antiferroelectric, PbZrO3 (PZ), and relaxor ferroelectric,
Pb(Ni1/3Nb2/3)O3 (PNN), was synthesized by the columbite method. The phase structure and phase
transition of Pb(Zr1-x(Ni1/3Nb2/3)xO3 (PZNN), where x = 0.0 x 0.50, were investigated. The
samples were kept at the calcination temperature of 900C for 4 h and at the sintering temperature
of 1,150C for 2 h. Phase formation and phase transition of PZNN were investigated by x-ray
diffraction (XRD) and thermal analysis, respectively. It was found that the structure of sintered
pellets is orthorhombic for 0.0 x 0.10, rhombohedral for 0.20 x 0.30 and pseudo-cubic for x
= 0.5. DSC measurement shows that in the antiferroelectric (AFE) phase ferroelectric (FE) phase
and FE to paraelectric (PE) phase; phase transformation temperatures decrease with increasing PNN
concentration. The AFEFE phase transformation was detected for compositions 0.00 x 0.08.
Introduction
Lead zirconate, PbZrO3 (PZ), is considered to be an excellent candidate as a key material of
antiferroelectric ceramics [1-3]. At room temperature, PZ has an orthorhombic structure, with a =
5.87 , b = 11.74 and c = 8.20 [4], and an antiferroelectric (AFE) phase. It undergoes the AFE
to a paraelectric (PE) phase and transforms from an orthorhombic structure to a cubic structure at
236C [4]. It is reported that a ferroelectric (FE) phase exists over a very narrow temperature range
(230-233C) [5-8]. Lead nickel niobate (Pb(Ni1/3Nb2/3)O3;PNN) has a perovskite structure and
typical relaxor ferroelectric properties. It exhibits a diffuse phase transition at around -120C, with a
much lower peak permittivity of about 4000 [9]. The crystal structure of PNN at room temperature
is cubic (Pm3m), with a lattice parameter of 4.03 [9]. PNN based systems, such as
Pb(Ni1/3Nb2/3)O3- Pb(Fe1/2Nb1/2)O3 [10] and Pb(Ni1/3Nb2/3)O3- Pb(Mg1/2W1/2)O3- PbTiO3 [11], have
been evaluated to possess low sintering temperatures and high dielectric constants. Thus, mixing
PNN with PZ is expected to decrease the sintering temperature of PZ-based ceramics, a desirable
move towards lower-cost electrodes [12].
In this work, the columbite precursor method was used to synthesize the Pb(Zr1-x(Ni1/3Nb2/3)xO3
(PZNN) with x = 0.0 0.5. The effect of PNN substitution on the phase transformation behavior of
PZ was investigated. Phase structure, phase transitions and the related properties were studied by a
differential scanning calorimeter.
Experimental
The perovskite structure of lead zirconate lead nickel niobate ceramic, Pb(Zr1-x(Ni1/3Nb2/3)xO3
(PZNN), was prepared by the columbite precursor method via the ball-milling technique. The
columbite structure (NiNb2O6) was synthesized first. Stoichiometric amounts of the precursor (NiO,
Nb2O5) were mixed and milled in ethyl alcohol for 18 h. The mixture was dried and calcined at
1,100C for 4 h. Then, NiNb2O6 and ZrO2 were mixed with PbO, according to the composition of
Pb(Zr1-x(Ni1/3Nb2/3)xO3 (PZNN), 0.0 x 0.5, with an excessive content of 2 mol% PbO. After remilling and drying, the mixtures were calcined at 850C for 4 h in a closed alumina crucible. Pellets

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of 15 mm in diameter were pressed using 5% PVA. The binder was burnt out by slowly heating to
500C over 2 h. The samples were sintered at temperatures ranging from 1,100C to 1,150C for 6
h. Phase formation and phase transition of PZ-PNN were investigated by x-ray diffraction (XRD)
and a differential scanning calorimeter (DSC).
Results and Discussion
The XRD patterns of Pb(Zr1-x(Ni1/3Nb2/3)xO3, (0.0 x 0.5) ceramics, sintered at 1,150C, are
shown in Figure 1. From the patterns, PZ powder was identified as a single-phase material with a
perovskite structure having orthorhombic symmetry, which could be matched with ICDD file no.
75-1607. The XRD patterns of the PZNN compositions showed a combination between PZ and
PNN patterns, which indicated a perovskite structure having a symmetry that varied from
orthorhombic to pseudo-cubic types. The ICDD file no. 34-0103 for PNN, with a cubic structural
symmetry, showed a better comparison. The Pb(Zr1-x(Ni1/3Nb2/3)xO3 was orthorhombic,
rhombohedral and pseudo-cubic for compositions where x = 0.00 x < 0.10, x = 0.10 x 0.40 and
x = 0.50, respectively.

Figure 1 XRD patterns of Pb(Zr1-x(Ni1/3Nb2/3)xO3 ceramics.


The DSC was used to investigate the phase transition in the Pb(Zr1-x(Ni1/3Nb2/3)xO3 system. AFE-FE
phase transition temperatures, enthalpy and paraelectric (PE) transitions are summarized in Table I.
Figure 2 shows results of the DSC analysis of the PZNN ceramics. Two distinct endothermic peaks
were observed for Pb(Zr1-x(Ni1/3Nb2/3)xO3 samples with 0.0 x < 0.08. The lower temperature
corresponds to the transition temperature of the AFE FE phase transition, while the higher
temperature corresponds to the FEPE phase transition.

Advanced Materials Research Vols. 55-57

119

Table 1 Phase transition temperatures of Pb(Zr1-x(Ni1/3Nb2/3)xO3 ceramics (R, Rhombohedral;


O, Orthorhombic; C, pseudo-cubic)

Composition
(x )
0.00
0.04
0.08
0.10
0.30
0.50

Crystal
Structure
O
O
O
R
R
C

Phase transition
Temperature (C)
AFEFE
FEPE
229.5
235.5
150.1
220.8
55
205.5
200.2
149.0
-

Enthalpy (J/g)
AFEFE
FEPE
1.53
2.34
1.33
2.89
0.29
2.44
1.88
0.16
-

Figure 2 DSC thermographs of Pb(Zr1-x(Ni1/3Nb2/3)xO3 ceramics.


Based on the results of XRD, and DSC data, the ferroelectric phase diagram for the
Pb(Zr1-x(Ni1/3Nb2/3)xO3 binary system has been established, as shown in Figure 3. The transition
temperature decreases at approximate linearity with x. The phase diagram consists of three distinct
crystallographic phases in this system; high temperature paraelectric cubic (Pm3m), rhombohedral
(R3m), and ferroelectric orthorhombic [P2cb (no. 32)]. At low concentrations of PNN x 0.08, the
symmetry can be defined as orthorhombic. The orthorhombic symmetry transforms into
rhombohedral at a composition near x = 0.08.

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Figure 3 Phase diagram of the Pb(Zr1-x(Ni1/3Nb2/3)xO3, x = 0.0-0.5 binary system.


Summary
The Structure of Pb(Zr1-x(Ni1/3Nb2/3)xO3 (PZNN) is orthorhombic, rhombohedral and pseudo-cubic
for compositions where x = 0.00 x < 0.10, x = 0.10 x 0.40 and x = 0.50, respectively. In the
antiferroelectric (AFE) phase ferroelectric (FE) phase and FE to paraelectric (PE) phase, phase
transformation temperatures decrease with increasing PNN concentration. The AFEFE phase
transformation is detected for compositions 0.00 x 0.08.

Acknowledgment
This work was supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), Thailand Graduate Institute of Science and Technology (TGIST) and King
Mongkuts Institute of Technology Ladkrabang (KMITL).

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]

E. Sawaguchi, G. shirane and S. Hosshino: Phys. Rev. Vol. 83 (1951), p. 1078.


E. Sawaguchi, G. shirane and Y. Takagi: J. Phys. Jpn. Soc. Vol. 6 (1951), p. 333.
N. Vittayakorn and S. Wirunchit, Smart Mater. Struct. Vol. 16 (2007), p. 851.
S. Roberts, J. Am. Ceram. Soc. Vol. 33 (1953), p. 63.
L. Goulpeau: Sov. Phys. Solid State. Vol. 8 (1967), p. 1970.
V. J. Tennery: J. Am. Ceram. Soc. Vol. 49 (1966), p. 483.
B. A. Scott and G. Burns: J. Am. Ceram. Soc. Vol. 55, (1972), p. 331.
R. W. Whatmore and A. M. Glazer: J.Phys. C: Solid state Physc. Vol. 12 (1979), p. 1505.
V. A. Bokov and I. E. Myl'nikova: Sov. Phys. Solid State. Vol. 3 (1961), p. 631.
T. R. Shrout, S. L. Swartz and J. M. Haun: Am. Ceram. Soc. Bull. Vol. 63 (1984), p. 808.
M. Yonezawa, Ferroelectrics. Vol. 68 (1986), p. 181.
Y. Xu, Ferroelectric Materials and Their Application (Elsevier Science Publishers B.V.,
1991).

Advanced Materials Research Vols. 55-57 (2008) pp 121-124


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.121

Synthesis, Crystal Structures, Phase Transition Characterization and


Thermal Properties of the (1x)PbZrO3-xPb(Co1/3Nb2/3)O3 Solid Solution
System
W. Banlue1, R. Muanghlua2, W. C. Vittayakorn3and N. Vittayakorn1,a
1

Materials Science Research Unit, Faculty of Science, King Mongkuts Institute of Technology
Ladkrabang, Bangkok, Thailand 10520

Electronics Research Center, Faculty of Engineering, King Mongkuts Institute of Technology


Ladkrabang, Bangkok Thailand 10520

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand 50200
a

naratipcmu@yahoo.com

Keyword: Antiferroelectric Materials, Ferroelectric, Lead Zirconate

Abstract The phase transition behavior of the (1x) PbZrO3-xPb(Co1/3Nb2/3)O3 (PZCN) solid
solution system (0 x 0.30) has been investigated by X-ray diffraction and DSC. In the solid
solution, for x 0.20, the transition shows a first-order phase transition behavior and its
antiferroelectric (AFE) crystal structure is orthorhombic. The transition temperature gradually
decreases with increased Co2+/Nb5+ concentration. On the composition range 0.20 x 0.30, a
typical relaxor-like behavior is displayed. The low temperature crystal structure is pseudo-cubic in
this composition range. With these data, the ferroelectric phase diagram between PZ and PCoN has
been established.
Introduction
Lead zirconate [PbZrO3, abbreviated as PZ] is an antiferroelectric ceramic with a Curie temperature
of 230C [1, 2]. PZ is a parent compound of PbZr1xTixO3 (PZT) solid solutions, which are of high
scientific and technological interest for their ferroelectricity and piezoelectricity observed over a
wide range of compositions [3]. It is reported that the antiferroelectric (AFE) to ferroelectric
transition (under the application of a strong electric field to the ceramic in the antiferroelectric state)
leads to significant energy storage for the DC field [4]. This feature of PbZrO3 makes it a candidate
material for energy storage applications [3]. Lead cobolt niobate [Pb(Co1/3Nb2/3)O3, abbreviated as
PCoN] is a relaxor ferroelectric, characterized by frequency-dependent dielectric maxima and a
diffuse phase transition [5, 6]. The diffuse phase transition characteristic of the PCoN was first
explained by Smolenskii and Agranovskaya on the basis of local compositional fluctuations on a
microscopic scale [6, 7]. PCoN-based ceramics are considered to possess low sintering
temperatures. Therefore, these materials can be applied for fabricating multilayer capacitors with
low-temperature melting inner electrodes [8]. There have been many studies concerning the solid
solution of PZ and other perovskite materials such as PbTiO3 [9], BaZrO3, [4, 10] PbSnO3 [11] and
SrZrO3 [9]. However, to the best of the authors knowledge, no work has been done on the solid
solution between PZ and PCoN. Therefore, the objective of our present study is to investigate phase
transition of (1x)PbZrO3 xPb(Co1/3Nb2/3)O3 (PZ PCoN ) with x = 0.00 0.30 as a function of
composition and temperature.
Experimental
The (1x)PbZrO3 xPb(Co1/3Nb2/3)O3 ceramics, where x = 0.00, 0.02, 0.04, 0.06, 0.08, 0.10, 0.20
and 0.30, were prepared by a columbite precursor. First, a columbite (CoNb2O6) precursor was
prepared using reagent-grade CoO and Nb2O5 in stoichiometric proportions. The powders were
thoroughly mixed in a ball mill for 18 h, using ethanol as a grinding medium, and the mixed powder
was calcined at 1,100C for 4 h to obtain the columbite precursor. Single-phase formation of the

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precursor was confirmed by X-ray diffraction. The columbite precursor was mixed with PbO (99%
purity), and ZrO2 (99% purity) in different proportions for making different compositions, and each
mix was calcined at 900C for 4 h to acquire the desired composition of (1x)PZxPCoN. Two
mol percent of excess PbO was added to all the compositions to compensate for the lead loss during
sintering. Single-phase formation was verified by powder XRD. Powders were compacted in disk
form with a diameter of 15 mm and thickness of 23 mm. These disks were sintered in PbO-rich
atmosphere at 1,150C for 2 h. The densities of the sintered samples were measured to ~ 95% of the
theoretical values. The crystal structure of the sintered pellets was determined by X-ray diffraction
(XRD). The phase transition temperatures and enthalpy (H) of the phase transitions were
determined by DSC. This was operated from room temperature to 250C with a heating rate of
10C/min.
Results and Discussion
Figure 1 illustrates the XRD patterns of (1-x)PZ-xPCoN sintered pellets for 0.00 x 0.30. It can
be seen that the sintered pellets are single-phase: all the lines in each XRD pattern could be indexed
with a perovskite cell. The diffraction peaks move gradually towards higher angles with increasing
PCoN contents, indicating smaller cell parameters.

Figure 1 XRD patterns of (1x)PbZrO3 xPb(Co1/3Nb2/3)O3 sintered pellets.

Advanced Materials Research Vols. 55-57

123

Figure 2 DSC thermographs of PZ-PCoN samples for: (a) x = 0, (b) x = 0.04 and (c) x = 0.10.
For the composition 0.00 x 0.10, superstructure lines along with strong peaks are clearly
observed, indicating that this composition belongs to the AFE orthorhombic phase. Furthermore,
the samples with x = 0.1, 0.2 and 0.3 had a split (1 1 1) and (2 2 0) reflection and single (2 0 0)
reflection, confirming that the crystal structure of the samples with x = 0.1, 0.2 and 0.3 is a
rhombohedral perovskite. The DSC technique was used to investigate the phase transition of PZPCoN ceramics, with increasing PCoN concentration. A typical result of the DSC of PZ-PCoN for
the composition x = 0, 0.04 and 0.10 is presented in Figure 2(a)-(c). Two distinct endothermic peaks
observed for PZ at about 208.4 and 225.6C are shown in Figure 2(a). The lower temperature
corresponds to the transition temperature of the AFEFE phase transition, while the higher
temperature corresponds to the FEPE phase transition. In Figure 2(b), two endothermic peaks are
shown at 92.8 and 216.1C for the composition, x = 0.04. The AFEFE phase transition was found
in the compositions of 0.00 x 0.10. The peaks shift to lower temperatures, with a higher
composition of x. This result corresponds to a decreasing AFE phase, with increasing amounts of
PCoN content. Table 1 gives the transition temperature, including AFEFE and FEPE
transitions of different PZ-PCoN compositions observed from DSC. The temperature range width
of the FE phase increases progressively with PCoN content. After accumulating all these data, the
ferroelectric phase diagram of (1-x)PZxPCoN has been finally established as a function of
temperature and composition, as shown in Figure 3.
Table 1 Phase transitions temperature of (1-x)PZ-xPCoN ceramics
Composition
x
0.00
0.02
0.04
0.06
0.08
0.10
0.20
0.30

Phase transition temperature (C)


AFEFE
FEPE
208.4
225.6
145.2
220.9
92.8
216.1
33.3
209.9
204.6
199.4
182.0
158.2

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Figure 3 Ferroelectric phase diagram of the (1-x)PZ xPCoN, x = 0.0-0.30 binary system.
The transition temperature decreases linearly with x, from approximately Tc = 235C for x = 0.0 to
158.2C for x = 0.3. At room temperature, the phase boundary between the orthorhombic,
antiferroelectric and rhombohedral ferroelectric phases was observed near x = 0.08. The phase
diagram consists of three distinct crystallographic phases in this system; high temperature
paraelectric cubic, rhombohedral, and ferroelectric orthorhombic.
Summary
Relaxor ferroelectric PCoN has been found to strongly influence crystal structure and thermal
properties of PZ ceramics. The crystal structure data obtained from XRD indicate that the solid
solution (1-x)PZ - xPCoN, where x = 0.0-0.3, successively transforms from orthorhombic to
rhombohedral symmetry with increased PCoN concentration. The AFEFE phase transition is
found in compositions of 0.0 x 0.08. The AFEFE phase transition shifts to lower temperatures
with higher compositions of x. The temperature range width of the FE phase increases with
increased PCoN.
Acknowledgment
This work was supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), and King Mongkuts Institute of Technology Ladkrabang (KMITL).
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

E. Sawaguchi, G. Shirane and S. Hoshino: Phys. Rev. Vol. 83 (1951), p. 1078.


F. Jona, G. Shirane, F. Mazzi and R. Pepinsky: Phys. Rev. Vol. 105 (1957), p. 849.
G. H. Haertling: J. Am. Ceram. Soc. Vol. 82 (1999), p. 797.
B. P. Pokharel and D. Pandey: J. Appl. Phys. Vol. 86 (1999), p. 3327.
K. Uchino: Ferroelectrics Vol. 151 (1994), p. 321.
G. A. Smolenskii and Isupov: Sov. Phys. doklady. Vol. 9 (1954), p. 653.
N. Setter and L. E. Cross: J. Appl. Phys. Vol. 51 (1980), p. 4356.
A. Halliyal, U. Kumar, R. E. Newham and L. E. Cross: Am. Ceram. Soc. Bull. Vol. 66 (1987),
p. 671.
[9] B. Jaffe and W. R. Cook: Piezoelectric ceramic (R.A.N. Publishers, 1971).
[10] B. P. Pokharel and D. Pandey, Phys. Rev. B. Vol. 65 (2002), p. 214108.
[11] Y. Xu, Ferroelectric Materials and Their Application (Elsevier Science Publishers B.V.,
1991).

Advanced Materials Research Vols. 55-57 (2008) pp 125-128


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.125

Effects of Zr/Ti Ratio on the Structure and Ferroelectric Properties in


PZT-PZN-PMN Ceramics Near the Morphotropic Phase Boundary
R. Muanghlua1, S. Niemchareon 1, W. C. Vittayakorn2 and N. Vittayakorn3,a
1

Electronics Research Center, Faculty of Engineering, King Mongkuts Institute of Technology


Ladkrabang, Bangkok Thailand 10520

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai, Thailand 50200
3

Materials Science Research Unit, Faculty of Science, King Mongkuts Institute of Technology
Ladkrabang, Bangkok, Thailand 10520
a

e-mail: naratipcmu@yahoo.com

Keyword: Ferroelectric Materials, Lead Zirconate titanate, Morphotropic phase boundary

Abstract The piezoelectric ceramics of Pb(ZrxTi1x)O3 Pb(Zn1/3Nb2/3)O3 Pb(Mn1/3Nb2/3)O3;


PZT-PZN-PMN with Zr/Ti ratios of 48/52, 50/50 and 52/48 were fabricated in order to investigate
the effect of compositional modifications on the ferroelectric properties of PZT-PZN-PMN
ceramics. The phase structure of ceramics sintered at 1,150C was analyzed. Results show that the
pure perovskite phase was in all ceramic specimens, and the phase structure of PZT-PZN-PMN
piezoelectric ceramics transformed from tetragonal to rhombohedral, with the Zr/Ti ratios increased
in the system. The PZT-PZN-PMN ceramics with a Zr/Ti ratio of 50/50 exhibited the most
promising properties including high remanent polarization and low coercive field of 25.95 C cm2
and 12.5 kV cm1, respectively. Furthermore, the transition temperature decreased when the Zr/Ti
ratio increased in the system.
Introduction
Lead zirconate titanate (PZT) is one of the most commonly used ferroelectric ceramic materials.
The material has been studied intensively since discovery of the miscibility of lead titanate and lead
zirconate in the 1950s. Due to their excellent dielectric, pyroelectric, piezoelectric and electro optic
properties, they have a variety of applications in high energy capacitors, non-volatile memories
(FRAM), ultrasonic sensors, infra red detectors, electro optic devices, and step-down multilayer
piezoelectric transformers for ACDC converter applications. Until now, many ternary and
quaternary systems, such as PNWPMNPZT [1], PMNPZNPZT [2], PZTPNNPZN [3], and
PZTPFWPMN [4] have been synthesized by modifications or substitutions to satisfy the
requirements of the multilayered piezoelectric transformers. In this work, we studied influences of
the Zr/Ti ratio on the crystal structure, and piezoelectric and dielectric properties of Pb(ZrxTi1x)O3
Pb(Zn1/3Nb2/3)O3 Pb(Mn1/3Nb2/3)O3; PZT-PZN-PMN ceramics for multilayered piezoelectric
transformer applications.
Experimental
The powders and ceramics with compositions of Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06
(Zr(1-x)Tix)0.87]O3 were prepared via a conventional mixed-oxide process, where x = 0.48, 0.50 and
0.52. Reagent-grade oxide powders PbO (99.0%), ZrO2 (99.0%), TiO2 (99.5%), Nb2O5 (99.5%),
ZnO(99.9%) and MnO2 (99.0%) were mixed, consecutively. The mixtures were milled in ethanol
using zirconium ball as media in a polyethylene jar for 18 h. The mixed slurry was dried at 80C
and calcined at 850C for 4 h. Then, the calcined powders were ground again under the same
condition in order to obtain fine uniform powders. After drying, the powders were added to 5 wt.%
polyvinyl alcohol (PVA) solution, and then pressed into15 mm diameter plates under a pressure of
100 MPa. The pressed plates were sintered at 9501,100C for 6 h in a sealed alumina crucible with
lead atmosphere. The sintered ceramics were examined by X-ray diffractometry (XRD, D8

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Advance) to determine the phase structure. Subsequently, the sintered disks were polished, and
silver-paste electrodes were fired at 850C. In addition, the polarization (P) was measured as a
function of electric field (E), using a ferroelectric tester system (Radiant Technologies, Inc.,
PT66A).
Results and Discussion
Figure 1 (a) and (b) show the XRD patterns of Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06
(Zr(1-x)Tix)0.87]O3 sintered pellets for x = 0.48, 0.50 and 0.52. The sintered pellets can be seen as a
single-phase: all the lines in each XRD pattern could be indexed with a perovskite cell. No
secondary reaction phases, such as PbO, Pb-based compounds, unreacted oxide and so on, are
observed in the pattern.

Figure 1 XRD patterns of Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06(Zr(1 - x)Tix)0.87]O3 sintered


pellets.
Based on the careful XRD study of (2 0 0) reflections in Figure 1(b), we found that a phase
transformation from the pseudo-cubic structure to the tetragonal structure occurs with increasing x
content. The ceramics with x = 0.48 exist as a pseudo-cubic phase revealed by the single (2 0 0)R
peak. At x = 0.50, the ceramics coexist as a tetragonal and pseudo-cubic phase revealed by the
coexistence of (0 0 2)T and (2 0 0)R peaks in the 2 range of 43.5 to 45.5. The ceramics exist as a
tetragonal phase when indicated by the splitting of (0 0 2) and (2 0 0) peaks in the 2 range of 43.5
to 46.5 at x = 0.52.
Table 1 Characteristics of Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06(Zr(1-x)Tix)0.87]O3 ceramics with
optimized processing conditions
Composition x

Crystal structure

0.48
0.50
0.52

PC
PC+T
PC

Theoretical Density
(%)
94.05
94.03
95.21

Grain Size (m)


2.84
2.72
2.94

Advanced Materials Research Vols. 55-57

127

In the first approximation, it could be said that the composition between x = 0.50 is close to the
morphotropic phase boundary (MPB) of this system, where the structure of the
Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06(Zr(1-x)Tix)0.87]O3 compositions is gradually changing
from pseudo-cubic to tetragonal. The physical properties do not vary significantly with the ceramic
compositions, as listed in Table 1.

Figure 2 Hysteresis loops of the Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06(Zr(1-x)Tix)0.87]O3 ceramics


with x = 0.48, 0.50 and 0.52 measured at 40 kV/cm.
Figure 2 illustrates the PE curves of the samples, with x = 0.48, 0.50 and 0.52 measured at
25 kV/cm. All compositions show symmetry in shape and reveal rectangular hysteresis loops,
which is typical of a phase that contains long-range cooperation between dipoles. No evidence of
pinning effect or asymmetric loop was detected in any electric field strengths. From the fully
saturated loops, the remanent polarization Pr and coercive field Ec were determined. The values of
Pr and Ec for composition x = 0.50 are 25.95 C/cm2 and 12.5 kV/cm, respectively, whereas the
remanent polarization Pr is 25.7 C/cm2 for composition x = 0.48. Maximum remanent polarization
was observed in the ceramic with composition x = 0.5. It has been seen that the samples with
compositions x = 0.5 exhibit the highest saturation and remnant polarization among all the
ceramics studied. As indicated by the above XRD, the composition with x = 0.5 contains both
tetragonal and pseudo-cubic phases, so it should favor a strong ferroelectric effect. This is due to the
increased ease of reorientation during poling by the transformation of a number of 180 domains
into 90 ones. Also revealed from these results, the MPB coexisting in the tetragonal and pseudocubic phases in the present system is a broad composition region of x = 0.5, which exhibits high
ferroelectric properties around the center of the MPB.
Summary
The Zr/Ti ratio has been found to influence crystal structure and ferroelectric properties of
Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06(Zr(1-x)Tix)0.87]O3 ceramics. The crystal structure data
obtained from XRD indicate that the solid solution Pb0.97Sr0.03[(Mn1/3Nb2/3)0.07(Zn1/3Nb2/3)0.06
(Zr(1-x)Tix)0.87], where x = 0.48, 0.50 and 0.52, successively transforms from pseudo-cubic to
tetragonal symmetry with increased x concentration. More interestingly, XRD analysis and
ferroelectric property measurements indicated the existence of the MPB composition at between
x = 0.50.

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Acknowledgment
This work was supported by the Thailand Research Fund (TRF), the Commission on Higher
Education (CHE), and Faculty of Engineering, King Mongkuts Institute of Technology
Ladkrabang and King Mongkuts Institute of Technology Ladkrabang (KMITL).
References
[1]
[2]
[3]
[4]

Z. Yang, R. Zhang, L. Yang and Y. Chang: Materials Research Bulletin. Vol. 42 (2007), p.
2156.
J. Yoo, K. Kim, C. Lee, L. Hwang, D. Paik, H. Yoon and H. Choi: Sensors and Actuators A:
Physical. Vol. 137 (2007), p. 81.
N. Vittayakorn and D. P. Cann; Appl. Phys. A. Vol. 86 (2007), p. 403.
Z. Yang, X. Chao, C. Kang and R. Zhang: Materials Research Bulletin. Vol. 43 (2008), p. 38.

Advanced Materials Research Vols. 55-57 (2008) pp 129-132


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.129

Impedance and Dielectric Properties of Nb-Doped Pb(Zr0.52Ti0.48)O3


Ceramics
P. Ketsuwan1, A. Ngamjarurojana1, Y. Laosiritaworn1, S. Ananta1,
R. Yimnirun1 and D. P. Cann2
1

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, thailand

Materials Science, School of Mechanical, Industrial, and Manufacturing Engineering, Oregon, State
University, Corvallis OR 97331, USA
1

ketsuwanpiyachon@gmail.com, cann@engr.orst.edu

Keywords: Dielectric properties, Electrical properties, Impedance spectra, Nb-doped PZT.

Abstract. The compositions of Pb(Zr0.52Ti0.48)O3 doped with 1-6 mole% Nb content were prepared
by a conventional mixed oxide technique. It was found that the phase formed depended on the
dopant concentration. At lower concentration, the dominate phase was the tetragonal. With
increasing Nb content the rhombohedral phase tended to increase. Furthermore, the Curie
temperature (Tc) and dielectric constant decreased with increasing Nb concentration and the
dielectric maximum peaks were broadened with more rhombohedral phase presence, causing the
diffused ferroelectric-paraelectric phase transition. The impedance of the samples decreased with
increasing temperature and it was also observed that the impedance increased with increasing Nb
concentration.
Introduction
Pb(Zr0.52Ti0.48)O3 is a composition near the morphotropic phase boundary (MPB) of Pb(Zr,Ti)O3. As
the MPB is nearly vertical on the phase diagram, intrinsic property persists over a wide temperature
range [1]. Almost all useful PZT ceramics are doped or modified to improve properties for specific
applications [2]. Lead zirconate titanate solid solution modifications are controlled by aliovalent
cation additions. One approach of modification is off-valent donor doping, such as Nb5+, which
makes domain wall move more easily and results in enhanced dielectric constant and coupling
factor but reduced electric coercivity [3]. This study is therefore aimed at detailed investigation of
the inflence of doping concentration on electrical properties of Nb-doped Pb(Zr0.52Ti0.48)O3
ceramics by using complex impedance analysis.
Experimental
The Pb(Zr0.52Ti0.48)O3 ceramics with addition of 1-6 mol% Nb2O5 were prepared by a conventional
mixed oxide technique. After ball milling in ethanol for 24 h, the slurry was dried and calcined at
975 oC for 2 h. Then, the calcined powder was pressed into disks (d =10 mm). The pellets were
placed inside a closed alumina crucible covered with lead zirconate (PbZrO3) powder to compensate
the PbO volatilization. In addition, 3 mol% PbO was added to each composition in order to
compensate for lead volatilization which is expected to take place during sintering at 1250 oC for 2
h. The x-ray diffraction (XRD) was used for structure and phase formation analysis. The dielectric
properties and the impedance were determined by automated LCR-meter and an impedance
analyzer, respectively.
Results and Discussion
The x-ray diffraction patterns of Pb(Zr0.52Ti0.48)O3 with addition of 1-6 mol% Nb2O5 ceramics are
shown in Fig.1. At lower Nb concentration, the dominant phase is identified as a tetragonal phase

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which was characterized by a (002)T and (200)T peaks between 43o 46o. However, a
rhombohedral phase increases with increasing Nb concentration, which was characterized by
(200)R.
(%)

40

30
20

(111) R,T

(200)T

(200)R

N b m o l%
(002)T

(100)T

(010)R

(001)T

10

(g )
(f)
(e )
(d )
(c )
(b )
(a )
20

25

30

35

40

45

50

55

Figure 1 XRD pattern of (a) undoped (b)-(g) Pb(Zr0.52Ti0.48)O3 with 1-6 mol% Nb2O5 ceramics, the
rhombohedral phase content is shown in inset.

The tetragonal and rhombohedral phases were quantified by the intensities of the overlapping of
(200), (002) and (200) peaks in the angle range of 43o 46o. For the determination of the
rhombohedral phase content, the Eq.1 was used [4].
I FR ( 200 )
% FR =
100
(1)
I FR ( 200 ) + I FT ( 002 ) + I FT ( 200 )
From XRD data, it was believed that Nb occupies the Zr site. Because the scattering factors for Nb5+
and Zr4+ are very similar. If the Nb occupies the Zr site, there is no changes in the peak intensities.
On the other hand, If Nb occupies the Ti site, the variation in the peak intensity should be observed
due to Ti4+ has a different scattering factor than Nb5+. Further, zirconium ions might be incorporated
into the rhombohedral phase, which would cause an increase in the amount of rhombohedral phase
and unit-cell volume that can be observed the peaks shifted towards lower angle of the (111) peaks
[5].
1 mol%
2 mol%
3 mol%
4 mol%
5 mol%
6 mol%

30000

0.6

0.4

20000
0.2

Dielectric Losses

Dielectric Constant

40000

10000

0
200

250

300

350

400

450

0.0
500

Temperature (0C)

Figure 2 Dielectric constant and loss tangent as a function of Nb concentration measured at 10 kHz.

Advanced Materials Research Vols. 55-57

131

From Figs.2 ,3(a) and 3(b), the dielectric constant and dielectric loss at room temperature tend to
increase with increasing Nb concentration while the maximum dielectric constant, dielectric loss
and Curie temperature tend to decrease with increasing Nb concentration. The increase in room
temperature dielectric constant and loss tangent can be explained to the effect of Nb doping caused
Pb vacancies in the PZT lattice, thereby facilitating the motion of ferroelectric domains. The
decrease in Curie temperature causes the decrease in lattice vibrations and the interaction between
the vacancies created by Nb content that can be responsible for the change in the dielectric
maximum and Curie temperature values [6].
0.025

50000

1.2

1300

1000

0.010

900

Dielectric Constant

0.015

1100

Dielectric Loss

Dielectric Constant

0.020
1200

0.005

1.0

40000

0.8

30000

0.6
0.4

20000

0.2

Dielectric Loss

1400

10000

800

0.0

700

0.000
0

Nb Concentration (mol%)

Nb Concentration (mol%)

(a)
(b)
Figure 3 Dielectric constant and losses tangent as a function of Nb concentration at (a) room temperature
(b) Curie temperature (measured at 10 kHz).
50000
400 oC
425 oC

40000

1 mol%
3 mol%
6 mol%

150000

450 oC
475 oC
500 oC

100000

Z''

Z''

30000

20000

50000
10000

0
0

20000

40000

60000

Z'

80000

100000

100000

200000

300000

400000

Z'

(a)
(b)
Figure 4 (a) Complex impedance plane plots at different temperatures and (b) Nb concentrations

Figure 4(a) and (b) shows the complex impedance spectrum measured at different temperatures and
Nb concentrations. The complex impedance plots Z versus Z, where Z and Z are the real and
the imaginary parts of the complex impedance. In general, three distinct arcs can be observed. In
order of increasing frequency from right to left side of the Z axis, arcs 1, 2 and 3 are due to
electrode effect, the grain-boundary effect and the grain or bulk effect, respectively. From Fig. 4(a)
and (b), the presence of a single semicircular arc indicates that the electrical contribution is from
bulk materials. The increase in temperature leads to the increase in the semicirculars, shifts toward
lower side indicating the decrease in the resistances. But the semicircluars shifts toward higher side
indicates the increase in the resistances (Fig. 4(b)). The impedance of the samples decreases with
increasing temperature and it is also observed that the impedance increases with increasing dopant
concentration. The bulk conductivity is evaluated from Eq. 2 [7].
t
=
(2)
Rb A
where Rb is the bulk resistance, t is the thickness, and A is the area of the samples. The value of
bulk resistance is obtained from the intercept of the semicircle on the real axis (Z).

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0
0 mol%
1 mol%
3 mol%
6 mol%

Ln (Ohm.m)-1

-2

-4

-6

-8

-10

-12
0.00125

0.00130

0.00135

0.00140

0.00145

0.00150

1/T (K)-1

Figure 5 Temperature dependence of conductivity of undoped, 1, 3 and 6 mol% of Nb-PZT ceramics.

The relation between log conductivity and inverse absolute temperature is shown in Fig.5, revealing
the decreasing of the conductivity. From earlier study, the PZT ceramics exhibit electric
conductivity of p-type caused by Pb vacancies, which act as the acceptor. The Nb5+ ions substituted
for B site play the role of donor that decreases the electric conductivity due to the compensation of
electrons-holes [8].

Summary
The electrical properties of Pb(Zr0.52Ti0.48)O3 ceramics with addition of 1-6 mol% Nb2O5 were
investigated. The dielectric constant and dielectric loss at room temperature tend to increase with
increasing Nb concentration, while the maximum dielectric constant, dielectric loss and Curie
temperature tend to decrease with increasing Nb concentration. The conductivity of the samples
increases with increasing temperature, but decreases with increasing dopant concentration due to the
compensation of electrons-holes.

Acknowledgments
This work was supported jointly by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science
and Technology, Thailand, through its program of Center of Excellent Network, Graduate School
and Faculty of Science, Chiang Mai University.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

L. E. Cross: Mater. Chem. Phys. Vol. 43 (1996), p. 108.


G. H. Haertling: J. Am. Ceram. Soc. Vol. 82(4) (1999), p. 797.
K. Okazaki and K. Nagata: J. Am. Ceram. Soc. Vol. 56 (1973), p. 82.
M. Hammer and M. J. Hofmann: J. Electroceramics Vol. 2(2) (1998), p. 75.

C.O. Paiva-Santos, C.F. Oliveira, W.C. Las, M.A. Zaghete, J.A. Varela and M.
Cilense: Mater. Res. Bull. Vol. 35 (2000), p. 15.
K. Ramam1 and M. Lopez: J. Phys. D: Appl. Phys. Vol. 39 (2006), p4466.
S. Sen, R. N. P. Choudhary, A. Tarafdar and P. Pramanik: J. Appl. Phys. Vol. 99 (2006), p.
124114.
J. J. Dih and R. M. Fulrath: J. Am. Ceram. Soc. Vol. 61 (1978), p. 448.

Advanced Materials Research Vols. 55-57 (2008) pp 133-136


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.133

Dielectric and Piezoelectric Properties of Zirconium-Doped Bismuth


Sodium Titanate Ceramics
a

A. Watcharapasorn and S. Jiansirisomboon

Department of Physics, Faculty of Science, Chiang Mai University,


Chiang Mai 50200, Thailand
a

anucha@stanfordalumni.org, sukanda@chiangmai.ac.th

Keywords: BNT, dielectric, piezoelectric, solid solution

Abstract. Zirconium-doped bismuth sodium titanate ceramics were prepared using the conventional
processing method. X-ray diffraction analysis indicated the materials were single phase with a
systematic shift due to increased unit cell size. The measured densities and grain size of the ceramic
samples were found to range from 5.79-6.03 g/cm3 and 0.5-1.6 m, respectively. The dielectric
constant as a function of temperature became broader as Zr content increased. The piezoelectric
constant was found to decrease with increasing Zr. Within the range of the solid solutions
investigated, the materials seem to be promising for high temperature applications where stable
dielectric constant is required.
Introduction
It is well known that a number of solid solution systems in ferroelectric ceramics are scientifically
and technologically important. These include Pb(Zr,Ti)O3, Pb(Mg1/3Nb2/3)O3-PbTiO3 and
Pb(Zn1/3Nb2/3)O3-PbTiO3, which have already been widely used in many sensor and actuator
applications [1, 2]. However, the lead-containing compounds are currently of environmental
concerns for future devices. Therefore, a number of non-lead material systems have been
investigated in order to to find suitable replacement for lead-based compounds. One of these nonlead systems is the solid solution of BaTiO3-BaZrO3 (BZT) which was found to possess high
dielectric constant, low loss, high-strain capability and large piezoelectric coefficient [3-9].
Besides BZT, bismuth sodium titanate having chemical formula, Bi0.5Na0.5TiO3 or BNT, has
recently been received more attention due to their interesting ferroelectric properties. These include
remanent polarization of 38 C/cm2, coercive field of 73 kV/cm and high Curie temperature (Tc =
320 C) [10-13]. Although a number of dopants have been used to modify properties of BNT
ceramics [13-15], the solid solution Bi0.5Na0.5(Ti,Zr)O3 have not yet been investigated in detail.
In this paper, the effects of Zr concentration on physical, dielectric and piezoelectric properties
of BNT are studied and discussed.
Experimental
Bi0.5Na0.5Ti1-xZrxO3 (where x = 0, 0.05, 0.10, 0.15 and 0.20) powders were prepared from binary
oxides, i.e. Bi2O3 (>98%, Fluka ), Na2CO3 (99.5%, Carlo Erba), TiO2 (>99%, Riedel-de Han) and
ZrO2 (>99%, Fluka). The powder mixtures were ball-milled for 24 h using zirconia milling media in
ethanol prior to calcination in alumina crucible at 800 C for 2 h. After phase analysis by X-ray
diffraction technique (XRD, JDX-8030), the powders were pressed into small pellets and sintered at
1100 C for 2 h. The sintered ceramics were characterized for their densities using Archimedes
method. The surface morphologies were studied using a scanning electron microscope (JEOL JSM5910LV) and the grain size was obtained using a linear interception method. The dielectric constant
as a function of temperature was measured using an LCR HITESTER connected to a high
temperature furnace. The piezoelectric constant was measured using a d33-meter (KCF PM-3001)
after poling each sample for 5 minutes in 60 C silicone oil under 40 kV/cm electric field.

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Results and Discussion


X-ray diffraction patterns of Bi0.5Na0.5Ti1-xZrxO3 (BNTZ) calcined powders and sintered ceramics
are shown in Fig.1. For samples having the same composition, there was virtually no difference
between X-ray patterns of powders and ceramics. The X-ray diffraction pattern of undoped BNT
indicated the rhombohedral crystal structure, in agreement with the standard powder diffraction file
no. 36-0340 and the pattern reported in literature [13,15]. Incorporation of Zr ions into BNT lattice
caused a slight systematic shift of X-ray patterns to the left without changing relative peak
intensities which suggested that the rhombohedral structure was maintained while the size of unit
cell increased with increasing amount of Zr. Similar increase in lattice parameter was also observed
for Zr-doped BaTiO3 due to the larger Zr-ion substitution in Ti4+ site [16].

Figure 1. X-ray diffraction patterns of BNTZ: (a) calcined powder and (b) sintered ceramics
The density and the average grain size of BNT and BNTZ ceramics are listed in Table 1. The
densities were within the range of 5.79-6.03 g/cm3, corresponding to the relative density of at least
95% of theoretical value. The average grain size ranged from 0.5-1.6 m and increased with
increasing Zr content. This indicated that the addition of ZrO2 did not significantly affect the
microstructures of BNTZ ceramics compared with that of BNT.
Table 1. Some room temperature properties of BNTZ ceramics.
BNT

BNTZ05

BNTZ10

BNTZ15

BNTZ20

Density (g/cm3)

5.95

5.79

5.94

5.93

6.03

Grain size (m)

0.5

1.0

1.1

1.2

1.6

d33 (pC/N)

68

57

52

47

40

524

620

655

572

562

tan

0.06

0.04

0.04

0.04

0.05

The dielectric constant and dielectric loss plotted as a function of temperature at 10 kHz are shown
in Fig. 2. The dielectric curve for BNT showed a normal behavior and had the maximum value at
320 C, which was the transition temperature commonly found by other researchers [10-15]. The
room temperature dielectric constant value of BNT (see Table 1) agreed well with the values
reported [13-15]. The room temperature dielectric constant slightly increased with increasing Zr
content up to 10 mol%Zr and then decreased with further addtion of Zr. Unlike the BaTiO3-BaZrO3

Advanced Materials Research Vols. 55-57

135

system [8,9] where addition of Zr decreased the Tc of the ceramics, the effect of Zr on the transition
temperature of BNTZ was rather small.
In Fig. 2, it can be seen that increasing Zr concentration caused the dielectric-temperature
curves to become more diffused with corresponding lower values of high-temperature dielectric
constant. Since no frequency dependence of the dielectric constant was observed (not shown), the
amount of Zr used in this study did not render the relaxor behavior of this material. This seems to be
in agreement with the study on BaTiO3-BaZrO3 solid solution in which the frequency dependence
of the dielectric constant was observed only when the amount of Zr used was equal to or greater
then 30 mol% [8,9].
From Fig. 2 (b), except for BNTZ20, the dielectric loss of other BNTZ ceramics showed a
relatively constant value for all samples up to about 150 C. Above this temperature, the values
slightly decreased and then increased as the loss became more significant at high temperature. This
behavior was also observed in BZT system [8,9]. The room temperature dielectric loss values for
BNTZ ceramics were comparable to that of BNT sample. The d33 piezoelectric constant of BNTZ
showed a decreasing trend with increasing Zr content (see Table 1). It seems therefore that the
random distribution of larger Zr ions inside BNT lattice caused some reduction in polarizability of
material. It would be interesting, however, to further investigate the BNTZ system in order to find
out whether the morphotropic phase boundary is present in order to obtain materials with good
dielectric and piezoelectric properties following the PZT and BZT systems.

Figure 2. Graph of (a) dielectric constant and (b) dielectric loss of BNTZ ceramics at 10 kHz plotted
as a function of temperature.
Summary
The single-phase Bi0.5Na0.5Ti1-xZrxO3 ceramics with x varied from 0 to 0.2 were successfully
prepared using conventional ceramic processing method. X-ray diffraction analysis showed a single
rhombohedral perovskite phase with systematic shift in peak position, indicating that substitution of
Zr4+ ions into Ti4+ site caused lattice expansion. The piezoelectric coefficient (d33) showed a
decreasing trend while the dielectric constant-temperature curves showed a broader peak with
increasing Zr concentration. This seems to suggest that the material might be used as a highstability dielectric material.
Acknowledgments
This work was financially supported by the Thailand Research Fund (TRF), the Commission on
Higher Education (CHE) and the National Science and Technology Development Agency
(NSTDA). The authors would also like to thank the Faculty of Science, Chiang Mai University

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References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

K. Uchino: Piezoelectric Actuators and Ultrasonic Motors (Kluwer, Boston 1997).


G.H. Haertling: J. Am. Ceram. Soc. Vol. 82, 4 (1999) p. 797.
P.W. Rehrig, S.E. Park, S.T. McKinstry, G.L. Messing, B. Jones and T.M. Shrout: J. Appl.
Phys. Vol. 86 (1999) p.1657.
Y. Zhi, R. Guo and A.S. Bhalla: J. Appl. Phys. Vol. 88 (2000) p. 410.
S.M. Neirman: J. Mater. Sci. Vol. 23 (1988) p. 3973.
J. Ravez and A. Simon: Eur. J. Solid State Inor. Chem. Vol. 34 (1997) p. 1199.
Z. Yu, R. Guo and A.S. Bhalla: Mater. Lett. Vol. 57 (2002) p. 349.
X.G. Tang, K.-H.Chew and H.L.W. Chan: Acta Mater. Vol. 52 (2004) p. 5177.
Z. Yu, C. Ang, R. Guo and A.S. Bhalla: Mater. Lett. Vol. 61 (2007) p. 326.
G.A. Smolensky, V.A. Isupov, A.I. Agranovskaya and N.N. Krainik: Sov. Phys. Solid State
Vol. 2 (1962) p. 2651.
C.F. Buhrer: J. Chem. Phys. Vol. 36 (1962) p. 798.
J. Suchanicz, K. Roleder, A. Kania and J. Handerek: Ferroelectrics Vol. 77 (1988) p. 107.
H. Nagata and T. Takenaka: J. Euro. Ceram. Soc. Vol. 21 (2001) p. 1299.
H.-D. Li, C.-D. Feng and W.-L. Yao: Mater. Lett. Vol. 58 (2004) p. 1194.
X.X. Wang, K.W. Kwok, X.G. Tang, H.L.W. Chan and C.L.Choy: Solid State Comm. Vol.
129, (2004) p. 319.
R. Panton, C. Dubourdieu, F. Weiss, J. Kreisel, G. Kbernik and W. Haessler: Mater. Sci.
Semicond. Process. Vol. 5 (2003) p. 237.

Advanced Materials Research Vols. 55-57 (2008) pp 137-140


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.137

Structural and Morphologies of (1-x)BaTiO3-xBaFe0.5Nb0.5O3


Solid Solution
S. Eitssayeam
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50202, Thailand
sukum99@yahoo.com
Keywords: solid solution, Barium Titanate, Barium iron niobate, phase evolution

Abstract. The structural and physical properties of(1x)BaTiO3 xBaFe0.5Nb0.5O3 ceramics system
were investigated as a function of the BaFe0.5Nb0.5O3 content by X-ray diffraction (XRD) and
dielectric measurement technique. Studies were performed on the samples prepared by solid state
reaction for x = 0, 0.2, 0.4 and 0.6. The XRD analysis demonstrated that with increasing BFN
content in (1x)BTxBFN, the structural change occurred from the tetragonal to the cubic phase at
room temperature. Changes in the morphology were then related to these structural depending on
the BFN content.
Introduction
Barium titanate (BaTiO3) is worthy of special mention, as it is the most widely utilized material for
capacitor applications. [1] The origin of the high dielectric constant (on the order of 103) in BaTiO3
stems from the presence of permanent electrical dipoles inherent to the crystal structure. However,
the dielectric constant of barium titanate rises sharply with temperature, exhibiting a peak at the
Curie point (TC = 130C), beyond which it falls hyperbolically, following the Curie-Weiss law. [2]
Since devices made from this material are to be used over a wide temperature range, pure barium
titanate cannot be utilized for practical applications. [2] It must be modified with various solid
solutions and additives, giving rise to varying temperature behavior of ceramics, as per the
application. [1-3] BaTiO3 and Ba(Fe0.5Nb0.5)O3 belong to the perovskites structural family with
general formula ABO3 (A = mono or divalent ions, B = tri- to pentavalent cations). It is well
established that the physical properties or device parameters of BT can be tailored by synthesizing
the materials with improved processing techniques and making suitable substitutions of A and/or B
sites. [3] The electrical properties of relaxor ferroelectrics are greatly influenced by the manner in
which the B site cations (B and B ions) are distributed and ordered on the B site sublattice. [4]
In spite of the evident effect of the BFN on the BT by solid state reaction, the phase evolution
and behavior of physical properties of dense ceramic bodies of materials obtained by the solid state
reaction are not clearly understood. Therefore,we decided to prepare (1x)BTxBFN (x = 0, 0.2, 0.4
and 0.6) powders and subjected the sintered to an extensive characterization and microstructure.
Experimental
The BTBFN ceramics used in this study are prepared powders with a conventional mixed-oxide
method. The (1-x)BaTiO3 xBaFe0.5Nb0.5O3 ((1-x)BT - xBFN) powders were first prepared by
mixing the starting materials BaCO3(>99%), TiO2(>99%), Fe2O3 (99.9%) and Nb2O5 (99.9%)
powders in the desired mole ratio, (x = 0, 0.2, 0.4 and 0.6). These powders were ball-milled for 24 h in
polyethylene container with zirconia balls. Ethanol was used as a milling medium. After drying at
120oC, the mixed powders were then calcined at 1200 C for 4 h with heating and cooling rate of
5oC/min. Subsequently, the most appropriate calcined samples were pressed into disc shape and
sintered at various 1350C. The samples were heated for 2 h with constant heating and cooling rates
of 5C/min. The phase formations of the calcined powders and sintered specimens were studied by an
X-ray diffractometer (Philips model X-pert) at 40kV and 30mA in the 2 range from 10 to 100

138

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degrees with step scan of 0.01. The microstructure was examined by the scanning electron
microscopy (Jeol SEM model 6335F).
Results and Discussion

(b)

(002)

(200)

(220)

(211)
(201)

(200)

(a)

(200)

(111)

(100)

(110)

The XRD results of sintered (1-x)BT xBFN ceramics showed that the perovskite structure (fig. 1).
No trace of pyrochlore phase was detected. The results indicated that change of crystal structure
occurred as a function of BT-BFN compositions. Ferroelectric tetragonal BT phase appeared as x =
0. Mixed tetragonal and cubic phases began to occur at x = 0.2 and completely transforms to
paraelectric cubic phase when x = 0.6, as can be seen at (002) and (200) peaks. Similar result was
also found by Vittayakorn et.al [5]. The lattice parameters of the two co-existing ferroelectric
phases in the ceramics were calculated by the refinement method. The cell parameters and
tetragonality (c/a) obtained for each BT-BFN composition is given in Fig 2. The result of the cell
refinement showed that the (1-x)BT xBFN system having BFN content in the range x = 0.6 has
single phase cubic symmetry, with cell parameters dependent on the BFN content. The value of the
c/a parameter decreased from 1.01 to 1.00 when the BFN content increased from x = 0 to 0.6. At
higher x values the unit cell volume of the BT was increased when adding BFN content and then
slightly decreases from 64.45 to 64.40.

Figure 1. (a) X-ray patterns of (1-x)BTxBFN ceramics and (b) selected regions of (1-x)BTxBFN
ceramics.

Figure 2. Lattices parameter of (1-x)PZT xBFN system.

(a)

(b)

(c)

Advanced Materials Research Vols. 55-57

139

The SEM micrographs of the (1-x)BT-xBFN ceramics were compared with that of pure BT
ceramic. It can be seen that the small addition of BFN of about x = 0.2 causes significant decrease
on grain size as shown in Fig 3 and reaches minimum of about 15 m at x = 0.4. Then the average
grain size is increased to approximately 8 m when increase the BFN content up to 0.6. Over this
point, the gradually decreasing in grain size is observed. These variations are mainly attributed to
the solubility of BFN in the BT system. The certain solubility value of BFN of about 0.6 is allowed
in this system and beyond this solubility limit it is believed to segregate at grain boundaries,
resulting in inhibition of grain growth. This is consistent with the work done by Yang et al. [6].
Moreover, the XRD pattern of (1-x)BT-xBFN ceramic at around this solubility limit of x = 0.6,
contains the mixing of both tetragonal and cubic structures. This may be assumed that the
morphotropic phase boundary of the (1-x)PZT-xBFN ceramic is near to x = 0.6.

(a)

(b)

(c)

(d)

Figure 3. SEM micrographs of (1-x)BT-xBFN as-sintered surfaces (a) pure BT ceramic,


(b) 0.8BT-0.2BFN ceramic, (c) 0.6BT-0.4BFN ceramic and (d) 0.4BT-0.6BFN ceramic.
Summary
The effect of BFN on the structure and morphology of (1-x)BT xBFN system was investigated for
various chemical compositions. The (1-x)BT xBFN (when x= 0, 0.2, 0.4 and 0.6) ceramics are
prepared by a mixed oxide method. Lattice parameters of the tetragonal phase and cubic phase were
found to vary with chemical composition. The evolution of the tetragonal phase, (200)/(002)
transformed to a single peak (200) which indicating cubic symmetry. They were identified as a
single BT phase material with a perovskite structure having the symmetry from tetragonal to cubic
when the ratio of BFN increased and completely transforms to paraelectric cubic phase when x =
0.6. BFN content also effective to morphology of (1-x)BT xBFN system.

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Acknowledgement
The authors would like to express their sincere thanks to financial support from the Thailand
Research Fund (TRF) and Graduate school and Faculty of Science, Chiang Mai University,
THAILAND.
References
[1]
[2]
[3]
[4]
[5]
[6]

A. Chelkowski: Dielectric Physics (Elsevier, New York, 1980).


Y. Xu: Ferroelectric Materials and Their Applications (Elsevier, New York, 1991).
S. L. Swartz: IEEE Trans. Elec. Ins. Vol. 25 (1990), p. 1.
S. Eitssayeam, U. Intatha, G. Rujijanagul, K. Pengpat and T. Tunkasiri: Appl. Phys. A. Vol. 83
(2006), p.295.
N. Vittayakorn, G. Rujijanagul, T. Tunkasiri, X. Tan and D. Cann: Mat. Sci. Eng. B. Vol.108
(2004), p.258.
Z. Yang, X. Zong, H. Li and Y. Chang: Mater. Lett. Vol.59 (2005), p.3476.

Advanced Materials Research Vols. 55-57 (2008) pp 141-144


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.141

Fabrication of 0-3 Non-Lead Based Piezoceramic/Polymer Composites


Using Suction Technique
T. Sareein, W. Thamjareea, W. Nhuapeng and T. Tunkasiri.
Department of Physics, Faculty of science, Chiang Mai University,
Chiang Mai, 50200, Thailand.
a

msrlwt@yahoo.com

Keywords: BNT, Lead-free piezoelectric, Piezocomposites

Abstract. In this research, 0-3 composites between non-lead based piezoceramic and polymer were
fabricated using the suction technique. Bismuth sodium titanate (Bi0.5Na0.5TiO3:BNT) which
prepared from conventional mixed oxide method was used as active phase whereas epoxy resin was
used as matrix phase. The 50% volumetric fraction of BNT/epoxy resin can obtain from suction
technique. The physical and piezoelectric properties of composites samples were examined. It can
be found that density of composite samples were about 1.78 g/cm3. Moreover, the piezoelectric
coefficient (d33) of sample was 13 pC/N. Furthermore, the microstructure of composites was
determined using SEM technique.
Introduction
Recently, lead oxide-based perovskite piezoelectric ceramics, for example, lead zirconate titanate
(Pb(Zr1-xTix)O3, PZT) are now widely used in many applications [1-2]. Since PZT exhibits the
superior piezoelectric properties. However, the lead oxide-based materials are hazard to human and
environment. Therefore, lead-free or non-lead based piezoelectric ceramics have now attracted
considerable interest to replace the lead-based material system [1]. Bismuth sodium titanate,
Bi0.5Na0.5TiO3 (BNT), a ferroelectric material which was first discovered by Smolenskii et al. in
1960 [2]. BNT ceramics is strongly ferroelectric materials and show the outstanding advantages in
a free control atmosphere which produce no PbO evaporation [3]. Thus, they have been considered
to be good candidates for non-lead based piezoelectric ceramics. Moreover, it is considered to
apply in hydrophone applications [2-3]. Since BNT ceramics are hard and brittle in nature which
may not be flexible enough to suit a curved surface. Therefore, piezocomposites which employed
an active piezoelectric material in conjunction with an active or passive polymer phase have been
suggested with different connectivity patterns [4]. In this work, the 0-3 composites between BNT
and polymer are fabricated using the suction technique. The physical and piezoelectric properties
of composites samples were examined. Furthermore, the microstructure of composites was
determined using SEM technique.
Experimental
(Bi0.5Na0.5)TiO3 ceramics were prepared by a conventional mixed oxide technique. Commercially
available Bi2O3 (98%), Na2CO3 (99.9%), and TiO2 (99%) were used as raw materials. The starting
powder were mixed and milled in ethanol (99%) for 24 h using a Y2O3-stabilized zirconia ball. The
mixture was then dried and calcined and at temperature of 800 C for 2 h with heating and cooling
rate of 3 C/min. To obtain ceramics powder, the calcined powder was then sieved and annealed at
1075 C for 2 h with heating and cooling rate of 3 C/min. Next, 0-3 piezocomposites between BNT
powder and epoxy resin were fabricated using the suction technique (Fig. 1). The BNT powders
and resin were filled in a syringe with a filter underneath. The syringe was plugged in a flask partly
filled with water. Suction was carried out through an air pump. The piezocomposites was cut into
disks with a thickness of 1 mm and 16 mm in diameter. The silver paste (Electrodrag 1415M,
Acheson) was used as electrodes and painted to the top and bottom surface of disk about 9 mm in

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diameter and left to dry at room temperature. Dielectric properties were measured using a LCZ
meter (model 4276, Hewlett-Packard). The specimens were poled in silicone oil at 120 C with a
poling field of 3 kV/mm for 5 min. The piezoelectric coefficient (d33) of the samples was
measured using a piezo d33 meter. Distributions of BNT powder phase in the composites were
investigated using SEM.

Figure 1. Schematic of the equipment to prepare 0-3 piezoceramic/epoxy resin composites.


Results and Discussion
The BNT ceramics powder annealed at the temperatures of 1075 C was scanned using a Siemens
Diffractometer with Ni filtered CuK radiation, covering the 2 ranges of 10-60, stepping scan of
0.5 and 1 sec counting time per step was employed. The corresponding diffractograms were
compared with JCPDS powder diffraction file of BNT powder [5]. The XRD result shows that
every peak can be attributed to BNT with orthorhombic structure which could be matched with
JCPDS no. 36-0340 [5]. Furthermore, it is also found that no impurities or secondary phases were
detected using this XRD method. Table 1 illustrates the physical and electrical properties of
BNT/epoxy composites compare with BNT ceramics and other work. From the results, it could be
seen that density of samples are much decrease since the quantity of polymer passive phase which
used to replace the BNT ceramics phase. Dielectric properties (measured at 1 kHz) and the
piezoelectric coefficient d33 of piezocomposites samples decreased when the volumetric ratio of
BNT active phase was decreased. Therefore, it can be said that properties of piezocomposites is
proportional to the volumetric ratio of ceramics phase. The dielectric and piezoelectric properties
of composites samples are 336 and 13 pC/N, respectively.

Advanced Materials Research Vols. 55-57

143

Figure 2. XRD pattern of BNT ceramics powder annealed at temperature of 1075 C


Moreover, it can be seen that dielectric constant of composites samples are much higher than those
of previous work [1] which used different of active and passive materials. Furthermore, the d33
values of obtained samples are close to work of K. Lam et al. [1] which used the piezopolymer
P(VDF-TrFE) as the passive phase and fabricated composites sample by using hot pressing
technique. Fig. 3 and Fig. 4 show a typical SEM micrograph of BNT powder and composites
sample, respectively. It has been found that the average particle size of BNT powder is about 10
m with the irregular shape (Fig. 3). Fig. 4 exhibits the fracture surface of 0-3 composites. The
dark area and bright areas are observed. The dark area belongs to the resin while the brighter area
belongs to the BNT powder. The BNT phase shows agglomeration of the particles which connected
by resin.
Table 1. Physical and electrical properties of piezoceramics and piezocomposites samples
Density
(g/cm3)

Vol
(%)

tan

d33
(pC/N)

BNT

5.804

100

621

0.18

98

BNT/Epoxy Resin

3.623

53

336

0.98

13

BNBT/P(VDFTrFE) [1]

40

32.2

0.95

-14

PZT 502/ P(VDFTrFE) [1]

40

34.0

Specimens

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Figure 3. SEM micrograph of BNT powder

Figure 4. SEM micrograph of the 0-3 composite


materials between the non-lead based ceramic
BNT and epoxy

Summary
BNT/epoxy resin 0-3 composites were fabricated via suction technique. It can be concluded that
the high volumetric ratio obtained from this technique. Density of piezocomposites (3.623 g/cm3) is
less than that of BNT ceramics (5.804 g/cm3). The dielectric and piezoelectric properties of
samples are 336 and 13 pC/N, respectively. It is also found that the dielectric constant is much
higher than composites samples which fabricated by using hot pressing and used different active
and passive phase. Furthermore, from SEM, the BNT particles were shown to be good packed
together, resulting in the composite being denser when fabricated the sample by using suction
technique.
Acknowledgements
The authors would like to express their sincere thanks to the Thailand Research Fund and the
Graduate School of Chiang Mai University for financial support. The authors also would like to
thanks Faculty of Science, Chiang Mai University for gratefully knowledge.
References
[1]
[2]
[3]
[4]
[5]

K. Lam, X. Wang and H.L. Chan: Composites Part A. Vol. 36 (2005), p.1595.
G.A. Smolenskii, V.A. Isupov, A.I. Agranovskaya and N.N. Krainik: Sov. Phys. Solid State.
Vol. 2 (1961), p. 2651.
T. Takanaka: Ultrason. Technol. Vol. 8 (2001), p. 2.
R.P. Tandon, D.R. Chaubey, R. Shngh and N.C. Soni: J. Mater. Sci. Lett. Vol. 12 (1993) p,
1182.
Powder Diffraction File, No.36-0340, International Centre for Diffraction Data, Swarthmore ,
PA, 2000.

Advanced Materials Research Vols. 55-57 (2008) pp 145-148


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.145

Microstructures of Zirconium Titanate Powders and Ceramics


Prepared by Solid-State Mixed Oxide Method
C. Puchmarka* and P. Tipparakb
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand
a*

kungmic2002@yahoo.com, bmanabuzung@hotmail.com

Keywords: Microstructure, Zirconium titanate powders, Zirconium titanate ceramics

Abstract. Zirconium titanate (ZrTiO4): ZT powders were prepared by solid-state mixed oxide
method. The mixed powder was calcined at various temperatures for 3 h ranging from 1100 to 1400
o
C with a heating rate of 5 oC/min. X-ray diffraction analysis of the powders was performed using a
diffractometer with Cu K. Pyrochlore phase was observed for calcinations below 1300 oC. In general,
the strongest reflections apparent in patterns could be matched with a JCPDS file number 74-1504.
The optimum calcination temperature for the formation of ZrTiO4 phase was found to be about 1300
o
C for 3 h with heating rate of 5 oC/min. The microstructures of calcined powders were examined
using scanning electron microscope (SEM). The particle size of powder increased with increasing
calcination temperature. The ZT ceramics sintered at 1450, 1500, 1550 and 1600 oC for 4 h with
heating rate of 5 oC/min, were checked for phase formation by X-ray diffraction. The density of
sintered samples was measured by Archimedes method. The microstructures of sintered samples were
examined using scanning electron microscope (SEM). The average grain sizes were checked by linear
interception method. It was found that, the samples sintered at 1450 and 1500 oC gave rise to high
purity ZT ceramics and the peaks matched well with ZrTiO4 phase in a JCPDS file number 74-1504.
Unknown phases were found in ZT ceramics sintered at 1550 and 1600 oC. The value of density was
in the range of 4.32 - 4.92 g/cm3 or 84.26 - 96.12 % of the ZT theoretical density. The densification of
ZT ceramics decreased with increasing sintering temperature. The ZT ceramics sintered at 1450 and
1500 oC showed the average grain size of 8.55 and 12.55 m, respectively. At sintering temperature
1550 and 1600 oC, morphology of grains changed to plate like crystals of second phases.
Introduction
The applications of ceramics based on zirconium titanate solid solutions are extremely wide. They
range from microwave telecommunications such as capacitors, dielectric resonators in filters,
oscillators, humidity sensors, high-temperature pigments and composites [1-3], to catalysis (as
effective acid-base bifunctional catalysts) [4]. The stoichiometry of zirconium titanate is known to be
an important factor for ensuring good properties [5]. In the present work, microstructures of ZrTiO4
powders and ceramics prepared by solid state reaction method are presented.
Experimental
ZrTiO4 powder was prepared by solid-state mixed oxide method on a mixture of ZrO2 and TiO2
powders. The mixture of these powders was ground for 12 h in ethanol using zirconia grinding media.
The mixed powder was calcined at various temperatures for 3 h ranging from 1100 to 1400 oC with a
heating rate of 5 oC/min. X-ray diffraction analysis of the powders was performed using a X-ray
diffractometer with Cu K. Microstructures of calcined powders were characterized using a scanning
electron microscope (SEM). After that, the calcined ZT powders were sieved and pressed into a disc
shape and sintered at 1450, 1500, 1550 and 1600 oC for 4 h with heating rate of 5 oC/min. The sintered
pellets were checked for perovskite phase formation by X-ray diffraction. The density of sintered
samples was measured by Archimedes method. The microstructures of sintered samples were

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examined using scanning electron microscope (SEM). The average grain sizes were checked by linear
interception method.
Results and Discussion
Fig. 1 shows XRD patterns of uncalcined and calcined ZT powders with calcinations temperature
from 1100 to 1400 C for 3 h with heating rate of 5 oC/min. Pyrochlore phase was observed for
calcination temperatures below 1300 oC. In general, the strongest reflections apparent in patterns
could be matched with a JCPDS file number 74-1504 [6] as shown in Fig.2. The optimum
temperature for calcinations the formation of ZrTiO4 phase, was found about 1300 oC for 3 h with
heating/cooling rate of 5 oC/min.

Figure 1. XRD patterns for ZT powder at various calcination temperatures.

Figure 2. XRD pattern of ZT powder calcined at 1300 oC for 3 h compared with JCPDS data file
no.74-1504.
Lattice parameters a, b and c of calcined ZT powder from 1300 to 1400 oC could be calculated by
X-ray program [7]. It was found that, the values of lattice parameters a, b and c of ZT powders
calcined at 1300 oC is a = 5.036(2), b = 5.461(8), c = 4.804(1), at 1350 oC is a = 5.033(8), b = 5.466(0),
c = 4.802(6) and at 1400 oC is a = 5.039(7), b = 5.458(0), c = 4.802(6) in angstrom unit. The
calculation lattice parameters a, b and c for calcination temperature between 1300 1400 oC were
closed to lattice parameters in the basis of Joint Committee on Powder Diffraction Standard (JCPDS)
data number 74-1504.

Advanced Materials Research Vols. 55-57

147

Fig. 3 shows microstructure of uncalcined ZT powders and those calcined at various temperatures
from 1100 to 1400 oC. For calcination temperatures below 1300 oC, the particles were agglomerated
and basically irregular in shape. For the powders calcined at high temperatures, the averaged particle
sizes and degree of agglomeration tended to increase with increasing calcination temperature. The
optimum condition for calcination temperature seemed to be at 1300 oC for 3 h with heating rate
5 oC/min.

Figure 3. SEM photographs of the ZT powders calcined for 3 h at (a) uncalcined, (b) 1100, (c) 1200,
(d) 1300, (e) 1350 and (f) 1400 oC.
Fig. 4 shows XRD patterns of ZT ceramics
sintered at 1450 to 1600 oC for 4 h with heating
rate of 5 oC/min. The samples sintered at 1450
and 1500 oC gives rise to high purity ZT
ceramics, the peaks matched well with ZrTiO4
phase in a JCPDS file number 74-1504 [6].
Unknown phases were found in ZT ceramics
sintered at 1550 and 1600 oC.

Figure 4. XRD patterns of ZT ceramics sintered at 1450 - 1600 oC.

Densitification of ZT ceramics as a function of sintering


temperature are plotted in Fig.5. The value of density is in
the range of 4.32 - 4.92 g/cm3 or 84.26 - 96.12 % of the ZT
theoretical density. The densification of ZT ceramics
decreased with increasing sintering temperature.

Figure 5. Density of ZT ceramics sintered at 1450 - 1600 oC.

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From the SEM micrographs in


Fig. 6, it can be seen that, the ZT
ceramics sintered at 1450 and
1500 oC showed the averaged
grain size of 8.55 m and
12.55 m, respectively. At the
sintering temperature 1550 and
1600 oC, the plate like crystals
of second phases were observed
with is corresponding to XRD
results. However, the phase
identification will be studied in
a further work.

Figure 6. SEM photographs of the ZT ceramics sintered for 4 h at (a) 1450, (b) 1500, (c) 1550 and
(d) 1600 oC.
Summary
ZrTiO4 phase of ZT powders as found at calcination temperature of 1300 oC for 3 h with heating rate
of 5 oC/min. Calculation of lattice parameters of unit cell is a = 5.036(2), b = 5.461(8), c = 4.804(1)
for powder calcined at 1300 oC. The averaged particle sizes and degree of agglomeration tended to
increase with increasing calcination temperature. The ZT samples sintered at 1450 and 1500 oC gave
rise to high purity ZT ceramics. The densification of ZT ceramics decreased with increasing sintering
temperature. The morphology of grains changed to plate like crystals of second phases at sintering
temperature above 1550 oC.
Acknowledgment
This work was supported by The Thailand Research Fund (TRF), Commission on Higher Education
(CHE) and Faculty of Science Naresuan University. The authors would like to thank Prof. Dr. Tawee
Tunkasiri for his help in many facilities.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

A.J. Moulson and J.M. Herbert, in: Electroceramics: Materials, Properties, Applications, 2nd
Edition (John Wiley & Sons Ltd, West Sussex, England, 2003).
A. Bianco, M. Paci and R. Freer: J. Eur Ceram. Soc., Vol. 18 (1998), p. 1235.
Information on http://www.integritytechnology.net/.../resonator.htm.
F.P. Daly, H. Ando, J.L. Schmitt and E.A. Sturm: J. Catal., Vol. 108 (1987), p. 401.
S. Ananta, R. Tipakontitikul and T. Tunkasiri: Mater. Lett., Vol. 57 (2003), p. 2637.
Powder Diffraction File, Card No.74-1504. Joint Committee on Powder Diffraction Standards
(JCPDS) PDF-4, Internation Centre for Diffraction Data (ICDD), (2000).
M. Calligaris and S. Geremia, in: X-ray powder program version 1.20A (Department of
Chemical Sciences, University of Trieste, Via Licio Giorgeri 1, 34100 Trieste, Italy).

Advanced Materials Research Vols. 55-57 (2008) pp 149-152


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.149

Preparation and Properties of B2O3-Doped Ba(Zr0.07Ti0.93)O3


Ceramics
P. Jarupoom, G. Rujijanagul*, K. Pengpat and T. Tunkasiri
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
*rujijanagul@yahoo.com
Keywords: BZT, ferroelectric ceramic, dielectric constant, perovskite

Abstract. In this work, barium zirconate titanate (Ba(Zr0.07Ti0.93)O3) ferroelectric ceramics doped
with B2O3 were prepared by the conventional mixed-oxide method. The properties of the ceramics
as a function of sintering temperature were investigated. Various technique such as X-ray
diffraction (XRD) technique, scanning electron microscopy, dielectric permittivity spectroscopy
and ferroelectric property measurement were used to obtain characteristic of the ceramics. The
optimum density was observed for 1250 oC sintered sample. An increase in sintering temperature
produced a decrease in dielectric constant. However, ferroelectric behavior was improved in 1275
o
C sintered sample. The results were discussed in term of microstructure and crystallinity of the
ceramics.
Introduction
Barium titanate (BaTiO3) is one of the most studied ferroelectric materials due to its excellent
properties, high dielectric constant and low dielectric loss [1]. Recently, the addition of zirconium
(Zr) into titanium (Ti) site in barium titanate has been chosen in fabrication of ceramic capacitors
because Zr4+ is chemically more stable than Ti4+ and has a larger ionic size (to expand the
perovskite lattice) [2]. Moreover, Zr-substitution at Ti-site has been found to be interesting features
in the dielectric behavior and to effectively to decrease the Curie temperature of BaTiO3 ceramics.
For over a number of years, many researchers have attempted to decrease the sintering temperature
of BaTiO3 based ceramics through the use of various sintering aids such as B2O3, Li2O, etc. [3].
However, very few works have reported on the preparation and dielectric properties of BaZrxTi1-xO3
ceramic sintered at low temperature. In this work, Ba(Zr0.07T0.93)O3 ceramics doping with 2 wt.% of
B2O3 were prepared by the conventional mixed-oxide method. The effect of sintering temperature
on the density and the electrical properties at room temperature of the ceramics were investigated.
Experimental
Ba(ZrxTi1-x)O3 (BZT) ceramics were prepared by the conventional mixed-oxide method. The
starting materials barium carbonate (BaCO3), titanium dioxide (TiO2) and zirconium oxide (ZrO2)
were weighed based on the stoichiometric composition of Ba(Zr0.07Ti0.93)O3. The weighed batch
was ball-milled in alcohol and zirconia milling media for 24 h. After drying, the mixtures were
calcined in an alumina crucible at 1200 oC for 2 h in air atmosphere. The doping addition of 2wt. %
B2O3 to the BZT powder was prepared. The calcined powders were again milled in alcohol for 24 h.
The obtained powders with the addition of 3w% polyvinyl alcohol (PVA) binder were pressed into
disc-shape pellets with a diameter 10 mm. The green pellets were sintered at temperatures ranging
from 1150 oC to 1475 oC for 2 h. Phase formation and crystallographic structure of the ceramics
were studied by XRD. The bulk densities of sintered samples were measured using Archimedes
method, ASTM C 373-88. Microstructural study of sintered samples was performed under an
scanning electron microscope (SEM). For electrical study, silver paste was painted on both sides of
the samples. The dielectric constants of the samples were measured using LCZ (Hewlett Packard)
from 20 Hz to 2 MHz at room temperature. The hysteresis loops were measured at room
temperature using a hysteresis circuit.

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Results and Discussion


XRD patterns of BZT ceramics doped with 2 wt. % of B2O3 are shown in Fig. 1. As revealed from
the XRD patterns, all the diffraction peaks matched well with the peaks of the perovskite phase. With
in the limit of detection, the second phase was not observed for all samples. An increase of sintering
temperature resulted in an increase of diffraction peak intensity, indicating that B2O3 help to
improve the degree of crystallinity in the ceramics.

Fig. 1 XRD patterns of B2O3 doped BZT ceramics.


Fig. 2 shows a plot of density as a function of sintering temperature. The density increased with
increasing sintering temperature up to 1250 oC and then decreased at 1275 oC (Fig.2). It is known
that the presence of a B2O3 liquid phase assists densification during sintering. At higher
temperature, however, high evaporation of B2O3 was occurred. Therefore, a drop in density was
observed for the sample sintered at 1275oC and above. The SEM micrographs of 2 wt. % doped
BZT ceramics are shown in Fig. 3. The microstructure for the sample sintered at lower temperature
was observed to be quite dense. Little porosity appeared for the sample sintered at high sintering
temperature. There was no change in the grain size, nor is there any evidence of abnormal grain
growth in the annealed sample. The grain size of the sample was found to increase with increasing
the sintering temperature.

Fig. 2 Bulk density of B2O3 doped BZT ceramics.

Advanced Materials Research Vols. 55-57

(a)

151

(b)

Fig. 3 SEM micrographs of B2O3 doped BZT ceramics sintered at; (a) 2wt. % of B2O3 sintered
1225 oC (b) 2wt. % of B2O3 sintered 1250oC
Fig. 4 presents dielectric constant measured at room temperature of the samples as a function of
frequency for 20 Hz to 2 MHz. It was found that BZT ceramics obtained the optimum dielectric
constant while BZT doped B2O3 samples exhibited the decrease of dielectric constant with an
increase of sintering temperature. It may be due to the effect of grain size that as suggested from Jin
et al. [5-6] that the dielectric constant depends strongly on grain size. Furthermore, the decrease of
dielectric constant also resulted from the difference in crystal structure caused by increasing in
tetragonality when boron ions were inserted in to an interstitial of BZT lattice.

Fig. 4 Dielectric constant at room temperature of B2O3 doped BZT ceramics.


The PE ferroelectric property measurements for the samples are shown in Fig. 4. Slanted
hysteresis curves were observed for the samples sintered at low temperatures. The hysteresis curve
became a square shape for the sample sintered at 1275C. The remanent polarization (Pr), was
observed to increase with increasing the sintering temperature. However, coercive field (Ec) was
found to be 4.0kV/cm for all sintering conditions. The better ferroelectric behavior may be due to
the better crystallinity of the sample sintered at high temperature.

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Fig. 5 P-E loops at room temperature of BZT ceramics with various sintering temperature.
Summary
B2O3 doped BZT ceramics were fabricated by a conventional solid state sintering. Various sintering
temperatures were performed to study effect of heat treatment on the properties of the ceramics. A
higher sintering temperature produced a better ferroelectric behavior. However, it resulted in a
lower dielectric permittivity.
Acknowledgements
This work was supported by The Thailand Research Fund (TRF) for financial support, including the
support given through the Royal Golden Jubilee Ph.D. Program, National Metal and Materials
Technology Center (MTEC), Faculty of Science and Graduate School Chiang Mai University, and
Commission on Higher Education (CHE) Thailand. The authors would like to thank Prof. Dr.
Tawee Tunkasiri for his help in many facilities.
References
[1]
[2]
[3]
[4]
[5]
[6]

Z. Yu, R. Guo and A. S. Bhalla: J. Appl. Phys. Vol. 88 (2000), p. 410.


B. L. Cheng, C. Wang, S. Y. Wang, H. Lu, Y. L. Zhou, Z. H. Chen and G. Z. Yang: J. Eur.
Ceram. Soc. Vol. 25 (2005), p. 2295.
T. Hu, T. J. Price, D. M. Iddles, A. Uusimaki and H. Jantunen: J. Eur. Ceram. Soc. Vol. 25
(2005), p. 2531.
Z. Yu, C. Ang, R. Guo and A. S. Bhalla: J. Appl. Phys. Vol. 92 (2002), p. 1489.
X. G. Tang, J. Wang, X. X. Wang and H. L. W. Chan: Solid State Commun. Vol. 131 (2004),
p. 163.
D. Z. Jin and X. M. Chen: Ceram. Int. Vol. 29 (2003), p. 371.

Advanced Materials Research Vols. 55-57 (2008) pp 153-156


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.153

Characterization of LiNbO3 Powder Prepared by Citrate Gel Method


S. Onnom1, D. Wongratanaphisn2, P. Supaphol3, P. Udomsamuthirun1,a,
T. Nilkamjon1, S. Radrang1, S. Sonkrua1 and S. Payoogthum1
1

Department of Physics,Faculty of Science,Srinakharinwirot University,Sukumvit 23,Bangkok


10110,Thailand.

Department of Physics,Faculty of Science,Chiang Mai University,Chiang Mai, 50200,Thailand.


3

The Petroleum and Petrochemical College,Chulalongkorn University,


Pathumwan,Bangkok,10330,Thailand.
a

udomsamut55@yahoo.com

Keywords: LiNbO3 powder, citrate gel method

Abstract. Lithium niobate powder (LiNbO3) were synthesized by citrate gel method using LiNO3,
Nb2O5, citric acid and HF as starting materials. LiNO3 was dissolved in distilled water that activated
into LiOH. Nb2O5 was dissolved in minimum amount of HF at 370C for 20 h. that activated into
NbF5. Then citric acid, LiOH, and NbF5 were mixed in stoichiometric ratio. On heating at 1000C for
3-4 h. a yellowish gel is formed. Lithium niobate powders were obtained after calcination at 5507000C. The effect of calcination temperature at various temperatures ranging from 5500C to 7000C
were investigated. The phase and chemical composition of the synthesized powders were
characterized by using XRD, SEM, TEM, FTIR and EDX. We found that the lithium niobate
crystallize phase formed when the calcination temperature at 6500C with average particle size of
around 100 nm .
Introduction
According to the excellent electro-optical and photo-refractive properties of LiNbO3 (LN) ceramics,
there are extensive applications as optical wave guides and modulators and surface acoustic wave
devices[1-5]. Conventionally, LN powders prepared by solid state reactions lead to the composition
deviation from stoichiometry because of lithium evaporation at higher temperatures [6,7] .The
potential advantage of wet chemical methods to over conventional methods lies in the improved
homogeneity expect. Navale, Samuel and Ravi[8] had applied a simple co-precipitation technique
for the preparation of pure ultrafine single phase LN . They found LN phase crystallized at 7000C
with average particle size of 100 nm. Samuel et al.[9] had synthesized LN by citrate gel method.
They found LN phase crystallized at 4000C with average particle size of 70 nm. Liu ,Xue and
Luo[10] had used a wet chemical method to synthesize LN powder from simple and inexpensive
niobium oxide, citric acid and lithium hydroxide as raw materials. They showed that the proper
sintering temperature for lithium niobate gels should be around 6000 C for pure LN. In this research,
we synthesized the LN by citrate gel method. A simple and inexpensive niobium oxide, citric acid
and lithium hydroxide were used as raw materials. We investigated the effect of calcination
temperature to the quality of obtained LN powders. X-ray diffraction(XRD), Scanning electron
microscopy (SEM), Transmission electron microscope(TEM), Fourier transform infrared
spectra(FTIR) and Energy dispersive X-ray(EDX) were used to characterized the properties of our
samples.
Experimental
For synthesis of LiNbO3 powder, we prepare the starting materials that are the inorganic salts by the
following chemical reactions.

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LiO3 + H 2 O LiOH + HO3


b2 O5 + 10 HF 2 bF5 + 5 H 2 O
LiNO3(purum), Nb2O5 (mesh),citric acid(assay) and hydrofluoric acid(70% by weight) were used as
starting materials of this process. A stoichiometric amount of LiNO3 was dissolved in distilled
water and Nb2O5 was dissolved in minimum amount of HF after heating a hot water bath at 37 0C
for 20 h.Then citric acid, lithium nitrate( LiOH ) and niobium fluoride ( bF5 ) were mixed in
stoichiometric ratio. There was no precipitation during mixing of citric acid and these metal salts.
On heating water bath at 100 0C a gel was formed after evaporation of water. The gel was yellowish
after heating for 3-4 h. Then the gel was decomposed at various temperatures ranging from 5500 C
to 7000C (step up and down 100C/minute) for 6 hours. Finally, we can get the black powders after
calcining at different temperatures for 6 hours. The effect of calcination temperature to the quality
of LN powders by varying the calcination temperatures (550, 600, 650 and 7000C)were
investigated. XRD, SEM,TEM,FTIR and EDX were used to characterize the properties of the
obtained LN powders. The powder X-ray diffraction patterns were recorded for all the samples
calcined at different temperatures by using a D8 Advance Bruker model X-ray diffractometer and
Cu K radiation with = 1.5405 . For lattice parameter calculation, the samples were scanned in
the 2 range of 20-500. The niobium and oxygen contents in the samples were determined by EDX
(JSM 5800LV, JEOL). SEM (JSM 5800LV, JEOL) investigation was performed on the
microstructure of the obtained LN powders. TEM (JEOL 2010) observation was made with the
accelerating voltage of 100 kV to study the particle size and morphology. FTIR (SpectrumOne,
PerkinElmer) measurement was measured in the ranging of 450-2000 cm-1.
Results and Discussion
According to the selected LN samples , XRD patterns at difference calcination temperature at
550,600,650 and 7000C were shown in Figure 1.

Figure 1. Shown the XRD patterns of the powders calcined at different temperatures.
When the temperature was raised at 650 0C, it can be observed that almost diffraction peaks were
assigned as the hexagonal LN structure with some peaks of cubic LiF as impurity. The
corresponding crystallographic planes of haxagonal peak were indexed and the lattice constant are
a= 5.1483 and c= 13.6831 . It was agree that the crystallinity of the synthesized LN powders
was clearly improved with the increased of temperature to 6500 C. It is well known that when the

Advanced Materials Research Vols. 55-57

155

temperature is high enough, lithium cation diffuses easily; even it can evaporate from the raw
material. As a result, it may cause a difference of lithium in the obtained sample such as the
appearance of LiNb3O8 phase and LiF phase at 700 0C. Our results were agreed with the discussion
of Liu, Xue and Luo[10,11] that when the calcination temperature was between 700 to 800 0C, the
Lib3O8 phase was found. In additional, LiF phase may occur from the reaction with lithium
corresponding to the fluoride found in the EDX analysis. The average crystallite size of 104 nm
was calculated from the Scherrers formula. The chemical composition of LibO3 were found by
EDX. The molar ratio of Nb : O contents were shown in Table 1. The LN3 was best fit in the molar
ratio. That result meaned that excellent composition of chemistry of LN powders when calcination
temperature was at 6500C. However,LN3 sample show that there was fluoride as impurity.
Table 1. Molar ratio and phase composition of obtained LN powders.
Sample
LN1
LN2
LN3
LN4

Nb:O molar ratio from EDX


1: 2.27
1 : 2.12
1 : 2.64
1 : 2.61

Phase composition from XRD


LiNbO2 and Nb2O5
LiNb3O8 and Nb2O5
LiNbO3 and LiF
LiNbO3 and LiNb3O8

LN 4
LN 3

LN 2
LN 1
Figure 2. FTIR spectra of the obtained LN powders.
The absorption band at 671, 679, 681 cm-1 is attributed to Nb-O vibration in the crystalline state
LN[5],which was the characteristic LN IR finger printing absorption. Our sample also show the
absorption band at 1627, 1628, 1633 cm-1 that were attributed to OH vibration which show that
this sample contains some organic compounds even though there was no indication from XRD
measurement. The LN3 show the best fit of LN IR finger printing absorption.

Figure 4. Shown the TEM of LN3 sample.

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Figure 5. SEM images of LN3 sample.


Because the LN3 was shown the excellent properties of LiNbO3 powder, the microstructure of LN3
powder were studied by SEM and TEM and their image are shown in Fig.4 and 5. It can be
observed that the samples were composed of nanocrystals and the average crystalline size is about
100 nm. The XRD, SEM and TEM estimation of the particle size are in satisfactory agreement is
about 100 nm. The excellent composition of chemistry of LN powders were obtained when the
calcination temperature was at 6500C.
Summary
A simple citrate gel method was used to prepare ultrafine particles of LiNbO3. The effect of
calcination temperatures to the quality of LN powders by varying the calcination temperature as
550,600,650 and 7000C, were investigated. XRD, SEM, TEM, FTIR and EDX were used to
characterized the properties of the obtained LN powders.The LiNbO3 powder was found to form at
650 0C with average particle size of around 100 nm.
References
[1]

P. Sen, P.K. Sen, R. Bhatt, S. Kar, V. Shukla and K.S. Bartwal: Solid State Commun. Vol.
129 (2004), p. 747.
[2] S.D. Chang, C.H. Kam, Y.Z. Zhou, Y.L. Lam, Y.C. Chan and S. Buddhudu: Mater. Lett. Vol.
45 (2000), p. 19.
[3] P. Afanasiev: Mater. Lett. Vol. 34 (1998), p. 253.
[4] E.R. Camargo and M. Karkihana: Solid State Ionics Vol. 151 (2002), p. 413.
[5] C. An, K. Tang, C. Wang, G. Shen, Y. Jin and Y. Qian: Mater. Res. Bull. Vol. 37 (2002), p.
1791.
[6] V.T. Kalinnikov, O.G. Gromov, G.B. Kunshima, A.P. Kuzmin, E.P. Lokshin and V.I.
Ivanenko: Inorg. Mater. Vol. 40 (2004), p. 411.
[7] M. Liu and D. Xue: Solid State Ionics Vol. 177 (2006), p. 2908.
[8] S.C. Navale, V. Samuel and V. Ravi: Ceram Int. Vol. 32 (2006), p. 847.
[9] V. Samuel, A.B. Gaikwad, A.D. Jadhav, S.A. Mirji and V. Ravi: Mater. Lett. Vol. 61 (2007),
p. 765.
[10] M. Liu, D. Xue and C. Luo: J. Alloys Compd. Vol. 476 (2006), p. 118.
[11] M. Liu and D. Xue: Solid State Ionics Vol. 177 (2006), p. 275.

Advanced Materials Research Vols. 55-57 (2008) pp 157-160


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.157

X-Ray Absorption Spectroscopy Study of Ba1-xSrxTiO3 (x = 0.0-0.2)


at the Ti-K and Ba-LIII Edges
W. Somphon1,a and S. Srilomsak2,b
1

National Synchrotron Research Center, Nakhon Ratchasima 30000, Thailand

School of Ceramic Engineering, Suranaree University of Technology, Nakhon Ratchasima


30000, Thailand
a

weenawan@nsrc.or.th, bsriloms@hotmail.com

Keywords: X-Ray Absorption Spectroscopy, BaTiO3, Ferroelectric, Barium Strontium Titanate

Abstract. Barium titanate, BaTiO3 is a significant material for electronic components. It was known
that Sr2+ substitution on Ba ion can strongly modify ferroelectric properties of BaTiO3 but the
structural change has not been fully understood. An X-ray absorption spectroscopy at the Ti K-edge
(4966 eV) and the Ba LIII-edge (5247 eV) was employed to investigate the structure of Ba1-xSrxTiO3
(BSTO) with 0<x<0.20. Results suggested that Ba2+ did not change its position with Sr2+
substitution. On the other hand, Ti4+ atoms gradually displaced as Sr2+ is increased.
Introduction
Barium titanate (BaTiO3) and strontium titanate (SrTiO3) are perovskite ceramics widely used in
many high technology devices [1,2]. BaTiO3 is a ferroelectric that undergoes a paraelectric (cubic)
to ferroelectric (tetragonal) phase transition (Tc) at 120 C; an orthorhombic transition at 5 C and a
rhombohedral transition at -80 C. SrTiO3 is paraelectric and shows dielectric properties at low
temperature [3].
Barium strontium titanate, Ba1-xSrxTiO3 (BSTO), is the solid solution of BaTiO3-SrTiO3 which
are important for tunable microwave device applications such as capacitors, oscillators, resonators,
positive temperature coefficient resistor (PTCR), and dynamic random access memory (DRAM)
[4,5] because of their ferroelectric, high dielectric constant and high resistivity [6]. A small
substitution of Sr2+ for Ba2+ into the BaTiO3 decreased the Curie point (Tc) towards room [7,8].
Recently, X-Ray Absorption Spectroscopy (XANES and EXAFS) was used as a tool to study
the local structure of BaTiO3 and Ba1-xSrxTiO3 [9,10]. Shuvaeva et al. [10] performed Ba K-edge
EXAFS spectra analysis of Ba1-xSrxTiO3 with x = 0-0.75 and found that the displacement of Ba
atom almost does not exist until Sr concentration (x)>0.3. On the other hand, Ti atoms were found
to have gradual displacement with Sr concentration when 0<x<0.7. Although much work has been
done to date, more studies need to be conducted to ascertain the effects of Sr2+ substitution on Ba2+
of BaTiO3. This study investigates the effect of Sr2+ substitution in BaTiO3 in order to understand
the local structure of the distorted ferroelectric materials. In this study BSTO with x = 0.0-0.2 was
examined by X-Ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) with Ti K and Ba
LIII-edges spectra analysis.
Experimental
Ba1-xSrxTiO3 samples with x = 0.0-0.2 were synthesized by solid state reaction. BaTiO3 and SrTiO3
powders were mixed and then calcined at 1400 C at a rate of 5 C/min with 1 h soaking. The
following powders were prepared: BaTiO3 (x = 0.0), Ba0.95Sr0.05TiO3 (x = 0.05), Ba0.9Sr0.1TiO3
(x = 0.1), Ba0.85Sr0.15TiO3 (x = 0.15), and Ba0.8Sr0.2TiO3 (x = 0.2).
Phase analysis of powders was accomplished by XRD. X-ray patterns were collected on a
Bruker Analytical X-ray Systems model D5005 diffractometer equipped with a Cu K sealed tube

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X-ray source operating at 40 kV and 40 mA. The data were collected in the range of 5.0-90.0 2 in
steps of 0.02 and a scan speed of 0.4 sec/step.
The X-Ray Absorption Spectroscopy (XAS) employed in this study was contributed at BL-8 by
Siam Photon Laboratory of the National Synchrotron Research Center (NSRC). Experiments were
performed at the Ti K-edge (4966 eV) and Ba LIII-edge (5247 eV) in transmission mode at room
temperature. X-Ray Absorption Near Edge (XANE) spectra were collected at the Ti K-edge and Ba
LIII-edge. A monochromatic beam was obtained by means of a InSb(111) double crystal
monochromator. The electron storage ring was operated at 1.2 GeV with an average beam current
of ~110 mA. Ti foil was used to calibrate the Ti K-edge (4966.4 eV) of the Ti metal. Several
standard samples were used for the XANES spectra, including TiO2 (Ti4+), Ti2O3 (Ti+3) and BaCO3.
XANES spectra of the samples were collected at Ti K-edge in an energy range between 4940-5040
eV, with energy steps of 0.5 eV and at Ba LIII-edge between 5220-5320 eV with energy steps of 0.5
eV. Samples were ground homogeneously in an agate mortar, put in kapton tape on the sample
holder and then analyzed.
Results and Discussion
XRD patterns of Ba1-xSrxTiO3 (x = 0.0, 0.05, 0.1, 0.15, and 0.2) are shown in Fig. 1(a) and Fig. 1(b)
for a wide and narrow range angle, respectively. It can be seen all peaks of XRD patterns of
undoped BaTiO3 (x = 0.0) correspond to the tetrahedral phase and all the d-spacing lines are
consistent with reference [11] (see Fig. 1(a)). Moreover, clear peaks of 2 degrees are shifted
toward higher angle by increasing the mole ratios of Sr to Ba. The merging of the doublets at 2 =
51.4, 56.4, 65.8 and 70.1 to singlets indicated a tetragonal-cubic phase transition (see Fig 1(b)).

(b)

x = 0.2
x = 0.15
x = 0.1

20

30

40

50

60

2 (degrees)

70

x = 0.2

Intensity (arb. unit)

Intensity (arb. unit)

(a)

x = 0.15
x = 0.1

x = 0.05

x = 0.05

x = 0.0

x = 0.0

80

90

50

55

60

65

70

75

80

2 (degrees)

Figure 1. XRD patterns of Ba1-xSrxTiO3 (x = 0.0-0.2), (a) a wide range angle and (b) a narrow range
angle.
XANES spectra at the Ti K-edge (4966 eV) are shown in Figure 2. Fig. 2(a) shows spectra of
BaTiO3 and SrTiO3 perovskites along with several Ti standard compounds: Ti foil (Ti0), Ti2O3
(Ti3+), TiO2 (Ti4+). These results show that the Ti in the BaTiO3 structure is located in a somewhat
different position compared with Ti-foil, TiO2, Ti2O3 and SrTiO3.
Fig. 2(b) displays the Ti K-edge spectra of Ba1-xSrxTiO3 (x = 0.0-0.2). It is clear that the Ti Kedge spectra in the energy region 4965-4975eV (marked by arrows) show subtle change with Sr2+
substitution. According to Krayzman et al. [12] the peaks in this region are caused by the excitation
of Ti 1s electron to either the t2g or eg orbitals of [TiO6] octahedrons. In addition, the intensity of
peaks in this range is strongly depends on [TiO6] distortions. Therefore, the subtle change of peaks

Advanced Materials Research Vols. 55-57

159

Intensity (abr. unit)

Intensity (abr. unit)

in 4965-4975 eV of Ti K-edge spectra in this work indicates that the Ti4+ gradually displaced with
Sr2+ replacement on Ba2+.
Fig. 3 shows XANES spectra at the Ba LIII-edge (5247 eV) of Ba1-xSrxTiO3 (x = 0.0, 0.05, 0.1,
0.15, and 0.2). BaCO3 was used as a reference. It appears that Ba LIII-edge spectra of all Ba12+
in Ba1xSrxTiO3 samples with 0<x<0.20 are almost the same. This result suggests that the Ba
2+
2+
Sr
TiO
is
very
slightly
off
center
compared
with
Ba
in
BaTiO
.
In
other
words
Ba
almost
does
x x
3
3
2+
not change its position with Sr substitution. This finding and the finding in previous paragraph are
substantial agree with Shuvaevas work [10], although Shuvaevas work was done by using Ba Kedge of EXAFS spectra.

Figure 2. Ti K-edge XANES spectra of, (a) BaTiO3 and SrTiO3 and three Ti standards (Ti foil,
TiO2, and Ti2O3) and (b) Ba1-xSrxTiO3 (x = 0.0-0.2).

Intensity (abr. unit)

Ba LIII-edge

x = 0.2
x = 0.15
x = 0.1
x = 0.05
x = 0.0
BaCO3

5220

5240

5260

5280

5300

5320

Energy (eV)

Figure 3. Ba LIII-edge XANES spectra of Ba1-xSrxTiO3 (x = 0.0-0.2) and BaCO3.

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Summary
The structure of Ba1-xSrxTiO3 (x = 0.0-0.2) was investigated with XRD and XAS techniques. The
XRD data showed that the BSTO structure changed from tetrahedral toward cubic with increasing
Sr2+ mole fraction. The XAS results showed that Ti4+ ion gradually shifted off-centre while Ba2+
ions almost did not relocate with Sr2+ substitution. Although these results confirm earlier finding of
Shuvaeva et al, it is recommend extending this study to cover wider range of Sr2+ substitution in
order to obtain more comprehensive information on effect of Sr2+ substitution in BaTiO3 structure.
References
[1]
[2]
[3]
[4]
[5]

L. Cross: Am. Ceram. Soc. Bull. Vol. 63 (1984), p. 586.


F. Jona and G. Shirane: Ferroelectric Crystals, (Dover Pub. Inc., New York, 1993).
K.A. Muller and H. Burkhard: Phys. Rev. B Vol. 19 (1979), p. 3593.
J.Y. Wang, X. Yao and L.Y. Zhang: Ceram. Int. Vol. 30 (2004), p. 1749.
N.A. Frey, R. Heindl, S. Srinath, H. Srikanth and N.J. Dudney: Mater. Res. Bull. Vol. 40
(2005), p. 1286.
[6] R. Jones, P. Zurcher, P. Chu, Dj. Taylor, Yt. Lii, B. Jiang, Pd. Maniar and S.J. Gillespie:
Microelectron. Engrg. Vol. 29 (1995), p. 3.
[7] V.V. Lemanov, E.P. Smirnova, P.P. Syrnikov and E.A. Tarakanov: Phys. Rev. B Vol. 54
(1996), p. 3151.
[8] S.K. Rout, S. Panigrahi and J. Bera: Mater. Sci. Eng. B Vol. 99 (2001), p. 8.
[9] B. Ravel, E.A. Stern, R.I. Vedrinskii, and V. Kraizman: Ferroelectrics Vol. 206-207 (1998),
p. 407.
[10] V. Shuvaeva, Y. Azuma, K. Yagi, H. Terauchi, R. Vedrinski, V. Komarov and H. Kasatani:
Phys. Rev. B Vol 62 (2000), p. 2969.
[11] H. Swanson and H. Fuyat: Natl. Bur. Stand. (U.S.), Circ. Vol. 539(3) (1954), p. 44.
[12] V. Krayzman, I. Levin, J.C. Woicik, D. Yoder and D.A. Fischer: Phys. Rev. B Vol. 74 (2006),
p. 224104.

Advanced Materials Research Vols. 55-57 (2008) pp 161-164


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.161

Synthesis of Na0.5Bi0.5TiO3 Submicron Particles in Molten Salt


P. Setasuwona and S. Kijamnajsuk
National Metal and Materials Technology, Pathumthani 12120
a

paisan@mtec.or.th

Keywords: Na0.5Bi0.5TiO3, SrTiO3, submicron particles, molten salt synthesis

Abstract. Powder size is a major factor determining the characteristics of processing variables and
end-products of ceramic materials. Na0.5Bi0.5TiO3 is one of the potential candidates for non-lead
piezoelectric materials, synthesis of Na0.5Bi0.5TiO3 particles in molten salt was studied. Two salt
systems, NaCl-KCl and Na2SO4-3K2SO4 were investigated. Only at 850C and above, BNT was
completely formed without any secondary phases in both eutectic chloride and sulfate salt. By
substituting chloride with sulfate, the particle size of BNT could be greatly reduced to a few
hundreds nanometer at 850C. Submicron particles of SrTiO3 could also be synthesized in eutectic
sulfate salt at 850C, It is evident that molten salt synthesis could be employed to produce
submicron particles of Na0.5Bi0.5TiO3 and SrTiO3. Molten salt synthesis is low-cost and capable to
produce fine powders of various complex-oxides.
Introduction
Powder size is a major factor determining the characteristics of processing variables and properties
of electroceramics. Submicron or nanoparticles have very large surface area, which enhances the
rate of reaction, reduces the reacting temperature, improves densification and develops
microstructure with fine grain. Fine powders with submicron size are preferred for lower processing
cost and enhanced properties
Nanoparticles are synthesized using two main techniques: gas phase synthesis and sol-gel
processing [1]. Gas phase synthesis includes combustion [2], flame spray pyrolysis [3], plasma [4]
and laser ablation [5], Sol-gel processing includes gelation [6], precipitation [7,8] and hydrothermal
synthesis [9]. These chemical preparations use costly chemicals as raw materials. There are also
some additional techniques for synthesis of nanoparticles, such as sonochemical processing,
microemulsion processing, and high-energy ball milling Except high energy ball milling, all
mentioned techniques are bottom-up approach. High-energy ball milling is the only top-down
approach [10], which reduces powders of micron ranges to submicron or nanoparticles by high
energy impact [11]. Although high-energy mechanical milling uses cheap metal-oxide powder, but
the energy cost is rather high and contamination may be introduced.
As the concern on environment and health is increasing, one of the potential candidates for nonlead piezoelectrics is Na0.5Bi0.5TiO3. Its properties are also depended upon powder size. In this
work, molten salt synthesis is investigated as a method to control the size of BNT particles.
Experimental
The starting materials are Na2CO3 (Fluka, 99%), SrCO3 (Fluka, 99% ), Bi2O3 (Fluka, 98%) , TiO2
(Fluka, 99%), NaCl (Analar, 99.5%), KCl (Riedel-de Han, 99.5%), Na2SO4 (BDH, 99%) and
K2SO4 (BDH, 99%). Na2CO3, Bi2O3 and TiO2 were mixed with stoichiometric amounts for
Na0.5Bi0.5TiO3. The mixtures were added with 75% volume of either eutectic mixture of chloride or
sulfate salt (1NaCl:1KCl and 1Na2SO4:3K2SO4, respectively). They were milled in acetone with
5 mm ZrO2 balls for 24 hr. After drying they were put in alumina crucibles and the lids were sealed
with alumina cement to reduce the evaporation of salts. The mixtures were heated to 450C, 650C,
850C and 1050C for 2 hrs, with the heating rate of 5C/min and cooling rate of 3C/min. After

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cooling, salts were removed by washing with hot distilled water several times. Phase and
morphology of the reactants were characterized with an X-ray diffractometer (XRD, Jeol JDX-3)
and a scanning electron microscope (SEM, JEOL, JSM-6301F). Later the stoichiometric mixtures
for SrTiO3 were treated with the same method at 850C and 1050C.
Results and Discussion
Fig. 1 displays the X-ray diffraction patterns
of Na0.5Bi0.5TiO3 (BNT) stoichiometry.
Synthesis in sulphate salt at 450C did not
produce the desired compound of BNT
(Fig.1a), TiO2 was still evidently present.
Raising temperature to 650C (Fig. 1b) , BNT
formation was almost complete. There is a
small peak near 30 degree 2, indicating a
secondary phase. That secondary phase is
probably a pyrochlore phase [12]. At 850C
and 1050C, BNT was fully formed.
The X-ray diffraction pattern at 450C in
chloride salt was not shown here as BNT had
not been formed yet. A secondary phase also
existed at 650C (Fig. 1e) with the peak at the
same position as in the case of sulphate salt.
Only at 850C and above, BNT was
completely formed without any secondary
phases.
Fig. 2 shows SEM micrographs of BNT
synthesized in chloride salt. At 1050C, BNT
particles were well crystallized with clear
facets. The crystal size are 0.5-2 micron. At
850C (Fig. 2a), the particle size is smaller,
mostly less than one micron. Although
molten salt synthesis was intentionally
employed to grow small to medium crystal
Figure 1. XRD patterns of molten salt synthesized particles, it is interesting that fine particles in
BNT in sulphate salt at a) 450C, b) 650C, c) submicron range could also be produced by
850C and d) 1050C and in chloride salt at e) reducing synthesizing temperature. At some
low temperatures the intended phase of BNT
650C, f) 850C and g) 1050C.
could still be completely formed in chloride
salt with submicron size.
At 1050C, with sulfate salt (Fig. 3), the BNT particles are finer than those synthesized in chloride
salt at even lower temperature of 850C. Reducing the temperature to 850C in sulfate salt, BNT
particles are much finer, in the range of a few hundreds nanometer. By substituting chloride salt
with sulfate salt, the size of molten-salt-synthesized particles was greatly reduced. The eutectic
temperature of NaCl-KCl is 650C while it is about 450C for the eutectic Na2SO4-3K2SO4. The
lower melting point of sulfate salt might comparatively increase soluability of starting materials and
the resulted BNT. When the temperature fell, nuclei in sulfate salt were formed at lower temperature
and had less time to grow, resulting in finer particle sizes. It was also possible that the surface
energy of BNT crystals might be higher in chloride system than in sulfate salt. The higher surface
energy would lead to reduction of surface area by crystal growth and, therefore, larger particle size.

Advanced Materials Research Vols. 55-57

163

Figure.2. SEM micrographs of BNT synthesized in chloride salt at a) 850C and b) 1050C and
in sulphate salt at c) 850C and d) 1050C.

To investigate further the application of molten salt in production of submicron particles, SrTiO3
was synthesized in eutectic Na2SO4-3K2SO4 at various temperatures. The employed procedure was
the same as in the case of BNT. It was found that some unreacted SrCO3 and TiO2 were still present
at 650C. Increasing the temperature to 850C, fully formed SrTiO3 was obtained. This is similar to
the synthesis of BNT earlier. Fig. 3 shows SEM micrographs of SrTiO3 particles synthesized in
sulfate salt at 850C and 1050C. The particles of SrTiO3 are not as fine as those of BNT. However,
the particle size is still less than one micron for both 850C and 1050C. The particles at 850C
were finer than those at 1050C. It was demonstrated that molten salt synthesis could be employed
not only for production of small to medium size crystals but also the synthesis of fine particles in
submicron range. Using cheap metal-oxide powders as raw materials comparing to chemical
methods, consuming much less energy than high energy ball milling and not requiring expensive
equipments, molten salt synthesis is possibly the most economical method to produce fine powders
of complex oxide compounds.

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Figure.3. SEM micrographs of SrTiO3 synthesized in Na2SO4-K2SO4 at (a) 850C and (b) 1050C.
Summary
Only at 850C and above, BNT was completely formed in both eutectic chloride and sulfate salt. By
substituting chloride salt with sulfate salt, the size of molten-salt-synthesized particles of BNT could
be greatly reduced to a few hundreds nanometer at 850C. Submicron particles of SrTiO3 could also
be synthesized in eutectic sulfate salt at 850C, Molten salt synthesis is potentially an economical
method to produce fine powders of complex oxide compounds
Acknowledgement
The authors would like to thank Dr. Aree Thanaboonsombut and Miss Narueporn Vaneesorn for
their help and good support.
References
[1]

R.W. Siegel, E. Hu and M.C. Roco: R&D Status and Trends in anoparticles,
anostructured Materials, and anodevices (FINAL REPORT, WTEC, 1999).
[2] A. Subramania, N. Angayarkanni, S.N. Karthick and T. Vasudevan: Mater. Lett. Vol.60
(2006), p. 3023.
[3] A.I.Y. Tok, F.Y.C. Boey and X.L Zhao: J. Mater. Process. Tech. Vol 178 (2006), p. 270.
[4] N.P. Rao, N. Tymiak, J. Blum, A. Neuman, H.J. Lee, S.L. Girshick, P.H. McMurry and J.
Heberlein: Nanostructured Materials Vol. 9(1) (1997), p. 129.
[5] M.F. Becker, J.R. Brock, H. Cai, N. Chaudhary, D. Henneke, L. Hilsz, J.W. Keto, J. Lee,
W.T. Nichols and H.D. Glicksman: Nanostructured Materials Vol. 10(5) (1998), p. 853.
[6] S. Daniele, M.N. Ghazza, L.G. Hubert-Pfalzgraf, C. Duchamp, C. Guillard and G. Ledoux:
Mater. Res. Bull. Vol. 41 (2006), p. 2210.
[7] Y.L. Zhang, X.J. Jin, Y.H. Ronga, T.Y. Hsu, D.Y. Jiang and J.L. Shi: Mater. Sci. Eng. A Vol
438440 (2006), p. 399.
[8] J. Mouzon, P. Nordell, A. Thomas and M. Oden: J. Eur. Ceram. Soc. Vol. 27 (2007), p.
1991.
[9] E. Lester, P. Blood, J. Denyer, D. Giddings and A.M. Poliakoff: J. Supercrit. Fluids Vol. 37
(2006), p. 209.
[10] M.I. Baraton: Synthesis, Functionalization and Surface Treatment of anoparticles
(American Scientific Publishers, 2003).
[11] Y. Osamu, M. Noboru and H. Ken: Br. Ceram. Trans. J. Vol. 90 (1991), p. 111.
[12] S. Kuharuangrong: Ceramics International, Vol. 33 (8) (2007), p.1403.

Advanced Materials Research Vols. 55-57 (2008) pp 165-168


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.165

Effects of Starting Materials on Molten Salt Synthesis of Bi4Ti3O12


P. Setasuwona and S. Kijamnajsak
National Metal and Materials Technology Center (MTEC)
National Science and Technology Development Agency, Pathumthani 12120, Thailand
a

paisan@mtec.or.th

Keywords: Bi4Ti3O12, molten salt synthesis, crystal size

Abstract. Na0.5Bi0.5TiO3 is one of the potential candidates for non-lead piezoelectric materials to
replace existing lead-based ones. Properties of BNT could be enhanced by reactive templated grain
growth (RTGG) technique through induction of grain orientation with crystals of Bi4Ti3O12.
Controlling the size of Bi4Ti3O12 crystals during the synthesis with molten salt is a major factor in
optimizing RTGG. It was found that molten salt synthesis of Bi4Ti3O12 crystals with NaCl-KCl
yielded larger particles, compared with Na2SO4-3K2SO4. Varying the proportion of chloride salt did
not produce noticeable changes in crystal size. Bi4Ti3O12 crystals were significantly affected by raw
materials treatment. Non-milling of starting powders could approximately double the crystal size
Introduction
Na0.5Bi0.5TiO3 (BNT) is one of the potential candidates for non-lead piezoelectric materials to
replace existing lead-based ones. This material and its variations are now being investigated [1-6].
Properties of BNT could be enhanced by templated grain growth technique, to utilize the better
properties along certain crystallographic directions by employing small crystals as seeds to induce
orientation of the matrix. Crystals of Bi4Ti3O12 were successfully employed as seeds for BNT [7].
However, the effects of processing parameters in molten salt synthesis of Bi4Ti3O12 crystals were
not thoroughly studied. It is advantageous to be able to control the crystals size to optimized TGG
process. In this work, effects of starting materials on synthesis of Bi4Ti3O12 crystals were studied.
Experimental
Bi2O3 (Fluka, 98%) and TiO2 (Fluka, 99%) were mixed in the proportion to yield Bi4Ti3O12. Salt
mixtures were added at 75 vol% except stated otherwise. Two salt mixtures were employed: NaClKCl and Na2SO4-3K2SO4. (NaCl (AnalaR, 99.5%), KCl (Riedel-deHan, 99.5%), Na2SO4 (AnalaR,
99%), K2SO4, (AnalaR, 99%)). The mixtures were milled with zirconia balls in acetone except
stated otherwise, dried and put in the alumina crucible. The lid was sealed with alumina cement.
The mixtures were heated to various temperatures for 2 hr with the heating rate of 300 C/hr and the
cooling rate of 180 C/hr. Salt was washed out with hot water several times. Characterizations were
performed with SEM (JEOL, JSM-6301F) and an X-ray diffractometer (Jeol JDX-3530).
Results and Discussion
Characterization of Bi4Ti3O12 in NaCl-KCl at 650, 850 and 1050C was shown in Fig.1. At 650 C,
there existed NaBi3O4Cl2 and Bi2Ti2O7. This indicates that NaCl has entered into the reaction. At
higher temperatures, Bi4Ti3O12 was completely formed. It is noticeable that, the relative intensities
at 1050C are quite different from those of 850C. The morphology of Bi4Ti3O12 particles are thin
platelet, with particle size of a few microns at 850C and larger than 10 m at 1050C. In-packing
arrangement of particles with very high aspect ratio, such as thin platelets, could result in preferred
orientation of particles or crystals [8] . Increase in (00l) relative intensities of X-ray diffraction
pattern of 1050C is clearly observable.

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10 m

10 m

10 m

Figure 1. X-ray diffraction patterns and SEM micrographs of Bi4Ti3O12 composition synthesized in
NaCl-KCl at 650, 850 and 1050 C.

10 m

10 m

6 m

Figure 2. X-ray diffraction patterns and SEM micrographs of Bi4Ti3O12 synthesized in


Na2SO4-3K2SO4 at 650, 850 and 1050 C.

Advanced Materials Research Vols. 55-57

167

When using Na2SO4-3K2SO4, Bi4Ti3O12, was produced at all temperatures of 650, 850 and 1050C
(Fig. 2). Sulfate salt did not enter into reaction as chloride salt did at low temperature of 650C. At
1050C, the particles is also platelet with smaller size but thicker than those from NaCl-KCl. At
lower temperature of 850C and 650 C., the particle size is much less to around one micron or less.
The smaller and thicker particles could be the result of higher surface energy of the particles in
sulfate salt, therefore chloride salt is the choice for synthesis of large crystals.
The proportion of salt was studied by varying from 25 to 95 %Vol. Bi4Ti3O12 were completely
formed in 25-75% salt but there were Na0.5Bi4.5Ti4O15 as a secondary phase with 95% salt (Fig. 3).
Salt became reactive when used in large amount. The sizes of synthesized crystals were not
noticeably different with varied salt proportions, but at 25-50% most crystals were agglomerated.
After studying the effects of salts, the starting powders were next to be studied by being subjected to
milling (ball milling) and non-milling (dry mixing by hand). Non-milling resulted in a small amount
of Na0.5Bi8.5Ti7O27 (Fig. 4) because of non-uniform dispersion of constituents. Interestingly, the
size of synthesized Bi4Ti3O12 crystals was significantly affected by starting materials treatment.
Large crystals, up to 20 m, were obtained by non-milling of starting powders.

10 m

10 m

10 m

10 m

Figure 3. X-ray diffraction patterns and SEM micrographs of Bi4Ti3O12 synthesized in 25-95%
NaCl-KCl at 1050C for 2 hours.

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10 m

40 m

Figure 4. X-ray diffraction patterns and SEM micrographs of Bi4Ti3O12 prepared from milled and
not-milled starting powders with 75% NaCl-KCl at 1050C for 2 hours.
Summary
Molten salt synthesis of Bi4Ti3O12 crystals with NaCl-KCl yielded larger particles, compared with
Na2SO4-3K2SO4. Varying the proportion of chloride salt did not produce noticeable change in
crystals size. The size of synthesized Bi4Ti3O12 crystals was significantly affected by starting
materials treatment. Non-milling of starting powders could approximately double the crystal size
Acknowledgements
The authors would like to thank Dr. Aree Thanaboonsombut and Miss Narueporn Vaneesorn for
their help and good support.
References
[1]

P. Pookmanee, G. Rujijanagul, S. Ananta, R.B. Heimann and S. Phanichphant: J. Euro.


Ceram. Soc. Vol. 24 (2004), p. 517.

[2]

D.Y. Wang, K. Li and H.L.W. Chan: Sensors and Actuators A Vol. 114 (2004), p. 1.

[3]

D.M. Lin, D.Q. Xiao, J.G. Zhu, P.Yu, H.J. Yan, L.Z. Li and W. Zhang: Cryst. Res. Technol.
Vol. 39(1) (2004), p. 30.

[4]

H. Li, C. Feng and W. Yao: Mat. Lett. Vol. 58 (2004), p. 1194.

[5]

X.X. Wang. K.W. Kwok, X.G. Tang, H.L.W. Chan and C.L. Choy: Solid State Commun. Vol.
129 (2004), p. 319.

[6]

C.Y. Kim, T. Sekino and K. Niihara: J. Am. Ceram. Soc. Vol. 86(9) (2003), p. 1464.

[7]

H. Yilmaz, S. Trolier-Mckinstry and G.L. Messing: J. Electroceram. Vol. 11 (2003), p. 207.

[8]

P. Setasuwon and S. Kijamnajsuk, Sci. & Technol. Adv. Mater. Vol. 7 (2006), p. 780.

Advanced Materials Research Vols. 55-57 (2008) pp 169-172


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.169

Effect of ZrO2 Doping on Crystal Structure, Microstructure and


Phase Transition of Lead Titanate Ceramics
P. Sittiketkrona, S. Sukkhob and T. Bongkarnc
Department of Physics, Faculty of science, Naresuan University, Phitsanulok, 65000, Thailand
a

may_panat@hotmail.com, bsaicholsukkho@hotmail.com cresearchcmu@yahoo.com

Keywords: Lead Titanate, ZrO2 Doping, Tetragonality, Mixed Oxide

Abstract. In this work, the effect of ZrO2 doping on the properties of PbTiO3 ceramics was
investigated. PbTiO3 powders were prepared via a mixed oxide method with a calcination
temperature of 750 C for 2 h. The various amounts of ZrO2, between 0 and 2 wt.%, were added to
the calcined powders to decrease the c/a ratio. The mixed powders were sintered at 1225 C for 2
h. The samples were characterized using Xray diffractrometer (XRD), scanning electron
microscopy (SEM) and differential scanning calorimeter (DSC). It was showed that the ZrO2
phase was not detected in all of the powder and ceramic samples. The highest density in the
ceramics was found in the sample with 0.5 wt.% of ZrO2. The average grain size slightly
increased with the increase of ZrO2. The phase transition temperature from tetragonal ferroelectric
to cubic paraelectric was about 465 to 466 C for all sintered samples.
Introduction
Lead titanate (PbTiO3; PT) ceramics is one of the most interesting and most studied perovskites,
possessing a ferroelectric phase under ambient conditions. The strong interrest in this compound is
caused by its high spontaneous polarization, low dielectric constant of about 200 and the wide
temperature stability of its ferroelectric phase: the ferroelectric-paraelectric phase transition
temperature (490 C) is the highest in the family of ferroelectric perovskites. Above 490 C, PT is
cubic, while at room temperatures it shows a tetragonal phase [1,2]. The PT ceramic is a useful
pyroelectric and piezoelectric material for high-temperature or high-frequency applications, such as
nonvolatile memories, infrared sensors, and capacitors [3]. It is difficult to prepare a pure-phase
PT ceramic with high density, because of a high c/a ratio of about 1.064 which gives rise to stresses
in these ceramics. They can be easily broken and difficult to prepare in a shape and size suitable for
device applications [4]. As PT ceramics are fragile during sintering, it is necessary to add some
cations in the A-or B-site to decrease its c/a ratio. The most widely used additives used to modify
the properties of pure PT, are rare earth elements and alkaline earth elements. For example Adding
ZrO2 to partially substitute Ti in the B-site is one of commonly used methods (PZT). The ZrO2 is a
most interesting addition to PT ceramics because PZT has great piezoelectric properties which can
be applied in transducer applications. Furthermore, it has a high Tc of 390 C which allows
piezoelectric devices to be operated at relatively high temperatures [5]. The properties of PT itself
are subsequently altered by the additives. It is also know that PT has good electrothermal properties
so stoichiometric PT is still needed [6].
There are a lot of processing techniques for preparing PT ceramics, including so-gle synthesis,
hydrothermal reactions, coprecipitation method, and molten salt preparation [7-10]. These are
normally complicated and expensive so they are not suitable for mass production. The conventional
mixed oxide method is more economical for large quantity processing of these ferroelectric
materials. In this paper, we studied the effect of adding a small amount of ZrO2 in order to keep the
properties of PT ceramics. The PT powders were prepared by a conventional mixed oxide method.
We also investigated the effect of ZrO2 doping on the crystal structure, microstructure and phase
transition of the PT ceramics.

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Experimental
The PT powders were prepared by a conventional mixed oxide method. The raw material PbO and
TiO3 were weighed and mixed by ball milling in ethanol using zirconia balls for 24 h. After drying
and sieving, it was calcined at 750 C for 2 h. In the present work, doping, the amount of ZrO2
between 0 and 2 wt.%, were added in calcined powders. The calcined powders were reground by
ball milling with a 5% PVA solution. The powders were then dried, crushed and sieved again. The
powders were pressed at 80 MPa. Finally, the pellets were sintered at 1225 C for 2 h in a covered
crucible. The Densities of sintered ceramics were measured by the Archimedes method and X-ray
diffraction [XRD] was employed to identify the phase formed. The grain morphology and size were
directly imaged, using scanning electron microscopy [SEM] and the average grain size was
determined by using a mean linear intercept method. The phase transition, transformed from
tetragonal ferroelectric to cubic paraelectric, was investigated by using differential scanning
calorimeter [DSC].
Results and Discussion
The XRD patterns of PT powders were calcined at 750 C for 2 h with various amounts of ZrO2 (0
2 wt.%) show in Fig. 1a. It was found that the PT powders indexed in a tetragonal structure and
thesematched with JCPDS file number 70-0446. Fig. 1b shows the XRD patterns of PT ceramics
sintered at 1225 C. The single phase PT was detected in all samples. There is no peak shift in any
samples. The pure perovskite phase was observed for sintered ceramics, showing a similar to the
results from calcined powders.

(a)
(b)
Figure 1. XRD patterns of PT samples with various amounts of ZrO2 doping (a) calcined powders
and (b) sintered ceramics.
The amount of ZrO2 to PT samples resulted in lattice parameter c, a and c/a ratio. The lattice
parameter c was 4.121 to 4.146 and the lattice parameter a was 3.909 to 3.915 for the samples
doping ZrO2 0 to 2 wt.%. The c/a ratios of ceramics tended to increase with increased amounts of
ZrO2. The c/a ratios were 1.054 and 1.059 for the samples doped with ZrO2 0 wt.% and 2 wt.%,
respectively, - these were less than the theoretical (1.064).

Advanced Materials Research Vols. 55-57

171

Fig. 2. shows SEM micrographs of PT ceramics surfaces with various ZrO2 contents. The
microstructure reveals that the grains are rectangular in shape with different grain sizes. The grain
sizes and porosity were increased with increasing amounts of ZrO2. By using the intercept method,
the average grain sizes increased from 5.38 to 12.14 m when ZrO2 was added from 0 to 2 wt.%
(Fig.3).

100m
Figure 2. SEM photomicrographs of PT ceramics sintered at 1225 C with various the amount of
ZrO2 doping (a) 0 wt.%, (b) 0.25 wt.%, (c) 0.50 wt.%, (d) 0.75 wt.%, (e) 1 wt.% and (f) 2 wt.%.
The density of PT ceramics with different amounts of ZrO2 is show in Fig. 4. The density of
0-1 wt.% samples tended to increased with an increase in the amount of ZrO2. The density of the
2 wt.% sample rapidly decreased, due to high porosity, as seen in Fig. 2(f).

Figure 3. The grain sizes of PT samples with


various the amount of ZrO2 doping.

Figure 4. The density of PT samples with


various the amount of ZrO2 doping.

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Fig. 5 demonstrated the DSC thermograms of


sintered samples. The distinct endothermic peak
can be attributed to Curie temperature, while it was
transforming from tetragonal ferroelectric to cubic
paraelectric. The Curie temperature of all samples
was between 465 and 466 C and the enthalpy is
approximately 3.524 to 3.883 J/g. It indicated that
small amounts of ZrO2 dopants did not result in
phase transition.

Figure 5. The DSC analysis of the PT samples


with various the amount of ZrO2 doping.
Summary
PbTiO3 ceramics were prepared by a conventional mixed oxide method with various amounts of
ZrO2 between 0 and 2 wt.%. The tetragonality increased when the amount of ZrO2 doping
increased. In addition, the ZrO2 doping also affected grain size, porosity and the density of the PT
ceramics. However, ZrO2 doping had no effect on the Curie temperature of sintered ceramics.
Acknowledgment
This work was financial supported by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE) and Faculty of Science, Naresuan University. Thanks also to Mr. Don Hindle for
his help in correcting the manuscript.
References
[1]
[2]
[3]

A.M. Glazer and S.A. Mabud: Acta Crystallogr. B. Vol. 34 (1978), p. 1065.
G. Shirane, R. Pepinsky and B.C. Frazer: Acta Crystallogr. Vol. 9 (1956), p. 131.
J. Moon, J.A. Kerchner, J.LeBleu, A.A Morrone and J.H Adair: J. Am. Ceram. Soc. Vol. 80
(1997), p. 2613.
[4] G. Shirane, J.D. Axe and J. Harad: Mater. Phys. Rev. B Vol. 2 (1970), p. 131.
[5] G.H Haertling: J. Am. Ceram.Soc. Vol. 82 (1999), p. 797.
[6] S. Shirasaki: Solid State Commun Vol. 9 (1971), p. 1217.
[7] J. Kim, M.C Jun and S.C. Hwang: J. Am. Ceram.Soc.Vol. 82 (1999), p. 289.
[8] G.R Fox and R.E. Breval: J. Mater. Res. Vol. 26 (1991), p. 2566.
[9] H. Idrissi, A. Aboujalil and B. Durand: J. Eur. Ceram. Soc. Vol. 19 (1999), p. 1997.
[10] A. Udomporn, K Pengpat and S. Ananta: J. Eur. Ceram. Soc.Vol. 24 (2004), p. 185.

Advanced Materials Research Vols. 55-57 (2008) pp 173-176


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.173

Fabrication of Barium Stannate Tatanate Ceramics via Combustion


Technique
C. Wattanawikkama and T. Bongkarnb*
Department of Physics, Faculty of science, Naresuan University, Phitsanulok, 65000, Thailand
a

pie_sci@hotmail.com, bresearchcmu@yahoo.com

Keywords: Barium Stannate Titanate, Combustion technique, Phase formation, Microstructure

Abstract. The effect of firing temperatures on phase formation and microstructure of barium
stannate titanate [Ba(Sn0.1Ti0.9)O3; BST10] ceramics were investigated. BST10 was synthesized via
a combustion method, at various calcination and sintering temperatures. It was found that, a single
perovskite of BST10 powders was obtained with a calcinations temperature of 1200 oC. The percent
of the perovskite phase and the lattice parameter were increased with increasing calcination
temperatures. The average particle size was increased from 0.48 to 1.69 m by increasing the
calcined temperature from 600 to 1200 oC. The average grain sizes were increased from 0.99 to
17.77 m by increasing the sintering temperature from 1250 to 1450 oC. The maximum density and
dielectric constant were observed in sintered samples at 1350 oC.
Introduction
Barium titanate (BaTiO3; BT) is well known and a widely investigate dielectric material. Because
of its interesting properties such as a high dielectric constant, low dielectric loss and piezo-electric
behavior [1]. To improve the properties of BT, it can be modified by the partial substitution of Pb,
Sr and Sn. [2-4]. Barium stannate tiatanate [Ba(Sn1-xTix)O3; BST] is a binary solid solution system
composed of ferroelectric barium titanate and non-ferroelectric barium stannate [4]. BST can be
synthesized by substituting either titanium or tin ions. Curie temperature or dielectric maximum of
BST can be widely shifted by changing the stannate or tin content. Furthermore, the permittivity is
very high and temperature is bias field sensitive. These allow this material to be used in various
applications; capacitors, balometers, actuators [5-6] and microwave phase shifters [7-8]. A survey
of the literature has revealed that the BST has been successfully prepared via a solid state reaction
[4, 9-10] and it suggested that this solid solution system is a mutual soluble and the lattice constant
increased by increasing the Sn content [4]. The strength relaxation behavior was observed in BST
with 0.2 x 0.3 [9]. Wei et al. reported that the BST with x = 0.1 showed abnormal dielectric
properties and strong electric non-linearity [10]. These make BST10 interesting for dielectric
amplifiers [10], and switching circuit snubbers [11-12].
However, it is well known that the ceramic powders which were synthesized by a solid state
reaction required a high temperature and the resulting powders exhibited many undesirable
characteristics: large particle size and wide particle size distribution. However, the combustion
method has use in the present, because of its simplicity, low cost, small particle size and low
preparation temperature [13]. In addition, the variation details of the synthesis and characterization
of BST10 ceramics via the combustion method has rarely been reported in the literature. Thus, in
the present work, we reported the effect of firing temperature on phase formation, microstructure
and dielectric properties of [Ba(Sn0.1Ti0.9)O3; BST10] ceramics, prepared via combustion method.
Experimental
The starting materials were commercial barium carbonate; BaCO3 (99%), stannate (IV) oxide; SnO2
(99%) and titanium oxide; TiO3 (99%). Barium stannate titanate [Ba(Sn0.1Ti0.9)O3; BST10] ceramics
were synthesized via the combustion method using a thoroughly ground mixture of BaCO3, SnO,
and TiO2 powders that were milled in the required stoichiometric ratio. Ball milling in a zirconia

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milling media under ethanol for 24 h was used an then, drying and sieving. After sieving, the
powders and urea were mixted in an agate motor. Then, various calcination temperatures, ranging
from 600 to 1200 oC, for 4 h at a heating/cooling rate of 5 oC/min were performed. The calcined
powders were then ball-milled for 24 h with 2wt.% binder. These calcined powders were pressed
into discs with a diameter of 15 mm at a pressure of 80 MPa. The pellets were sintered between
1250 oC and 1450 oC for 2 h and cooled in a furnace.
The reaction of uncalcined BST powders and urea fuel taking place during heat treatment were
investigated by thermogravimetric and differential thermal analysis (TG-DTA). X-ray diffraction
(XRD) was employed to identify the phase formed the optimum temperature for BST powders and
ceramics. The particle and grain morphology used scanning electron microscopy (SEM). Densities
of sintered ceramics were measured by the Archimedes method and the average grain size was
determined by using a mean linear intercept method. The dielectric constant at room temperature
was also measured by LCR meter.

Results and Discussion


The TG-DTA simultaneous analysis of mixed
powders in the stoichiometric proportion of
BST10 is displayed in Fig.1. The TG curve shows
three distinct weight loss. The first weight losses
appeared at temperatures between 150 to 240 oC,
due to the melting of the urea. It was related with
the endothermic peaks in the DTA curves at 152
and 232 oC. The second one occurred between 350
and 550 oC caused by the evaporation of water and
gas. This was related to the endothermic peak at
352, 418 and 512 oC. The last peak was at about
720 oC, which corresponded to a small
endothermic peak at 720 oC, which represented
Figure 1. TG-DTA curves for the mixture
the reaction of BaCO3, SnO2 and TiO2. In
of BST10 powders.
o
addition, the endothermic peaks, at about 1200 C,
were also observed. This data was used to define the range of calcination temperatures.
Fig.2 showed the XRD pattern of BST10 with various calcination temperatures between 600
and 1200 oC for 4 h. After calcinations at 600 oC, the precursor of BaCO3, SnO2, BaO, TiO2,
BaTiO3 and BaSnO3 were detected, which agrees with the data listed in JCPDS file number 050378, 03-3174, 21-1272, and 06-0395, respectively. When the temperature went above 800 oC, the
crystalline phase of BST10 was accompanied by BaCO3, BaO, and TiO2 as separate phases. As the
temperature increased to 1000 oC, the second phase of BaSnO3 and BaTiO3 was appeared. At
between 1050 oC and 1150 oC, the minor phase of BaTiO3 was remained. While at the 1200 oC, the
pure phase perovskite of calcined samples is formed. This investigation matched with data received
from the TG-DTA results. The percent perovskite phase of BST10 was calculated by the major
XRD peak intensity of the perovskite and impurity phase. The calcinations temperature ranging
from 600 to 1150 oC did not achive 100% perovskite phase. The single perovskite phase occured at
1200 oC. The percentage of BST10 perovskite phase was increased with increasing of calcination
temperatures, demonstrated in Table 1.
The lattice parameter a was calculated and shown in Table 1. The lattice parameter a tended to
increase with increasing calaination temperatures. The result suggested that the calcination
temperature has directly affected the crytal structure of BST10.
The SEM morphology of the BST10 powders calcined at 800 and 1000 oC are shown in Fig. 3.
Generally, it can be seen that the particles were agglomerate and irregular in shape. The particle
size, which is calculated from the cutting lines in SEM, is about 0.48 - 1.69 m with the sample
calcination temperature at 600 - 1200 oC. The influence of various calcination temperatures on the

Advanced Materials Research Vols. 55-57

175

particle size is also given in Table 1. The results indicated that the average particle size tended to in
creased with increased the calcination temperatures.

(a)

(b)

Figure 2. XRD patterns of BST10 powders


with various calcination temperatures; (*)
BaCO3, (o) SnO2, (+) BaO, () TiO2, ()
BaTiO3 and () BaSnO3.

Figure 3. SEM morphology of


BST10 powders calcined at
(a) 800 oC and (b) 1000 oC.

Fig. 4 shows the SEM morphology of BTS10 ceramic samples sintered at 1300 and 1400 oC for 4 h.
These photographs show well-developed grain size and dense microstructure. The average grain
size is about 0.99 - 0.77 m with sintering temperatures of 1250 - 1450 oC, Table 1. The average
grain size was increased with increasing sintering temperatures.
The density, shrinkage and dielectric properties at room temperature of BST10 ceramics, with
sintering temperature ranging between 1250 and 1450 oC, can also be seen in Table 1. The density,
shrinkage and dielectric constant at room temperature were increased by sintering temperatures to a
maximum of 1350 oC. A further increase in the sintering temperature resulted in a drop of all
values. The maximum density, shrinkage and dielectric constant occurred at 1350 oC with 5.9
g/cm3, 16.33% and 553, respectively. These results indicate that the dielectric constant is relative to
the density of ceramic.

(a)

(b)

Figure 4. SEM morphology of BST10 ceramics sintered temperature at (a) 1300 oC and (b) 1400 oC.

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Summary
Barium stannate titanate, BTS10 can be formed by the reaction of barium carbonate, stannate oxide
and titanium (IV) oxide at 1200 oC. The pure cubic perovskite phase was found in all sintered
samples. The particle and grain size increased with the increase in the calcination and sintering
temperatures. The maximum density, shrinkage and dielectric constant were obtained in ceramics
sintered at 1350 oC. These results suggested that the calcination and sintering temperature has
directly affected the phase formation, microstructure, density, shrinkage, and dielectric properties of
BST10.

Table 1. % perovskite phase, lattice parameter a, average particle size, average grain size, density,
shrinkage and dielectric constant of BST10
Calcined powder

Sintered ceramic

Lattice
parameter
a
()
-

Average
particle
size
(m)
0.48

Sintering
temperature
(oC)

Average
grain size
(m)

Density
(g/cm3)

Shrinkage
(%)

Dielectric
constant

600

%
perovskite
phase
(%)
48.86

1250

0.99

5.8

10.33

515

800

75.21

3.9975

0.48

1300

1.24

5.9

13.67

541

1000

84.26

4.0017

0.52

1350

1.80

5.9

16.33

553

1050

93.41

4.0056

0.69

1400

15.69

5.2

13.33

532

1100

95.47

4.0077

0.87

1450

17.77

5.5

12.66

526

1150

96.52

4.0093

1.09

1200

100.00

4.0101

1.69

Calcined
temperature
(oC)

Acknowledgments
This work was financially supported by the Thailand Research Fund (TRF) and Commission on
Higher Education (CHE). Thanks also to Department of Physics, Faculty of Science, Naresuan
University for supporting facilities. Acknowledgements are also to Mr. Don Hindle, for helpful
comments and corrections of the manuscript.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]

J.H. Cho and M. Kuwabara: J. Eur. Ceram. Soc. Vol. 24 (2004), p. 2959.
R. Vold, R. Biederman, G. Rossetti JR and A. Sacco: J. Mater. Sci. Vol. 36 (2001), p. 2019.
C. Fu, C. Yang, H. Chen, Y. Wang and L. Hu: Mat. Sci. Eng. B Vol. 119 (2005), p. 185.
X. Wei and X. Yao: Mat. Sci. Eng. B Vol. 137 (2005), p. 184.
U. straube, H. Langhammer, H. Abicht and H. Beige: J. Eur. Ceram. Soc. Vol. 19 (1999), p.
177.
R. Steinhausen, A. Kouvatoy, H. Beige, H. Langhammer, and H. Abicht: J. Eur. Ceram. Soc.
Vol. 24 (2004), p. 1677.
X. Wei, Y. Feng and X. Yao: Appl. Phys. Lett. Vol. 83 (2003), p. 2031.
S. Lu, Z. Wu and H. Chen: Appl. Phys. Lett. Vol. 85 (2004), p. 5319.
X. Wei, Y. Feng, X. Wan and X. Yao: Ceram. Int. Vol. 30 (2004), p. 1397.
X. Wei, Y. Feng, L. Hang, S. Xia, L. Jin and X. Yao: Mat. Sci. Eng. B Vol. 120 (2005), p. 64.
C.K. Campbell, J.D. van Wyk, M.F.K. Holm and J.J. Scoeman: IEEE Trans. Comp. Hybrid.
Mnuf. Technol. Vol. 15 (1992), p. 245.
C.K. Campbell, J.D. van Wyk, M.F.K. Holm, J.J.R. Prinsloo and J.J. Schoeman: IEEE Trans.
Comp. Hybrid. Mnuf. Technol Vol. 16 (1993), p. 418.
K.C. Patil, S.T. Aruna and S. Ekambaram: Curr. Opin. Solid. ST. M. Vol. 2 (1997), p. 158.

Advanced Materials Research Vols. 55-57 (2008) pp 177-180


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.177

The Effect of Excess PbO on Crystal Structure and Microstructure of


(Pb0.925Ba0.075)TiO3 Ceramics
T. Bongkarna* and R. Sumangb
Department of Physics, Faculty of Science, Naresuan University,Phitsanulok, 65000, Thailand
a

researchcmu@yahoo.com, brattiphorn_11@hotmail.com

Keywords: Lead Barium Titanate, Tetragonality, Mixed Oxide, Excess PbO

Abstract. In this work, we studied the effect of excess PbO doping on lead barium titanate
[(Pb0.925Ba0.075)TiO3; (PBT)] ceramic. PBT was prepared via a mixed oxide method with various
PbO levels (-3, 0, 1, 3, 5 and 10 wt.%). The excess PbO was added to compensate the loss from
evaporation during calcination and sintering at 800 oC and 1150 oC. It was found that lead barium
titanate powders indexed in a tetragonal structure. Impurity phases of lead oxide (PbO), titanium
oxide (TiO), and lead dioxide (PbO2) were detected in the calcined powders with higher than 1 wt%
of excess PbO. The impurity phase was not obtained in any ceramic samples. The c/a ratios
decreased with an increasing excess of PbO in both calcined powders and sintered pellets. The
average particle size and the average grain size of the PBT increased with the increase of PbO. The
shrinkage plots showed a maximum peak for the 1 wt.% sample which was also the most dense
sample.
Introduction
(Pb1-xBax)TiO3 (PBT) is an excellent material in micro electric technology to exploit its properties,
such as spontaneous polarization. PBT thin film was prepared by a sol gel method. It exhibited a
nano-metric size about 30-50 nm and its specific surface area was 21.91 m2/g [1]. PBT (0 x 1.0)
ceramics prepared by a precursor route showed particle sizes of 50-54 nm in all compositions and
the dielectric constant () decreased with lead-doping [2]. Xing et al, prepared the PBT (0 x 1.0)
ceramics by a solid state reaction method. All solid solution compounds were indexed in tetragonal
symmetry with lead titanate at room temperature. The tetragonality continuously decreased when x
increased [3]. The conventional method of synthesizing PBT relies on a solid-state reaction between
PbO, BaCO3 and TiO2 at a high temperature, raising the cost above that of a conventional solid-state
reaction which is more economical for large quantity processing of these ferroelectric materials.
Synthesis of PBT ceramics in this way also suffers from the problem of PbO loss because of the
high temperature [4]. Evaporation of PbO also changes the properties of the materials due to the
change of stoichiometry. In order to compensate the lead loss in the samples, some excess PbO is
usually added during preparation [5]. Therefore, the effect of excess PbO on the microstructure and
crystal structure of (Pb0.925Ba0.075)TiO3 (PBT) ceramics was investigated in this study.
Materials and Methods
The (Pb0.925Ba0.075)TiO3 powders were prepared by a conventional mixed oxide method. The raw
materials of lead oxide (PbO), titanium oxide (TiO2) and barium carbonate (BaCO3) were weighed
and mixed by ball milling for 24 h in ethanol. After drying and sieving, the mixture was calcined at
800 C for 1 h. An excess of PbO, equivalent to -3, 0, 1, 3, 5, or 10 wt%, was added prior to ball
milling. Subsequently, the calcined powders were then pressed into discs with a diameter of 15 mm
at a pressure of 80 MPa. The pellets were fired in a sealed, alumina crucible and sintered at 1150 oC
for 2 h. Finally, the crystal structure and microstructure of the calcined powders and sintered
ceramics were analyzed by an X-ray diffractometer (XRD) and scanning electron microscope
(SEM). Lattice parameters c, a, c/a ratios were obtained by a calculation based on XRD peaks. The
reactions of the uncalcined powders, taking place during heat treatment, were investigated by

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differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The average grain size
and average particle size of the sample were determined using the linear interception method. The
density and shrinkage were also observed.
Results and Discussion
Fig. 1. shows the results of thermogravimetric and differential thermal analysis techniques (TGADTA). The TGAs sharp decrease curve between 270 and 340 C indicated a major weight loss due
to the process of getting rid of the left over burned plastic during the ball milling. The second
weight lost occurred at 755 C which is related to the peak change in the main substance as a
reaction to the heat absorbance at 788 C. It is to be noted
that a significant weight loss in the TGA curves associated
with large thermal changes in the DTA curves were observed
at temperatures above 788 C. Therefore, the calcinations on
lead barium titanate at the temperature of 800 C were
conducted.
Fig. 2(a). Shows XRD patterns of PBT powders made
from starting mixtures containing different levels of PbO,
which could be matched with the JCPDS file number 060452 [6]. It was indexed as a tetragonal structure. Small
amounts of PbO, TiO and PbO2 were clearly present in the 10
Figure 1. The DTA-TGA curves for
wt.% excess PbO sample and there was also some evidence
the mixture of PbO-BaCO3-TiO2
of these phases being present in the 5 wt.%, and, to much
powders.
lesser extent, in the 3 and 1 wt.% samples. The second phase
was not obtained in any ceramic samples, as seen in Fig. 2(b). It indicated that the excess PbO was
beyond that required to maintain compositional control (assumed) in the PBT powders and was
eliminated from the sample by volatilization during sintering at 1150 C.

(a)
(b)
Figure 2. XRD patterns of (a) calcined powders and (b) sintered ceramic made from starting
powders contained different amounts of excess PbO: ()PbO, () TiO and () PbO2.
Table 1. shows the percent perovskite phase of calcined powders. The pure perovskite phase was
found in deficient -3 and 0 wt% samples. With higher than 1 wt%, the percent perovskite phase
decreased with the increase of excess PbO. The percent perovskite phase of ceramics reached a
hundred percent in all samples.
Figure. 3(a) and (b) show the lattice parameters a, c of the PBT calcined powders and sintered
ceramics which is calculated from formula (1). The data for calculation is desived from (002) and
(200) XRD [6].

Advanced Materials Research Vols. 55-57

1
h2 + k 2 l 2
=
+ 2
2
d hkl
a2
c

179

(1)

The lattice parameter a increased, while the lattice parameter c decreased with the increase of
excess PbO content. Furthermore, the c/a ratio of powders decreased with the increased excess PbO
levels, (Table 1). These results indicated that the introduction of excess PbO decreases the
proportion of the tetragonal phase in PBT calcined powders and sintered ceramics. The structural
reasons for this are uncertain at this stage, but the result may indicate that Pb and O ion vacancies in
uncompensated compositions stabilize the tetragonal structure.

(a)
(b)
Figure 3. The lattice parameter a, c of PBT (a) calcined powders and (b) sintered pellets made from
starting powders contained different amounts of excess PbO.
The SEM photomicrographs of PBT calcined powders with various PbO excess are shown in Fig. 4
(a) and (b). The average particle size increased with increasing excess PbO. These powders
exhibited an almost spherical morphology and have a porous agglomerated form. It is believed that
at the chosen calcinations temperature the sintering process starts and, as a consequence, the
agglomerates are formed in the calcined PBT powders [7]. Fig. 4 (c) and (d) reveal the SEM
photomicrograph of PBT sintered pallets. The average grain size first decreased with excess PbO
and reach its minimum at 3 wt.%. Increasing the excess PbO resulted raise of all values (Table 1).

(a)

(b)

(c)
(d)
Figure 4. SEM photomicrographs of PBT made from starting with different PbO contents:
(a) 0 wt.% of calcined powders (b) 10 wt.% of calcined powders (c) 0 wt.% of sintered ceramics
(d) 10 wt% of sintered ceramics.

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The density and linear shrinkage of PBT sintered ceramics is listed in Table 1. One can see that the
density and linear shrinkage increases with increasing amounts of PbO until 1 wt.%, then slightly
decreases, for all samples. The presence of a PbO-rich liquid phase usually assists densification
during sintering [8,9]. However, a large amount of a PbO liquid phase can produce an initial rapid
densification but a lower final density as a result of a void formation due to PbO evaporation [8,9].
As a consequence the porosity of the pellet increases and this porosity is not removed by solid state
sintering [10,11].
Table 1. Percent perovskite phase, c/a ratio, average particle size, average grain size, density and
shrinkage of PBT calcined powders and sintered ceramics

Excess
PbO (wt%)
-3
0
1
3
5
10

Calcined powder
Percent
c/a ratio Average
particle
perovskite
size
phase (%)
(m)
100
1.061
0.3
100
1.060
0.7
99
1.060
3.5
98
1.059
3.8
96
1.058
4.6
92
1.056
5.9

c/a ratio

1.058
1.057
1.055
1.053
1.053
1.048

Sintered ceramic
Average
Density
grain
(g/cm3)
size
(m)
6.8
6.83
4.8
7.67
4.7
7.75
2.4
7.47
3.2
7.42
5.5
7.37

Shrinkage
%

16.2
18.1
19.0
18.6
17.6
16.7

Summary
The crystal structure of PBT calcined powders and sintered ceramics is tetragonal perovskite. The
unreacted PbO and PbO2 in calcined powder were employed to compensate lead loss in the
sintering process. The excess of PbO affected lattice parameters and tetragonality of the calcined
powders and sintered ceramics. The microstructure of excess PbO samples also indicated that the
liquid phase sintering occurred in the calcined process. The results also demonstrated that 1 wt.%
excess PbO produced the highest density ceramics exhibiting the maximum linear shrinkage.
Acknowledgements
This work was financially supported by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), Faculty of Science, Naresuan University. Thanks also to Mr. Don Hindle for his
help in correcting manuscript.
References
[1]
[2]
[3]
[4]
[5]
[6]

W.D. Yang and M.H. Sossina: J. Eur. Ceram. Soc. Vol. 26 (2006), p. 3203.
P.R. Arya, P. Jha, G.N. Subbanna and A.K. Ganguli: Mater. Res. Bull. Vol. 38 (2003), p.617.
X. Xing, J. Deng, Z. Zhu and G. Liu: J. Alloy. Comp. Vol. 353 (2003), p. 1.
L.B. Kong, J. Ma, H. Huang and R.F. Zhang: J. Alloy. Compd. Vol. 345 (2002), p. 238.
T. Bongkarn, G. Rujijanagul and J.M. Steven: Mater. Lett. Vol. 59 (2005), p. 1200.
Powder Diffraction File No. 06-0452, International Center for Diffraction Data, Newton
Square, PA, 2003.
[7] D. Kuscer, J. Korzekwa, M. Kosec and R. Skulski: J. Eur. Ceram. Soc. Vol. 7 (2007), p.4499.
[8] F. Xia and X. Yao: J. Mater. Sci. Vol. 36 (2001), p. 247.
[9] L. Zhou, A. Zimmermann, Y. Zeng and F. Aldinger: J. Mater. Sci-Mater. El. 15 (2004), p.
145.
[10] A.I. Kingon, J.B. and Clark: J. Am. Ceram. Soc. Vol. 66 (1983), p. 253.
[11] A.I. Kingon, J.B. and Clark: J. Am. Ceram. Soc. Vol. 66 (1983), p. 256.

Advanced Materials Research Vols. 55-57 (2008) pp 181-184


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.181

The Preparation of Barium Stannate Titanate Ceramics


via Solid State Reaction Method
T. Bongkarna,* and W. Khiawwangthongb
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, Thailand
a

reseachcmu@yahoo.com, bwaraphornk@hotmail.com

Keywords: barium stannate titanate, microstructure, phase formation, solid state reaction

Abstract. In this work, the optimum conditions for the preparation of barium stannate titanate
(Ba(Sn0.05Ti0.95)O3 ; BST5) ceramics by solid state reaction method were investigated. The samples
were heated at calcination temperatures from 600 to 1200 oC for 4 h and sintering temperatures
from 1250 to 1400 oC for 2 h. Thermogravimetric analysis (TGA) and differential thermal analysis
(DTA) were used to evaluate the optimum conditions for calcination. The phase formation was
carried out by X-ray diffractometer (XRD). The microstructure was studied by using a scanning
electron microscope (SEM). It was found that, a high purity of perovskite powders were obtained
with a calcinations temperature at 1200 oC. The percent of the perovskite phase and lattice
parameter a were increased by increasing the calcination temperatures. The average particle size
was increased from 0.6 to 1.0 m when increasing the calcination temperatures from 600 to 1200
o
C. A pure cubic perovskite phase was found in all the sintered samples. The average grain size is in
the range of 1.2 to 43.3 m when increasing of sintering temperatures from 1250 to 1400 oC. The
maximum of density and dielectric constant was observed in a 1400 oC sintered pellet.
Introduction
Barium titanate, BaTiO3 (BT) is a typical ferroelectric material with a perovskite structure [1]. BT
is known as a typical ferroelectric material with Curie temperature (Tc) around 120 oC. BT and has
been widely used for condensers, filters, oscillators and so on, due to its ferroelectric, pyroelectric
and optoelectric properties [2]. Barium stannate titanate, Ba(SnxTi1-x)O3 (BST) is obtained by
substituting ions at the Ti-site of BaTiO3 with Sn ions. The effect of this substitution makes it
possible to reduce temperature dependence and to control the room temperature values of the
dielectric in a fairly wide range. By increasing the Sn-content, the Tc temperature of the
paraelectric-ferroelectric phase transition decreases considerably [3]. Therefore, it can be used in
various applications, such as capacitors, bolometers, actuators and electromechanical sensors [4].
BST (0 x 1) ceramics prepared by hydrothermal showed a Curie temperature below the
temperature of liquid nitrogen when x = 0.40. Relaxation behavior of BST ceramics can be
observed in the sample with x = 0.30 and the dielectric peak of the phase transition becomes
diffused when x = 0.10 [4]. BST ceramics can also be prepared by a solid state reaction method
[3,5-6]. It was reported that, the grain size increased with increasing sintering temperature [3] and
the relaxor behavior is stronger with higher tin substitution [5]. BST with x = 0.20 is a ferroelectric
with a diffused phase transition and BST with x = 0.275, 0.30 is a relaxor ferroelectrics [5]. The
high tenability of the BST with x = 0.10 ceramics, measured at room temperature under biasing
field 10 KV/cm, are 53 % [6]. However, to the authors best knowledge, no preparation of x = 0.05
studies by the solid state reaction method have been reported yet. Therefore, in this present work,
the structure phase, densification and microstructure of BST ceramics prepared by a solid state
reaction method were investigated.
Experimental
Ba(Sn0.05Ti0.95)O3 (BST5) ceramics were prepared by a solid state reaction method. The raw
materials of barium carbonate, BaCO3; stannium oxide, SnO2 and titanium oxide, TiO2; were

182

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wighed and mixed by ball milling for 24 h in ethanal. After being dried and sieved, the mixture was
calcined from 600 to 1200 oC for 4 h. The calcined powders were reground by wet ball milling
with 1 wt% binder for 24 h. The calcined powders with binder were dried and sieved again. The
powder mixtures were isostatically pressed at 80 MPa into a pellet 15 mm in diameter. The green
pellets were sintered from 1250 to 1400 oC for 2 h. Thermogravimetric and differential thermal
analysis (TG-DTA) techniques were used to monitor the thermal behavior of the reaction between
the oxides precursors carried out on the powder mixtures. The phase formation of the calcined
powders was analyzed by X-ray diffractrometer (XRD). The microstructure of the sintered samples
was examined using a scanning electron microscopy (SEM). The density measurement was by
Archimedess method.
Results and Discussion
The TGA and DTA curves, recorded at a heating rate of 10 oC/min in air for an equimolar mixture
of barium carbonate, stannium oxide and
titanium oxide where the ratio of Sn:Ti is
0.05:0.95, are given in Fig. 1. The TGA curve
shows weight loss occurs between 550-980 oC.
This corresponds to the endothermic in DTA
curves around 820, 970 and 1200 oC and is due
to a solid state reaction between BaCO3, SnO2
and TiO2. The broad endothermic characteristic
of the DTA curve showed that these chemicals
reacted most strongly at a minimum peak of
1200 oC. These data were used to define the
range of optimum calcination temperatures.
Fig. 1. TGA and DTA curves for the mixture of
BaCO3, SnO2 and TiO2 powders.
XRD patterns of the BST5 powders formed with different calcination temperatures are given in
Fig. 2. After calcination at 600 oC, the precuser phases with BaCO3, BaO, TiO2 and SnO2 were
detected. The minor X-ray peaks matched the JCPDS file numbers: 05-0378, 03-3174, 21-1272 and
06-0395, respectively [7-10]. The crystalline phase of BST5 was accompanied with BaCO3, BaO,
TiO2 and SnO2, when the powder was calcined at 800 oC. As the temperature increased in range of
1000-1150 oC, the intensity of the BaCO3, SnO2 BaTiO3 and BaSnO3peak become minor phases.
This correlates with JCPDS file numbers 05-0378, 06-0395, 05-0626 and 03-0675 [7,10-12].
Evidently, a single phese of BST5 is formed by calcination at 1200 oC. This observation agrees with
those derived from the TGA and DTA result.
The relative amount of perovskite and impurity phases were determined by measuring the major
XRD peak intensities of the perovskite and impurity phase. The percentage of the perovskite phase
was estimated by the following equation:

I perov
% perovskite =
I perov + I BaCO + I SnO + I BaO + I TiO + I BaTiO + I BaSnO
3
2
2
3
2

100

The calcination temperatures from 600 to 1150 oC did not achieve hundred percent of the perovskite
phase. The pure perovskite phase occurred at 1200 oC. The percentage of the BST5 phase was
increased with increasing calcination temperatures shown in table 1.
The lattice parameter a as a function of calcination temperatures are shown in table 1. The lattice
parameter was increased with the increasing of calcination temperatures. This indicated that the
calcination temperatures have a direct bearing on lattice parameter and cell volume.

Advanced Materials Research Vols. 55-57

183

SEM photographs of BST5 powders calcined at 800 and 1200 oC for 4 h are shown in Fig. 3.
These powders exhibited an almost spheriacal morphology and have a porus agglomerated form.
Particle size is in the range of 0.59 to 0.86 m and was found to slightly increase with the
increasing of the calcination temperature (table 1).
Fig. 4 shows the SEM photographs of BST5 ceramic
samples sintered at 1350 and 1400 oC. These
photographs show a well-developed grain size and dense
microstructure. Grain size of the samples range from
1.24 to 34.65 m. Correspondingly, the average grain
size increased with the increase in the sintering
temperature (table 1).
The density and dielectric properties at room
temperature of BST5 ceramics and those after sintering
temperatures ranging between 1250 and 1400 oC, are
listed in table 1. The density and dielectric constant at
room temperature increased as sintering temperatures
increased. The maximum density and dielectric constant
occurred at 1400 oC with 5.94 g/cm3 and 3865,
respectively. These results indicate that the dielectric
constant is relative to the density of the ceramics.
Fig. 2. XRD pattern of calcined powders of BST5
(*)BaCO2; (o) SnO2; (#)BaO; ()TiO2; ()BaTiO3
and ( )BaSnO3: (a) 600 oC, (b) 800 oC, (c) 1000 oC,
(d) 1100 oC, (e) 1150 oC and (f) 1200 oC.

(a)

(b)
Fig. 3. SEM morphology of BST5 powders
calcined at (a) 800 oC and (b) 1200 oC.

(a)

(b)
Fig. 4. SEM morphology of BST5 ceramics
sintered at (a) 1350 oC and (b) 1400 oC.

Table 1. % perovskite phase, lattice parameter a, average particle size, average grain size, density
and dielectric constant of BST5.

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Calcined powders

Sintered ceramics

Calcined
Temperture
(oC)

%
perovskite
(%)

Lattice
parameter a
()

Average
particle size
(m)

Sintered
temperture
(oC)

Average
grain size
(m)

Density
(g/cm3)

600
800
1000
1100
1150
1200

54.5
76.7
94.2
95.8
97.3
100

4.0025
4.0067
4.0088
4.0138
4.0185

0.59
0.45
0.51
0.68
0.73
0.86

1250
1300
1350
1400

1.24
8.77
13.69
34.65

5.86
5.92
5.89
5.94

Dielectric
constant

945
1562
3593
3865

Summary
Barium stannate titanate, BST5 can be formed by the reaction of barium carbonate, stannium oxide
and titanium oxide at 1200 oC of calaination temperture. The particle size and grain size were
increased with increasing calcination and sintering temperatures. The maximum density and
dielectric constant were obtained at 1400 oC. These result suggested that the calcination and
sintering temperature directly related to the phase formation, microstructure, density and dielectric
properties of BST5.
Acknowledgments
This work received financial support by the Thailand Research Fund (TRF) and the Commission on
Higher Education (CHE). Thanks also to the Department of Physics, Faculty of Science, Naresuan
University for supporting facilities. Acknowledgements are to Mr. Don Hindle, for his helpful
comments and editing of the manuscript.
References
[1]
[2]
[3]

L. Gao, Y. Huang, Y. Hu and H. Du: Cream Int. Vol. 33 (2007), p. 1041.


Y. Park, K. Cho and H.G. Kim: J. Mater Res. Vol. 81 (1998), p. 1893.
L. Geske, V. Lprenz, T. Muller, L. Jager, H. Beige, H.P. Abicht and V. Mueller: J. Am.
Ceram Soc. Vol. 25 (2005), p. 2537.
[4] X. Wei and X. Yao: Meter Sci. Eng, Vol. 137 (2007), p. 184.
[5] X. Wei, Y. Feng, X. Wan and X. Yao: Ceram Int. Vol. 30 (2004), p. 1397.
[6] X. Wei, Y. Feng, L. Hang and X. Yao: Ceram Int. Vol. 30 (2004), p. 1401.
[7] Powder Diffraction File No. 05-3878, International Center for Diffraction Data, Newton
Square, PA, 2003.
[8] Powder Diffraction File No. 03-3174, International Center for Diffraction Data, Newton
Square, PA, 2003.
[9] Powder Diffraction File No. 21-1272, International Center for Diffraction Data, Newton
Square, PA, 2003.
[10] Powder Diffraction File No. 06-0395, International Center for Diffraction Data, Newton
Square, PA, 2003.
[11] Powder Diffraction File No. 05-0626, International Center for Diffraction Data, Newton
Square, PA, 2003.
[12] Powder Diffraction File No. 03-0675, International Center for Diffraction Data, Newton
Square, PA, 2003.

Advanced Materials Research Vols. 55-57 (2008) pp 185-188


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.185

Preparation of Barium Strontium Titanate Ceramics


via Combustion Method
T. Bongkarna* and C. Wicheanratb
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, Thailand
a

researchcmu@yahoo.com, bmai_mixa@hotmail.com

Keywords: Barium Strontium Titanate, Phase Formation, Microstructure, Combustion

Abstract. This study concentrated on the crystal structure and microstructure of [(Ba0.75Sr0.25)TiO3;
(BST)] ceramics at different firing temperatures. The BST powders were prepared by a combustion
method. (CO(NH2)2) was used as a fuel. Crystallinity of the calcined powders was improved by
increasing the calcining temperature, as indicated by the increase in intensity of the X-ray
diffraction peak. The pure perovskite phase of BST powders was obtained with a calcinations
condition of 1200 oC. The a axis lattice constant of BST calcined powders and sintered ceramics
were calculated and it was found that the crystal structure is a cubic phase. The microstructure of
BST calcined powders and sintered ceramics were analyzed by a scanning electron microscope
(SEM). The SEM result indicated that the average particle size and average grain size increased
with the increase of calcinations and sintering temperatures, respectively. The apparent density of
the samples was measured by the Archimedes method.
Introduction
Barium strontium titanate, BaxSr1-xTiO3 compounds, are the continuous solid solution between
BaTiO3 and SrTiO3 over the whole composition range. They are promising candidates for
microelectronic devices that can be integrated with capacitor, turnable microwave and
semiconductor technologies [1]. There are reports that BaxSr1-xTiO3 [2] has been synthesized using
an established solid-state reaction method. The intensity of the X-ray diffraction peak indicated that
crystallinity and lattice parameters of the calcined powders were improved by increasing the
calcining temperature. The particle size distribution also increased at higher calcining temperatures.
Fu et al [3], reported that the crystal structures of BaxSr1-xTiO3 (0.45 x 0.9) ceramics are in a
tetragonal phase when x 0.65 at room temperature. The values of the coercive electric field (E c)
and remanent polarization (Pr) increases as the Ba/Sr ratio of BaxSr1-xTiO3 ceramics increases
except for x 0.5. The conventional method of synthesizing Ba xSr1-xTiO3 relies on a solid-state
reaction between BaCO3, SrCO3 and TiO2 at a high temperature. Un-fortunately, this method has a
tendency to produce coarse BaxSr1-xTiO3 powder with compositional inhomegeneity, partial particle
agglomeration and the completion of the reaction requires a very high temperature [4]. The
combustion method has tremendous present interest; it helped to decrease the temperature in the
preparation and has a small particle size [5]. The combustion reaction method also has interesting
characteristics such as its simplicity, its relatively low cost and the fact that it usually results in
products with the desired structure and composition [6]. Thus, the aim of this study was to prepare
BaxSr1-xTiO3 (BST) ceramics via the combustion method and also to investigate the effect of firing
temperatures on its phase formation and microstructure.
Experimental
Ba0.75Sr0.25TiO3 (BST) was fabricated using an established combustion method. BaCO3, SrCO3 and
TiO2 powders were used as starting materials. The powders were mixed by ball milling for 24 h
with ethanol as a solution media. The mixed powders were dried at 100 120 oC for 6 h. Prior to
sieving, the powders and urea were mixed in agate motor and calcined at 600 1200 oC for 4 h. The
calcined powders were reground by wet ball milling with 1 wt% binder for 24 h. The obtained

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powders were pressed into pellets with a diameter of 15 mm prior to sintering at 1200 - 1400 oC for
2 h. X-ray diffraction (XRD) was performed to examine the phase constitution of the specimens at
room temperature. The microstructures of the BST samples were examined using a scanning
electron microscopy (SEM). Densities of the sintered ceramics were measured by the Archimedess
method and the average grain size was determined by using a mean linear intercept method.
Results and Discussion
XRD patterns of BST powders calcined at 600 - 1200 oC are shown in Fig.1. For the powders
calcined at below 1200 oC, X-ray peaks of precursors and impurities, BaCO3, BaO and TiO2,
appeared, while the high purity of the cubic perovskite phase was discovered in powders calcined
above 1200 oC, which could be matched with JCPDS file number 39-1395 [7]. The XRD pattern
showed a major X-ray reflection peak in the perovskite BST phase, indicating the polycrystalline
nature of the powder with (011) as the major peak. Crystallinity of the calcined powders was
improved by increasing the calcination temperature, as indicated by the increase in intensity of the
X-ray diffraction peak.
The percent perovskite phase of BST compounds
are calculated and listed in Table 1. The purity of the
perovskite phase rose with increasing temperatures and
100% of the perovskite phase was found above 1200
o
C.
The a axis lattice constant of BST calcined powders
are calculated in Table1. The lattice parameter of the
powders decreased with an increase in the calcining
temperature. This indicates that at low calcining
temperatures, the powders exist in a more strained
form with the atomic entities in non-equilibrium
positions, which relax to an equilibrium position at
higher temperatures. Another possible reason may be
that the domain mobility is restricted due to pinning of
Figure 1. XRD patterns of BST
the domain boundaries by crystal defects [2].
The SEM photomicrographs of BST calcined
powder:
powders at 1000 and 1200 oC are illustrated in Fig. 2.
With the increasing of calcinations temperatures, the average particle size increased. These powders
exhibited an almost spherical morphology and have a porous agglomerated form. The average
particle size was discovered to be about 0.43, 0.37, 0.39, 0.52 and 0.55 m for the samples calcined
at 600, 800, 1000, 1100 and 1200 oC, respectively.

(a)
(b)
Figure 2. SEM micrographs of BST powders calcined at: (a) 1000 oC and (b) 1200 oC.

Advanced Materials Research Vols. 55-57

187

The phase formation behavior of the sintered ceramics was revealed by an XRD method. The
XRD patterns of the BST ceramics sintered at sintering temperatures (1200-1400 oC) are shown in
Fig. 3. From the pattern, a single perovskite cubic phase BST could be obtained in all sintered
samples. This indicates that the conventional combustion technique is a simple and effective
method to produce BST ceramics. Note that the crystal structure of BST at room temperature,
which was prepared via a combustion and mixed oxide method ,[3] was tetragonal and cubic. It
suggested that the Curie temperature of BST, prepared by combustion temperature, shifted when
below room temperature. However, the structural reasons for this are uncertain at this stage.
The lattice parameter of the ceramics also decreased with an increase in the sintering
temperature (Table 1). This result was the same with the calcined process.
The SEM photographs of BST ceramics sintered at 1200 and 1400 oC are shown in Fig. 4. The
results indicated that grain size tends to increase with increasing sintering temperature (Table 1).
The average grain size was discovered to be about 0.87, 0.93, 0.96, 5.40 and 7.12 m for the
samples sintered at 1200, 1250, 1300, 1350 and 1400, respectively. In addition, the porosity was
obviously decreased with an increase of sintered temperature.

Figure 3. XRD patterns of BST ceramics sintered at various temperatures

(a)
(b)
Figure 4. SEM micrographs of BST ceramics sintered at: (a) 1200 oC and (b) 1400 oC.

The variation of the measured density and shrinkage of BST ceramics with different sintering
temperatures are also shown in Table 1. The density and shrinkage increased with an increased
sintering temperature. The density increased from 90.5% to 97.6% when the sintering temperature
increased from 1200 oC to 1400 oC.

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Table 1. Percent perovskite phase, lattice parameter a, density and shrinkage of BST
Calcination
Temperature
(C)
600
800
1000
1100
1200

Calcined powders
%perovskite
Lattice
phase
Parameter a
(%)
()
6.4
3.984
44.9
3.982
94.0
3.980
98.9
3.979
100.0
3.978

Sintering
Temperature
(C)
1200
1250
1300
1350
1400

Sintered ceramics
Lattice
Density
Parameter a
(g/cm3)
()
3.954
5.24
3.947
5.33
3.947
5.34
3.946
5.55
3.929
5.64

Shrinkage
(%)
10.67
11.56
15.33
15.33
15.56

Summary
Perovskite (Ba0.75Sr0.25TiO3) powders and ceramics can be obtained successfully by a conventional
combustion technique. The pure perovskite cubic phase has been discovered at calcinations
temperature above 1200 oC. The lattice parameter a was decreased when calcinations and sintering
temperature increased. The average particle size and average grain size was observed to increase at
higher calcining and sintering temperature. The highest density and shrinkage was obtained in the
sample that sintered at 1400 oC.
Acknowledgements
This work was financial supported by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), Faculty of Science, Naresuan University. Thanks are also to Mr. Don Hindle for
his help correcting the manuscript.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

Y.B. Khollam, S.V. Bhoraskar, S.B. Deshpande, H.S. Potdar, N.R. Pavaskar, S.R. Sainkar and
S.K. Date: Mater. Lett. Vol. 57 (2003), p. 1871.
S. Kongtaweelert, D.C. Sinclair and S. Panichphant: Curr. Appl. Phys. Vol. 6 (2006), p. 474.
C. Fu, C. Yang, H. Chen, Y. Wang and L. Hu: Mat. Sci. Eng. B. Vol. 119 (2005), p. 185.
F. Zhang, T. Karaki, M. Adachi: Powder. Technol. Vol. 159 (2005), p. 13.
K.C. Patil, S.T. Aruna and T. Mimani: Curr. Opim. Solid. St. M. Vol. 2 (1997), p. 158.
K.C. Patil, S.T. Aruna and T. Mimani: Curr. Opim. Solid. St. M. Vol. 6 (2002), p. 507.
Powder Diffraction File No. 39-1395, International Center for Diffraction Data, Newton
Square, PA, 2003.

Advanced Materials Research Vols. 55-57 (2008) pp 189-192


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.189

Effect of MnO2 Impurity on the PZT-PMN System Ceramics for


Piezoelectric Transformer
Y. Suwan1, A. Niyompan1, a, R. Tipakontitikul1, b and P. Laoratanakul2
1

Department of Physics, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190,
Thailand
2

National Metal and Materials Technology Center, Pathumthani 12120, Thailand


a

anuson@rocketmail.com, brungnapa@rocketmail.com

Keywords: PZT-PMN ceramics, piezoelectric transformer, MnO2 doping

Abstract. The PZT-PMN ceramics system was derived from Pb(Zr0.5Ti0.5)O3 and Pb(Mg2/3Nb1/3)O3
based compositions those obtained via the columbite method. The effect of MnO2 addition on
microstructure, physical properties and piezoelectric properties were investigated. In this study, the
composition with PZT/PMN ratio of 1:1 was selected. To observe the effect of MnO2 adding, its
concentration was varied in range 0-10 mol%. Green pellets were sintered at temperature 1250oC
for 4 hours. For piezoelectric investigation, the ceramics pellets were subjected to a poling process.
The XRD results show that there is no phase transformation observed for all sintered PZT-PMN
samples with presence of MnO2. The SEM micrographs reveal that MnO2 can enhance sinterability
as evidenced by lowering of porosity and increasing of grain size with increasing of MnO2 content.
Increasing of linear shrinkage and apparent densities also confirmed such effect. Improvement of
d33 from 28 to 114 pC/N could only found for MnO2 in range 0 to 4 mol%. For higher MnO2
content, there is only slightly increased. However, increasing of kp with increasing of MnO2 is
clearly observed. While dielectric constant measured at room temperature and at frequency 1 kHz
is higher for ceramics without MnO2 doping and it decreases with increasing MnO2 concentration.
The temperature dependence of relative dielectric constant go to peak of value about 6000 at
temperature around 180oC and shifting of these peaks with frequency can only be observed for
samples with higher MnO2 content. This indicates a normal ferroelectric behavior for sample with
lower MnO2 and there are converted to relaxor after MnO2 increased.
Introduction
Formation of binary solid solution ceramics system comprised a normal and a relaxor ferroelectric
material, has been proposed and investigated intensively [1-5]. Combination between these two
distinctive ferroelectric materials has been aimed to reduce dielectric loss found in the normal
ferroelectric material by the relaxor. The PZT-PMN binary system has been the particular example.
PZT (Pb(Zr0.5Ti0.5)O3) has been known to exhibit an excellent dielectric respond but some time it
also shows a high dielectric loss which limits its practical use. Thus, the relaxor PMN
(Pb(Mg2/3Nb1/3)O3) is introduced. In order to obtain desired ceramic for specific application, several
dielectric and piezoelectric parameters have to be optimized by extending to ternary system or by
oxide doping. The PMN-PZN-PZT [6], PNW-PMN-PZT [7] and PMN-PNN-PZT [8] are the
examples of proposed system.
For Piezoelectric transformer application, doping an oxide to the ceramic has been also
considered to be able to improve piezoelectric properties. Mn doping on PZT based normal
ferroelectric materials are the most frequently found in literature as it reported to have an effect on
enhancement both electromechanical coupling factor (kp) and mechanical quality factors (Qm) [9].
In this study, PZT-PMN system was selected as it shows large dielectric constant and
electrostriction. The effect of Mn adding was then investigated in the terms of phase formation,
microstructure, dielectric constant, electromechanical coupling factor (kp) and mechanical quality
factor (Qm). The effect on bulk density and dielectric loss of the ceramics were also reported.

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Experimental
According to the study, the composition with PZT/PMN ratio of 1:1 was selected. PZT and PMN
powders were well-mixed with MnO2 by ball milling for 20 h. To observe the effect of MnO2
adding, its concentration was varied from 0 to 2, 4, 6, 8 and 10 mol%, respectively. Disc shape
ceramics pellets with diameter of 25 mm and about 2.5 mm thick were formed by a dry pressing
technique. The green pellets were then sintered at temperature 1250oC for 4 h with heating/cooling
rate of 5oC/min. Phase formation was then checked by XRD and microstructural arrangement was
studied by SEM technique. Bulk density measurement was also performed using Archimedes
principle. For dielectric and piezoelectric investigation, the ceramics pellets were subjected to a
poling process which silver paste was used as electrodes and high electrical field of 2.0 kV/mm was
applied. For dielectric measurement, r and dielectric loss were acquired at room temperature and at
frequency 1 kHz. Finally, several piezoelectric parameters were determined; d33 by d33 meter, kp
and Qm by impedance/gain-phase analyzer (Hewlett Packard 4164 A)
Results and Discussion

Intensity (a.u.)

(310)

(220)

(211)

(210)

(200)

(111)

(100)

(110)

Fig. 1 shows the X-ray diffraction patterns of the sintered samples. In all samples, pyrochlore phase
and secondary phases due to MnO2 addition are not found. The pattern profiles of doped samples
are similar to that of undoped sample. This indicates that entering of Mn4+ into the perovskite
structure of this system does not lead to phase transformation. This is because Mn4+ can participate
in B-site which only changes lattice parameters slightly. Fig. 2 shows the scanning electron
micrographs of fracture surfaces of the samples. It can be seen that MnO2 addition induces higher
grain development. Also, the grain size increased with MnO2 concentration. The observed grain
sizes are 0.92, 1.09, 1.19, 1.36, 1.59 and 1.90 m for samples with 0, 2, 4, 6, 8 and 10 mol% of
MnO2, respectively. Increasing of MnO2 also reduces porosity and gives sample with higher
densification as evidenced by density values reported in Table 1. Similar observation was also
reported for other doping [10, 11]. From these results, it seems that there were no significant
modifications in crystallographic phases with the MnO2 addition but development of microstructure
due to MnO2 addition is clearly observed.
The dielectric constant and dielectric loss
(tan ) acquired at frequency 1 kHz and at
room temperature of PZT-PMN ceramic
samples are reported in Table 1. It can be
seen that MnO2 doping seems to lower the
dielectric constant. While, dielectric losses
reduces to a minimum value of 0.0059 at 4
(f)
mol% MnO2 before increases to 0.0101
(e)
when MnO2 approaching 8 mol%.
(d)
Increasing of tan at higher MnO2 content
may be associated with larger relaxor
(c)
behavior of the ceramics as reported
(b)
elsewhere [12]. Fig. 3 shows variation of
(a)
d33 with MnO2 content. Increasing of d33
10
20
30
40
50
60
70
80
from 28 to 114 pC/N could be found only
2 (degrees)
for MnO2 in range 0 to 4 mol% and it
Figure 1. XRD powder patterns of PZT/PMN saturated after MnO2 exceeding 6 mol%.
ceramics sintered at 1250oC for various MnO2 Improvement of d33 at lower MnO2 content
concentration: 0, 2, 4, 6, 8 and 10 mol% for (a)- is thought to result from the increase of the
remnant polarization due to higher degree
(f), respectively.
of domain wall movement.

Advanced Materials Research Vols. 55-57

Table 1. Summarized bulk density values, r and


tan acquired at room temperature for PZT-PMN
with MnO2 addition
MnO2
(mol% )
0

Density
(g/cm3)

r
at 1 kHz

tan

7.238

1952

0.0406

7.047

1164

0.0078

7.131

983

0.0059

7.329

957

0.0064

7.428

936

0.0101

10

7.556

1011

0.0140

191

(a)

(b)

(c)

(d)

Figure 2. SEM photograph of fracture surfaces


for PZT-PMN+ x mol% MnO2: (a) undoped (b)
x = 2, (c) x = 4 and (d) x = 8.
0.24

120

0.22
100

80

kp

d33 (pC/N)

0.20
0.18
0.16

60

0.14
40

0.12
20

0.10

10

MnO2 content (mol%)

10

MnO2 content (mol%)

Figure 3. The d33 value (a) and electromechanical planar coupling coefficient, kp (b) as a function of
MnO2 content in PZT-PMN ceramics.
1800
1600
1400

Qm

1200
1000
800
600
400
200
0

10

12

MnO2 content (mol%)

Figure 4. Variation of Qm as a function of MnO2 content for doped PZT-PMN ceramics.


For higher MnO2 content, the domain wall movement was inhibited which results to the saturation
state. Fig. 3(b) shows the behaviors of kp as a function of the MnO2 content. The kp are lied between
0.12 and 0.23 for amount of MnO2 in range 0-10 mol%. Variation of Qm as a function of MnO2

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content is shown in Fig. 4. It is clearly seen that introduction of Mn4+ into the PZT-PMN structure
enhance Qm from 115 for undoped sample to 1669 for sample with 8 mol% MnO2, after that it
reduce slightly to 1048 for 10 mol% MnO2. From the present results, it may come to a prediction
that Mn behaves as an acceptor and a domain wall pinning as has been proposed in the previous
report [9].
From this study it is seen that improvement of Qm and kp factors for PZT-PMN ceramic samples
can be achieved by MnO2 addition. These two factors also show higher values for MnO2 in range 68 mol%. After investigation of obtained values of various parameters: phase, density, d33, r, Qm, kp
and dielectric loss, the ceramic PZT-PMN added with 6 mol% MnO2 seems to be the most
appropriate composition for piezoelectric transformer application as it exhibits some reasonable
good properties.
Summary
Physical and dielectric properties of PZT-PMN ceramics system doped with MnO2 were
investigated. The results show that increasing amount of MnO2 improved sinterability as evidenced
by SEM and density investigation. Participation of MnO2 also had pronounced effect on
piezoelectric properties as kp and Qm increased with MnO2 content. The d33 also increased but
almost went to saturation after MnO2 exceeded 6 mol%. This study has demonstrated that both
physical and piezoelectric properties of understudied ceramics system can be enhanced and could
lead to desired characteristic requiring for piezoelectric transformer application.
Acknowledgement
This research was supported by The National Research Council of Thailand. Y. S. would like to
thanks to the Young Scientist and Technologist Programme (YSTP) under supervision of National
Science and Technology Development Agency (NSTDA), Thailand.
References
[1]

A. V. Shilnikov, A. V. Sopit, A. I. Burkhanov and A. G. Luchaninov: J. Euro. Ceram. Soc.


Vol. 19 (1999), p.1295.
[2] J. H. Park, K. H. Yoon, D. H. Kang and J. Park: Mater. Sci. Eng. B Vol. (2002), p.1.
[3] K. Sumi, H. Qiu, H. Kamei, S. Moriya, M. Murai, M. Shimada, T. Nishiwaki, K. Takei and
M. Hashimoto: Thin Solid Films. Vol. 349 (1999), p. 270.
[4] J. H. Park, K. H. Yoon and D. H. Kang: Thin Solid Film. Vol. 396 (2001), p. 84.
[5] C. H. Wang: J. Euro. Ceram. Soc. Vol. 22 (2002), p. 2033.
[6] Z. Yang, X. Chao, R. Zhang, Y. Chang and Y. Chen: Mater. Sci. Eng. B Vol. 138 (2007), p.
277.
[7] L. Hwang, J. Yoo, E. Jang, D. Oh, Y. Jeong, I. Ahn and M. Cho: Sensors and Actuators A
Vol. 115 (2004), p. 73.
[8] Y. Jeong, J. Yoo, S. Lee and J. Hong: Sensors and Actuators A Vol. 135 (2007), p. 215.
[9] J. H. Park, J. Park, J. G. Park, B. K. Kim and Y. Kim: J. Euro. Ceram. Soc. Vol. 21 (2001), p.
1383.
[10] C.-Y. Chen and H.-L. Lin: Ceram. Inter. Vol. 30 (2004), p. 2075.
[11] J. Yoo, C. Lee, Y. Jeong, K. Chung, D. Lee and D. Paik: Mater. Chem. Phy. Vol. 90 (2005),
p. 386.
[12] S. Wongsaenmai, Y. Laosiritaworn, S. Ananta and R. Yimnirun: Mater. Sci. Eng. B Vol. 128
(2006), p. 83.

Advanced Materials Research Vols. 55-57 (2008) pp 193-196


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.193

Effect of Excess PbO on Crystal Structure, Microstructure and


Phase Transition of Lead Titanate Ceramics
W. Tangkawsakula, P. Sittiketkronb and T. Bongkarnc*
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, THAILAND
a

tangkawsakul@hotmail.com, bmay_panat@hotmail.com, cresearchcmu@yahoo.com

Keywords: Excess PbO, Lead Titanate, Crystal Structure, Microstructure

Abstract. In this work, we studied the effect of excess PbO on crystal structure, microstructure and
phase transition of lead titanate (PT). PT was prepared via a mixed oxide method with various PbO
levels (0, 1, 3 and 5 wt.%). The raw materials were calcined at 750 oC for 2 h and sintered at 1225
o
C for 2 h. The characteristics of PT were analyzed by a X-ray diffractometer (XRD), scanning
electron microscopy (SEM) and differential scanning calorimeter (DSC). It was found that calcined
powders and sintered ceramics indexed in a tetragonal structure. For PT powders, the impurity
phases of lead oxide (PbO) and lead dioxide (PbO2) were detected in 3 and 5 wt.% of excess PbO
samples, but they were not detected in all sintered ceramic samples. The increase of excess PbO
levels resulted in a decreased c/a ratio in both calcined powders and sintered ceramics. Average
particle sizes increased from 0.64 to 4.24 m when excess PbO levels increased from 0 to 5 wt.%. It
was also clearly seen that the liquid phase of the sintering process was obtained in the PT calcined
powders which had an excess of PbO. The DSC result indicated that the phase transition
temperature, from a ferroelectric to a paraelectric phase with a high PbO content (5 wt.%), was
higher than those with low PbO contents (0, 1 and 3 wt.%).
Introduction
Lead titanate, PbTiO3 (PT), belongs to the most important ferroelectric family [1]. It is a material
with a perovskite structure (ABO3) in which a ferroelectric phase transition occurs around 490 oC.
Above this temperature its crystal structure is cubic and below the Curie point the cubic phase
changes to a tetragonal phase [2]. PT is useful as a pyroelectric and piezoelectric base material for
high-temperature or high-frequency applications, such as nonvolatile memories, infrared sensors,
micro actuators, capacitors, and eletrooptic devices [3]. The preparation of pure dense PT ceramics
of high resistivity is very difficult. Because PT ceramics gradually disintegrate into a powder when
they are cooled below the cubic-tetragonal phase transition temperature [4-5]. Because of its large
lattice tetragonality, c/a (~1.064) [6]. PT is generally synthesized by a solid state reaction, a sol-gel
process, chemical precipitation, and hydrothermal treatment [7-10]. The solid state reaction (mixed
oxide) is the simplest method for prepared PT, but the preparation temperature of the mixed oxide
method is higher than the PbO melting point (880 oC) and it causes evaporation of PbO in sintering
process. Much research have suggested that PbO loss during firing affects the physical properties of
the lead base and the performance of these devices [11]. In order to compensate for the lead loss in
the sample, some excess PbO is usually added during the batch preparation [12]. The effect of
excess PbO on crystal structure, microstructure and the phase transition of PT were studied in this
works.
Experimental
The PT was prepared by a conventional mixed oxide route. The raw materials of PbO and TiO2
were weighed and mixed. The mixture of the starting powders was milled and mixed in a ball mill,
as well as wet-homogenized with ethanol for 24 h. using a zirconium grinding media. The
suspensions were dried and the powders were ground using an agate mortar and sieved into a fine
powder. All obtained powders were calcined at 750 oC for 2 h. in a closed alumina crucible. An

194

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excess of PbO, equivalent to 0, 1, 3 and 5 wt.% was applied prior to ball milling and before
calcinations. The PT powders were reground by wet ball-milling with a 2 wt.% binder. The calcined
powders with binder were dried, crushed and sieved again. The powdered mixtures were
isostatically pressed, at 60 MPa, into a pellet. Finally, the pellets were fired in an alumina crucible
and sintered at 1225 oC for 2 h. The crystal microstructure and phase transition of PT were analyzed
by X-ray diffractometer (XRD), scanning electron microscopy (SEM) and a differential scanning
calorimeter (DSC).
Results and Discussion
Fig.1 (a) and (b) show XRD patterns of calcined powders and sintered ceramics with various excess
PbO levels. The diffraction lines could be indexed with respect to tetragonal structure and matched
with JCPDS file number 06-0452. In the case of calcined powders, the impurity phase of PbO and
PbO2 were detected in 3 and 5 wt.% of excess PbO. The pure perovskite phase was detected in all
sintered ceramics samples indicating that the excess PbO, beyond that required to maintain
compositional control (assumed) in the calcined powders, was eliminated from the sample by
volatilization during sintering at 1225 oC [13]. The percentage of the perovskite phase was
decreased with increased excess of PbO, as seen in table 1. The adding of PbO also affected lattice
parameters a and c. The lattice parameter a increased, with rates of 0.0006 and 0.0010 /wt.%, in
calcined powders and sintered ceramics (Fig.2). Lattice parameter c decreased with rate of 0.0006
and 0.0010 /wt.% in calcined powders and sintered ceramics. Furthermore, the c/a ratio was
decreased with an increase of excess PbO levels (Table 1).

(b)
(a)
Fig.1 XRD patterns of (a) calcined powders and (b) sintered ceramics containing different amounts
of excess PbO: () PbO () PbO2.

(b)
(a)
Fig.2 Lattice parameter c and a of (a) calcined powders and (b) sintered ceramics have different
levels of excess PbO.

Advanced Materials Research Vols. 55-57

195

Pb and O ion vacancies in uncompensated compositions stabilize in the ferroelectric phase. In the
previous work, T. Bongkran et al, said the proportion of the rhombohedral ferroelectric phase was
increased when the excess PbO increased [13]. These indicated that the excess PbO had a direct
effect on the crystal structure of lead base materials.
Table1 % perovskite phase, c/a ratio, average particle size, and average grain size of PT
Excess
PbO level
(wt.%)
0
1
3
5

% perovskite
phase
100.0
100.0
98.8
93.4

Calcined powder
Average particle
c/a ratio
size(m)
1.0623
0.7
1.0619
2.4
1.0614
2.7
1.0610
4.0

Sintered ceramic
Average grain
c/a ratio
size (m)
1.0621
32.63
1.0614
4.58
1.0608
7.68
1.0601
11.33

Fig.3 Shows SEM micrographs of calcined powders. The calcined powders were irregular in shape
with a substantial variation in particle size (Table 1.). The particle size and degree of agglomeration
tended to increase with the increase of excess PbO. It is believed that the liquid phase sintering
process starts in the chosen calcinations temperatures and as a consequence the agglomerates are
formed in the calcined powders [14]. The SEM micrographs of sintered ceramics are shown in Fig.4
and the average grain size is shown in Table 1. The average grain size decreases with increasing
amounts of PbO until 1 wt.%, then slightly increases with further excess PbO.

(a)

(b)

Fig. 3 SEM micrographs of calcined powders with excess PbO (a) 1 wt.% and (b) 5 wt.%.

(a)

(b)

Fig. 4 SEM micrographs of sintered ceramics surface with excess PbO (a) 1 wt.% and (b) 5 wt.%.

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Fig. 5 DSC result of sintered ceramic


samples.
Fig. 5 DSC results of sintered ceramic samples.

Fig. 5 shows the DSC results of sintered


samples. The distinct endothermic peak can
be attributed to Curie temperature, which was
transforming from tetragonal ferroelectric to
cubic paraelectric. It indicated that phase
transition temperatures from the ferroelectric
to the paraelectric phase of high PbO content
(5 wt.%) was higher than the low PbO
contents ( 0, 1 and 3 wt.%). The phase
transition temperatures of 0, 1 and 3 wt.%
ceramics samples were about 479.5 oC, while
the 5 wt.% ceramic sample increased at
484.12 oC. It is shown that when the PbO
concentration in PT compositions exceed a
threshold value of about 5 wt.%, the Curie
temperature was slightly increased.

Summary
Excess PbO directly affected lattice parameters c, a and tetragonality of PT calcined powders and
sintered ceramics. The unreacted PbO and PbO2 in calcined powder were employed to compensate
lead loss in the sintering process. The excess PbO caused a decrease in the melting point; hence the
liquid phase sintering occurred in a calcined process. The Curie temperature slightly shifted when
the PbO was added 5 wt.%
Acknowledgments
This work was financially supported by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE) and Faculty of Science, Naresuan University. Thanks also to Mr. Don Hindle for
his help in editing this manuscript.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

C. Chandler, C. Roger and M. Hampdansmith: Chem. Rev. Vol. 300 (2006), p. 569.
P. Duran, J. F. Lozano, F. Capel and C. Moure: Mater Sci. Vol. 23 (1988), p. 4463.
I. Moon, J. A. Kerchner, J. Lebleu, A. A. Morrone and J. H. Adair: J. Am. Ceram. Soc. Vol.
80 (1997), p. 2613.
H. D. Megaw: Proc. Phys. Soc. Vol. 58 (1946), p. 133.
G. Shirane and S. Hoshino: J. Phys. Soc. Jpn. Vol. 6 (1951), P. 265.
T. Chen, S. Chu and Y. Juang: Mater. Lett. Vol. 57 (2003), p. 1251.
S. Ikegami, I. Ueda and T. Nagta: J. Acoust. Soc. Am. Vol. 50 (1971), p. 1060.
G. B. Blum and S. R. Gurkovich: J. Mater Scien. Vol. 20 (1989), p. 4479.
A. Safari, H. Y. Lee, A. Halliyal and R. E. Newham: Am. Ceram. Soc. Bull. Vol. 66 (1987), p.
668.
H. Idrissi, A. Aboujalil, J. P. Deloume, G. Fantozzi and B. Durand: J. Eur. Ceram. Soc. Vol.
19 (1999), p. 1997.
S. R. Dhage, Y. B. Khollam, H. S. Potdar, S. B. Deshpande, B. D. Sarwade and S. K. Date:
Mater. Lett. Vol. 56 (2002), p. 564.
T. Bongkran and G. Rujijanagul: Curr. Appl. Phys. Vol. 6 (2006), p. 319.
T. Bongkran, G. Rujijanagul and S. J. Milne: Mater. Lett. Vol. 59 (2005), p. 1200.
D. Kuscer, J. Korzekwa, M. Kosec and R. Skulski: J. Eur. Ceram. Soc. Vol. 27 (2007),
p.4499.

Advanced Materials Research Vols. 55-57 (2008) pp 197-200


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.197

Effects of Calcination Temperatures on Phase and Morphology


Evolution of (Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 Powders Synthesized via SolidState Reaction and Combustion Technique
A. Thongthaa, K. Angsukasedb and T. Bongkarnc*
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, THAILAND
a
jerran99_@hotmail.com, bSam_s2h@hotmail.com, cresearchcmu@yahoo.com
Keywords: Phase Formation, Microstructure, Solid-State Reaction, Combustion Technique

Abstract. The effect of calcination temperatures (1000-1400 oC) on the phase formation and
microstructure of barium strontium zirconate titanate [(Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 ; BSZT] powders
were investigated. BSZT powders were prepared and compared by the solid state reaction method
and the combustion technique. The higher calcination temperatures increased the percentage of the
perovskite phase, but decreased the lattice parameter a. The same crystallographic pure perovskite
phase of BSZT powders, which were prepared via the combustion technique were detected above
1300 oC ; which was lower than the calcinations temperature of mixed oxide method by 50 oC. The
TGA-DTA results corresponded to XRD investigation. The microstructure of BSZT powders,
which were prepared using both techniques, exhibited an almost-spherical morphology and had a
porous agglomerated form. The average particle sizes of BSZT powders prepared via the
combustion technique (0.13-0.30 m) and the solid state reaction method (0.18-0.38 m) were
increased with the increase of calcinations temperatures.
Introduction
A solid solution of barium titanate and strontium zirconate; (1-x)BaTiO3xSrZrO3 exists in a single
phase for wide range of composition. The solid solution exhibited paraeletric properties, was
chemically more stable, had a lower transition temperature (Tc) and had a high dielectric constant
for x value above 0.2 [1]. (1-x)BaTiO3xSrZrO3 compounds have been applied in microwave
dielectric resonators which are miniature resonating devices used in microwave integrated circuits
[2]. The tunability and figure of merit of (Ba0.75Sr0.25)(Zr0.25Ti0.75)O3 thin films prepared by pulsed
laser deposition are 53% and 38 which were a promising candidate as microwave tunable devices
[1,3]. A literature survey has revealed: the sol-gel technique reaction has been used for preparing
(1-x)BaTiO3xSrZrO3 powders [4-6]. It is well known that this processing of samples preparation is
complex and expensive [7]. The mixed oxide synthetic route is probably one of the most
fundamental, practical, routine methods which has been used, developed and modified in both
scientific research and industrial mass production for many years [8,9]. The combustion technique
is interesting because it can decrease the calcinations temperature [10], obtains a pure phase and
nanosized particles because of its high surface energy and driving force [11].
A detailed study of the synthesis and characterization of (Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 powders by
the solid-state reaction and the combustion technique have rarely been reported in the literature. So,
in this present work, the (Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 powders were prepared via the solid-state
reaction and the combustion technique. The effect of calcinations temperatures on the phase
formation and microstructure of BSZT powders were also investigated.
Experimental
The starting materials were commercially available: BaCO3 (99%), SrCO3 (99%), ZrO2 (99%) and
TiO2 (99%). Barium strontium zirconate titanate ((Ba0.25Sr0.75)(Zr0.75Ti0.25)O3) powder was
synthesized by the solid state reaction method and the combustion technique. For the solid state
reaction method, a thoroughly ground mixtures of raw materials were milled in the required

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stoichiometric ratio. Instead of employing a ball milling procedure (zirconia milling media under
ethanol for 24h) drying was carried out at 120 oC for 4 h. After sieving, the reaction of uncalcined
powders taking place during heat treatment were investigated by thermogravimetric and differential
thermal analysis (TGA-DTA) using a heating rate of 10 oC/min, in air, from room temperature up to
1300 oC. The uncalcined powders were calcined in temperatures ranging from 800 to 1400 oC, with
a dwell time of 4 h and a heating/cooling rate 5 oC/min. The calcined powders were subsequently
examined by X-ray diffraction (XRD) to identify the phase formed and optimum calcination
temperatures of BSZT powders. Powder morphologies and particle sizes were directly imaged,
using scanning electron microscopy (SEM). For the combustion technique, the mixtures of raw
materials and the fuel, urea, was well-mixed before the calcination step and the other processes
were as same as the solid state reaction method.
Results and discussion
The TGA and DTA curves obtained for the powders in the stoichiometric proportions of BSZT and
BSZT with urea are shown in Fig.1 (a) and (b). The composite powders prepared via the solid state
reaction method in Fig.1(a) demonstrates a small exothermic peak in the DTA pattern at around 120
o
C, which can be attributed to the vaporization of water. However, no anomaly was observed in the
TGA pattern at this temperature. The weight loss observed around 770 oC. It related to a small
endothermic peak in the DTA curve around 825 oC, and showed the chemical reaction between
BaCO3, SrCO3, ZrO2 and TiO2. Moreover, the endothermic peak with a minimum temperature
around 995 and 1022 oC was also observed.
Fig.1(b). The TGA curve showed four distinct weight losses. The first weight loss occurred
below 200 oC, which was related to the melting of urea at about 135 oC [12], and related to the
endothermic peak at 141 oC. The second occurred between 200 and 500 oC due to the rapid
vaporization of water and gas [13], and corresponded to the endothermic peak in the DTA curves at
193, 339 and 475 oC. The third occurred above 500 oC, which correlated with the small endothermic
peaks around 626 oC, and showed the chemical reaction of the raw materials. The last weight loss
occurred at more than 790 oC, and continued with the third weight loss. This correlates with the
endothermic peak at 784, 815 and 1002 oC. The reactions, involved the decomposition of the raw
materials were not finished at about 1300 oC, because the base of the DTA-TGA instrument was
limited to 1300 oC.

(a)

(b)

Fig.1. TGA-DTA curves for the mixture of raw materials synthesized via (a) solid state reaction and
(b) combustion technique.
Fig.2 (a) and (b) shows XRD patterns of BSZT powders prepared by a solid state reaction method
and a combustion technique at different synthesis conditions. The diffraction synthesis lines could
be indexed on the basis of a cubic structure matched with JCPDS file number 03-0632. Raw
materials of BaCO3, SrCO3, ZrO2 and TiO2 were discovered at calcination temperatures below 1350
o
C and 1300oC for both the solid state reaction method and the combustion technique. The pure
cubic perovskite phase was found in powders calcined higher than 1350 oC and 1300 oC for the
solid state reaction method and the combustion technique. The preparation temperature of the

Advanced Materials Research Vols. 55-57

199

combustion technique was lower than the solid state reaction method by about 50 oC. The XRD
results corresponded to the TGA-DTA investigation.

(a)
(b)
Fig. 2 XRD patterns of BSZT powders calcined at various temperatures for 4 h prepared via (a) the solid
state reaction and (b) the combustion technique : (u) ZrO2; ()BaO; ()BaTiO3; ()TiO2 ; ()SrTiO3.

The percent perovskite phase of BSZT calcined powders is listed in Table 1. The highering of
phase purity with the increasing calcination temperature was evident in both methods. The lattice
parameter a of BSZT calcined powders were caculated by the following equation:

1
h2 + k 2 + l 2
=
2
d hkl
a2
Table 1 The percent perovskite phase, lattice parameter a and average particle size of BSZT powders
Solid state reaction technique

Combustion technique

Calcined
temperature
(oC)

Percent
perovskite
phase (%)

Lattice
parameter a
()

Average
particle size
( m )

Calcined
temperature
(oC)

Percent
perovskite
phase (%)

Lattice
parameter a
()

Average
particle size
( m )

1000

71.5

4.1146

0.18

1000

66.5

4.1146

0.13

1100

73.5

4.1137

0.19

1100

73.0

4.1128

0.15

1200

77.1

4.1128

0.20

1200

85.0

4.1040

0.16

1300

95.3

4.0855

0.25

1250

95.3

4.0846

0.18

1350
1400

100
100

4.0829
4.0785

0.32
0.38

1300
1400

100
100

4.0829
4.0811

0.22
0.30

The data for calculation was received from (110), (200) and (211) XRD peaks. The lattice
parameters a decreaseed with the increasing calcination temperatures, listed in table1. This
indicated that the calcination temperatures affected the crystal structure and the phase formation.

(a)

(b)

Fig. 3 SEM micrographs of the


BSZT powders prepared via the
solid state reaction method
calcined at: (a) 1300 oC and
(b) 1400 oC, for 4 h.

Fig.3 and fig.4 showed the


SEM photographs of BSZT
powders synthesized via a solid state reaction and a combustion technique with different
calcinations temperatures. These powders exhibited an almost spherical morphology and have a
porous agglomerated form. The average particle size of BSZT powders, synthesized by a solid state
reaction method, was 0.18-0.38 m and from the combustion technique were 0.13-0.30 m, when
calcined between 1000 and 1400 oC. In each calcination temperature, the average particle size, via

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combustion technique, was smaller than with the solid state reaction method. The average particle
size, with both techniques, increased as calcinations temperatures increased, as shown in table1.

(a)

(b)

Fig. 4 SEM micrographs of the BSZT powders synthesized via the combustion technique calcined at:
(a) 1300 oC and (b) 1400 oC, for 4 h.
Summary
(Ba0.25Sr0.75)(Zr0.75Ti0.25)O3 powders can be obtained from a combustion technique and a solid-state
reaction method. The pure cubic perovskite phase was obtained with a calcination temperature of
1300 oC by the combustion technique. It was a lower temperature than the solid state reaction
method by about 50 oC. The lattice parameter a of the both techniques increased with increasing
calcination temperatures. The calcinations temperatures have a strong influence on the crystal
structure, lattice parameter and homogeneity of the calcined powders. The resulting BSZT powders
were more agglomerated as the calcination temperature increased.
Acknowledgments
This work was supported financially by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), Faculty of Science, Naresuan University. Thanks also to the Science Lab Center,
Faculty of Science, Naresuan University for support facilities. Acknowledgements also to Mr. Don
Hindle, for his helpful correction of the manuscript.
References
[1] X. Tang, J. Wang and H.L.W. Chan: J. Cryst. Growth, Vol. 276 (2006), p. 453.
[2] J.S. Kim and S.G. Yoon: J. Vac. Sci. Technol. B Vol. 18 (2000), p. 216.
[3] W.J. Kim, W. Chang, S.B. Qadri, J.M. Pond, S.W. Kirchoefer, D.B. Chrisey and J.S. Horwitz:
Appl. Phys. Lett. Vol. 76 (2000), p. 1185.
[4] X.G. Tang, K.H. Chew and H.L.W. Chan: Acta. Mater. Vol. 52 (2004), p. 5177.
[5] X.G. Tang, X.X. Wang, K.H. Chew and H.L.W. Chan: Solid State Commun. Vol. 136 (2005),
p. 89.
[6] M. Veith, S. Mathur, N. Lecerf, V. Huch, T. Decker, H.P. Beck, W. Eiser and R. Haberkorn:
J. SolGel Sci. Technol. Vol. 15 (2000), p. 145.
[7] T. Ahmad and A.K. Ganguli: J. Am. Ceram. Soc. Vol. 89 (2006), p. 3140.
[8] T.R. Shrout, P. Papet, S. Kim and G.S. Lee: J. Am. Ceram. Soc. Vol. 73 (1990), p. 1862.
[9] B.V. Hiremath, A.I. Kingon and J.V. Biggers: J. Am. Ceram. Soc. Vol. 66 (1983), p. 790.
[10] F. Boschini, B. Robertz, A. Rulmont and R. Cloots: J. Eur. Ceram. Soc. Vol. 23
(2003), p. 3035.
[11] A. Zhang, M. lu, S. Wang, G. Zhou, S. Wang and Y. Zhou: J. Alloy Compd. Vol. 433 (2007),
p. L7.
[12] D. Xue, J. Xu and C. Yan: Mater. Lett. Vol. 59 (2005), p. 2920.
[13] I. Ganesh, R. Johnson, G.V.N. RaO, Y.R. Mahajan, S.S. Madavendra and B.M. Reddy: Ceram.
Int. Vol. 31 (2005), p. 67.

Advanced Materials Research Vols. 55-57 (2008) pp 201-204


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.201

Phase Formation and Microstructure of PBZT Powders Prepared via


Mixed Oxide Method
T. Bongkarna* and C. Thiangchitb
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, Thailand
a

researchcmu@yahoo.com, bthaingchit@hotmail.com

Keywords: Lead Barium Zirconate Titanate, Mixed Oxide, Phase Formation, Microstructure

Abstract. In this study, lead barium zirconate titanate [(Pb0.975Ba0.025)(Zr1-xTix); (PBZT)] powders
with 0 x 1 were prepared via the mixed oxide method. The calcinations were performed between
800 and 1000 oC for 1 h. The phase formation and microstructure was studied by X-ray diffraction
(XRD) and scanning electron microscopy (SEM). It was found that the structural phase indexed in
the orthorhombic phase for x = 0. The tetragonal phase was detected in 0.25 x 1 samples. TG
and DTA curves corresponded to XRD results. The SEM result indicated that the particle size of
the powders were nonconsistant and ranged from ~0.5 to ~1.3 m.
Introduction
Lead Barium Zirconate, (Pb0.975Ba0.025)ZrO3 (PBZ) is a material with a perovskite structure. At
room temperature, it has an antiferroelectric phase (AFE) which has an orthorhombic structure [14]. It changes from the AFE to a ferroelectric phase (FE), and transforms from a orthorhombic
structure to a rhombohedral structure at 190 oC. The FE changes to a paraelectric phase (PE), and
transforms from a rhombohedral structure to a cubic structure at 223 oC [3,4]. The AFE-FE phase
transition of PBZ produced a large volume expansion (~1%). This make PBZ ceramics an
interesting material potentially useful for high displacement electromechanical actuator applications
[3,4]. Lead Barium Titanate, (Pb0.975Ba0.025)TiO3 (PBT) is a perovskite type ferroelectric material
with a Curie temperature of 420 oC and it has a tetragonal structure at room temperature [5]. It has
been used to manufacture many electric and optical devices by utilizing their xcellent dielectric,
piezoelectric and optical properties [6].
(Pb0.975Ba0.025)(Zr1-xTix)O3; (PBZT) is solid solution of (Pb0.975Ba0.025)ZrO3 (PBZ) and
(Pb0.975Ba0.025)TiO3 (PBT). It is clearly seen that the structural phase and Curie temperature of PBZ
absolutely differ from PBT. This suggested that the amounts of Zr4+ and Ti4+ ions on the B-site
were directly effected by the phase formation and properties of PBZT. However, the crystal
structure and microstructure of PBZT powders has rarely been reported in the literature. Therefore,
in this work, (Pb0.975Ba0.025)(Zr1-xTix)O3; (PBZT) for 0 x 1 powders were prepared by a mixed
oxide method. The structural phases and microstructure of PBZT powders are also investigated.
Experimental
The (Pb0.975Ba0.025)(Zr1-xTix)O3; (PBZT) powders with 0 x 1 were prepared using a conventional
mixed oxide method. The proper amounts of reagents: PbO, BaCO3, ZrO2, and TiO2 were weighed.
Then the starting powders were homogeneously mixed via ball-milling for 24 h with a zirconia
media in ethanol and dried. The reaction of the uncalcined powders taking place during heat
treatment was investigated by themogravimetric and differential thermal analysis (TG-DTA), using
a heating rate of 10 oC/min. The well-mixed powders were calcined between 800 and 1000 oC for
1 h in an alumina crucible. Calcined powders were subsequently examined at room temperature Xray diffraction (XRD) using CuK radiation to indentify the phases formed and optimum
calcinations conditions for the formation of PBZT powders. Powder morphologies and particle
sizes were checked using scanning electron microscopy (SEM).

202

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Results and Discussion


The TG and DTA curves, recorded at a heating rate of 10 oC/min in air with an equimolar mixture
of lead oxide, barium carbonate, zirconium oxide and lead oxide, barium carbonate, titanium oxide
of PBZ and PBT, are shown in Fig. 1a and 1b. The TG curve shows two distinct weight losses (Fig
1a). The first weight loss occurs around 275 oC and the second one above 750 oC. The sample
shows a small endothermic peak in the DTA curve ~100 oC. This DTA peak can be attributed to
the vaporization of water [4]. However, no anomaly was observed from the TG pattern at this
temperature. This may indicate that the small amount of vaporization of water could not be
detected by the TG measurement. The first weight loss relates to the elimination of the organic
residue from the milling process [7]. After the first weight loss, the sample shows nearly zero
weight loss up to 750 oC. During to the second fall in specimen weight, by increasing the
temperature up to 700 oC, the solid-state reaction between PbO, BaCO3 and ZrO2 was observed.
The broad endothermic characteristic in the DTA curve represents that reaction, at a minimum, at
706 o C. Moreover, another endothermic peak, with a minimum at 963 o C, was also observed in
this profile. While, the DTA event at 522 oC is associated with the allotropic transition
- BaCO3 - BaCO3, this kind of transition does not result in weight loss [8]. The result
greed with Gomez Yanez et al [9], who analyzed the reaction of the milled powders of BaCO3 and
TiO3 of PBZ. The composite powders demonstrate two distinct weight losses below 800 oC (Fig
1b). The first weight loss occurred around 270 oC and the second one above 680 oC. In
temperatures ranging from 50 to ~150 oC, the sample shows a small endothermic peak in the DTA
curve ~100 oC. This DTA peak can be attributed to the vaporization of water. The first weight loss
relates to the elimination of the organic residue from the milling process [7]. The second weight
loss corresponded to the endothermic peak in the DTA curve, which began around 675 oC. A
chemical reaction between PbO, BaCO3 and TiO2 was also observed at this temperature. The broad
endothermic characteristic in the DTA curve represents that reaction which has a minimum at 800
o
C. These data were used to define the range of temperatures for the XRD investigation.

(b)
(a)
Figure 1. TG-DTA curves for the mixture of raw materials (a) PbO, BaCO3 and ZrO2 and (b)
PbO, BaCO3 and TiO2.
Fig. 2a and 2b show the XRD patterns of PBZT powders with x = 0.25 and 0.50 ratio. The high
purity of tetragonal perovskite phase appeared at 950 and 900 oC for x = 0.25 and x = 0.50,
respectively. Below optimum temperatures (600 - 950 oC for x = 0.25 and 800, 850 oC for x = 0.50),
the precursor phases such as TiO, BaTiO3, ZrO2, BaCO3, PbO and PbO2 were detected. While,
above optimum temperature (1000 oC for x = 0.25 and 950, 1000 oC for x = 0.50), the secondary
phases of BaTiO3, ZrO2 and PbO2 were observed. For x = 0, 0.75 and 1, the optimum temperatures
were 1000, 850 and 800 oC, respectively. The results of XRD measurement corresponded with the
TG-DTA investigation. Therefore, the solid state reaction between the raw materials was gained at

Advanced Materials Research Vols. 55-57

203

optimum calcinations temperature of: 1000, 950, 900, 850 and 800 oC for x = 0, 0.25, 0.50, 0.75
and 1, respectively.

(a)
(b)
Figure 2. XRD patterns of PBZT powder for (a) x = 0.25 and (b) x = 0.50 calcined at
600-1000 oC; (t) TiO, () BaTiO3, () ZrO2, () BaCO3, () PbO and () PbO2.
Fig. 3 shows the XRD patterns of PBZT powders
with 0 x 1 ratio calcined at 800-1000 oC for 1
h. The diffraction lines of x = 0 could be indexed
with respect to a orthorhombic structure matched
with JCPDS file no 35-0739 [10]. While, powders
PBZT with 0.25 x 1 ratio indexed with respect
to a tetragonal structure matched with JCPDS file
no 06-0452 [11]. Table 1 shows the crystal
structure, lattice parameter and unit cell volume of
PBZT obtained by the least square refinement
method. It is clearly seen that the lattice parameter
and unit cell volume decreases with increasing x
contents. For tetragonal phase ceramices the c/a
ratio incresed when contents of x increased.
The SEM micrographs of the calcined PBZT
powders with x = 0.25 and 0.75 ratio are shown
in Fig. 4. These powders exhibited an almost
spherical morphology and the average particles
size of the powders is nonconsistant of ~0.5 to
~1.3 m as demonstrated in table 1.
Figure 3. XRD patterns of PBZT powder
for 0 x 1 calcined at 800-1000 oC.

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(a)

(b)

Figure 4. SEM micrographs of the PBZT powders for (a) x = 0.25 and (b) x = 0.75.
Table 1. Crystal structure, lattice parameters, unit cell volume, c/a ratio and average particle size
of PBZT powders.
Compositions
(x)

Crystal
structure

0
0.25
0.50
0.75
1

Orthorhombic
Tetragonal
Tetragonal
Tetragonal
Tetragonal

c/a
ratio

Unit cell
volume
(3)

Average
particle
size (m)

9.079
4.141
4.127
4.113
4.112

1.027
1.030
1.044
1.061

764.07
67.34
66.22
63.87
61.74

0.8
1.0
0.8
1.3
0.5

Lattice parameters ()
a
6.497

b
12.953
4.033
4.006
3.940
3.875

Summary
The Zr4+ and Ti4+ ions have a strong influence on the structural phase, but do not directly affect
the microstructure of PBZT powders. In addition as the Ti contents, increased the calcination
temperatures was reduced.
Acknowledgments
This work was financially supported by the Thailand Research Fund (TRF), Commission on Higher
Equcation (CHE) and Faculty of Science, Naresuan University. Thank are also to Science Lab
Center, Faculty of Science, Naresuan University for supporting facilities. Acknowledgement to Mr.
Don Hindle, for help correcting the manuscript.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

G. Shirane and S. Hoshino: Acta Crystallogr. Vol. 7 (1954), p. 203.


G. Shirane: Phys. Rev. Vol. 86 (1952), p. 219.
T. Bongkarn and G. Rujijanagul: Curr Appl. Phys. Vol. 6 (2006), p. 319.
N. Vittayakorn, T. Bongkarn and G. Rujijanagul: Physica B. Vol. 387 (2007), p. 415.
T. Bongkarn and P. Panya: J. Mater. Eng. Perform, (inpress).
J. S. Wright and LF. Francis, J. Mater. Res. 8 (1993), p. 1712.
J. Fang, J. Wang, L. M. Gan and S. C. Ng: Mater. Lett. Vol. 52 (2002), p. 304.
R. H. Perry and D. Green, Perrys: Chemical Engineers Handbook (McGraw Hill, Tokyo,
1984).
[9] C. Gomez-Yanez, C. Benite and H. Balmori-Ramirez: Ceram. Inter. Vol. 26 (2000), p. 271.
[10] Powder Diffraction File no. 35-0739, International Centre for Diffraction Data, Newton
Square, PA, 2000.
[11] Powder Diffraction File no. 06-0452, International Centre for Diffraction Data, Newton
Square, PA, 2000.

Advanced Materials Research Vols. 55-57 (2008) pp 205-208


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.205

Effect of Calcination Temperatures on Microstructure and Phase


Formation of Ba(Zr0.25Ti0.75)O3 Powders
T. Bongkarn1,a*, N. Phungjitt2,b and N. Vittayakorn3,c
1

Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, Thailand

Department of Physics, Faculty of Science, Uttaradit Rajabhat University, Uttaradit, Thailand

Department of Chemistry, Faculty of Science, King Mongkuts Institute of Technology Ladkrabang,


Bangkok,Thailand
a

reseachcmu@yahoo.com, bnalinee_amp@hotmail.com, cnaratipcmu@yahoo.com

Keywords: Barium zirconate titanate, Microstructure, Phase formation, Solid state


reaction
Abstract. In this work, the effect of calcination temperatures on the microstructure and phase
formation of Ba(Zr0.25Ti0.75)O3 (BZT) powders were investigated. The BZT powders were prepared
via the solid state reaction method under various calcination temperatures. It was found that the
second phases such as BaCO3, ZrO2, BaZrO3 and Ba2ZrO4 existed in samples with calcination
temperature below 1200 oC. Homogeneity and a highly pure perovskite phase of the BZT powders
were obtained with calcination condition at 1300 oC for 4 h. Lattice parameter a and the percentage
of cubic perovskite phase tended to increase with increasing calcination temperatures. The TG-DTA
results corresponded to the XRD investigation. The microstructures of calcined powders exhibited
an almost-spherical morphology and had a porous agglomerated form in all samples. The average
particle sizes were increased from 0.2 to 1.1 m when calcination temperatures were increased from
800 to 1350 oC.
Introduction
Barium titanate (BaTiO3; BT) is well known as a fundamental ferroelectric perovskite oxide and is
often used in multilayer ceramic capacitors (MLCs) due to its high dielectric constant [1,2]. BaTiO3
displays dielectric anomalies at 130, 0, and -90 oC with respective transformations in symmetry
from cubic to tetragonal, from tetragonal to orthorhombic, and from orthorhombic to rhombohedral.
Those anomalies are accompanied by a high dielectric constant near the phase transition [3].
Barium zirconate titanate Ba(ZrxTi1-x)O3 is obtained by substituting ions at the B site of BaTiO3
with Zr ions. This substitution results were in a decrease of the temperature and a broadening of the
permittivity maximum [4-6]. At a Zr/Ti ratio greater than 0.10, the three dielectric constant peaks
coalesce into a single broad maximum [7]. Moreover, the transition temperature of BZT shifts to a
lower temperature region with the increase of the Zr content. The dielectric study of the [Ba(ZrxTi1x)O3] ceramics with x=0.20 and 0.25 showed a normal ferroelectric with weak diffuse phase
transition behaviors [8]. The diffuse phase transition and a relaxor-like behavior were found at
higher Zr contents (x=0.30 and 0.35). The high tunability and the value of figure of merit (FOM) of
the [Ba(ZrxTi1-x)O3] with x=0.25 ceramic measured at room temperature under the biasing field 20
kV/cm are 58% and 135, respectively [8,9]. This makes [Ba(ZrxTi1-x)O3] ceramic a promising
material for tunable capacitor applications. Successfully, [Ba(ZrxTi1-x)O3] ceramics were prepared
via sol-gel process and mixed oxide method [8,9]. However, the detail of calcined temperatures
affected crystal structure and morphology evolution of [Ba(ZrxTi1-x)O3] powders, which synthesis
by solid state reaction method have been reported yet. Therefore, in the present work, the effect of
calcination temperatures on microstructure and the phase formation of [Ba(Ti0.75Zr0.25)O3; BZT]
powders prepared via a solid state reaction method was studied.

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Experimental
The starting materials were commercially available barium carbonate; BaCO3 (99%), titanium (IV)
oxide; TiO2 (99%) and zirconium (IV) oxide; ZrO2 (99%). Barium zirconate titanate
[Ba(Zr0.25Ti0.75)O3, BZT] powder was synthesized by the solid state reaction of thoroughly ground
mixtures of BaCO3, TiO2 and ZrO2 powders that were by a ball milling procedure (zirconia milling
media under ethanol for 24 h). Drying was carried out at 120 oC for 4 h. After sieving, various
calcination temperatures, ranging from 800 to 1350 oC, with a dwell time of 4 h and a heating
/cooling rate of 5 oC/min, were performed. The reaction of the uncalcined BZT powders taking
place during heat treatment were investigated by thermogravimetric and differential thermal
analysis (TG-DTA) using a heating rate of 10 oC/min from room temperature up to 1350 oC.
Calcined powders were subsequently examined at room temperature by X-ray diffraction (XRD;
Philip PW3040/60 X Pert Pro) to identify the phase formed and the optimum calcination
temperature of BZT powders. Powder morphologies and particle sizes were directly imaged, using
scanning electron microscopy (SEM; LEO 1455 VP).
Results and discussion
The TG-DTA curves recorded at a heating rate of 10
o
C/min in air for an equimolar mixture in the
stoichiometric proportion of BZT is displayed in Fig.
1. The TG curve shows two distinct weight losses. The
first weight loss occurs around 780 oC and the second
one above 1190 oC. The sample shows a small
exothermic peak in the DTA curve ~107 oC. This DTA
peak can be attributed to the vaporization of water. No
anomaly was observed from the TG pattern at this
temperature. This may indicate that the small amount
of vaporization of water could not be detected by the
TG measurement. The first weight loss is attributed to
the transition from witherite orthorhombic BaCO3 to
the rhombohedral phase [10]. In the second fall of
Figure 1. The DTA-TGA curve for the
specimen weight, a solid state reaction between
mixture of BZT powders.
BaCO3, TiO2 and ZrO2 was observed. The broad
endothermic characteristic of the DTA curve showed
that these chemicals reacted most strongly at a minimum peak of 914 oC. Moreover, another
endothermic peak with a minimum at 1270 oC was also observed in this profile. These data were
used to define the range of optimum calcination temperatures from 800 to 1350 oC.
To further study the phase development with increased calcination temperatures in the powders,
they were calcined for 4 h in normal air at various temperatures up to 1350 oC, followed by phase
analysis using XRD. XRD patterns of the BZT powders formed with different calcinations
temperatures are given in Fig. 2. After calcination at 800 oC, the crystalline phase of BZT was
accompanied with BaCO3 and ZrO2 as separate phases, whose X-ray peak matched with the JCPDS
file number 41-0373 and 24-1165. As the temperature increased to 1000 oC, the peaks
corresponding to the raw materials disappeared, while the intensity of the BaZrO3, BaTiO3 and
Ba2ZrO4 peaks become minor phases, which can correlate with JCPDS file number 41-0726 and 240130, respectively. After calcination at 1250 oC, the peaks corresponding to BaZrO3 and Ba2ZrO4
were not detectable, whereas the BaTiO3 phase remained. Evidently, a single phase of BZT is
formed by calcination at 1300 oC. This observation agrees well with those derived from the TGDTA results.
The strong reflections in the majority of the XRD patterns indicate the formation of the BZT
perovskite phase, which can be matched with the JCPDS file number 36-0019. To a first
approximation, this phase has a cubic perovskite type structure in the space group Pm-3m (no.221)

Advanced Materials Research Vols. 55-57

207

with a cell parameter a = 4.0520 . The lattice parameter a as a function of calcination


temperatures of this study is shown in Fig. 3. The lattice parameter was increased with the
increasing of calcinations temperatures. This indicated that the calcination temperatures have a
direct significance on lattice parameter and unit cell volume. The relative amount of perovskite and
impurity phases were determined by measuring the major XRD peak intensities of the perovskite
and impurity phases. Fig. 4 shows the percentage of the BZT perovskite phase as a function of
calcination temperatures. The percentage of the BZT perovskite phase was increased with
increasing calcination temperatures. The calcined powders, ranging from 800 to 1250 oC, were not
achieved 100% of the time. The single phase of perovskite of the calcined samples at higher
temperatures than 1300 oC is formed.

SEM photographs of BZT powders calcined at 1000 and 1300 oC are shown in Fig. 5. These
powders exhibited an almost spherical morphology and have a porous agglomerated form. As the
temperatures increased, more agglomerate particles could be observed. The average particle size
tended to increase as calcination temperatures increased. The average particle size was 0.2, 0.3, 0.6,
0.8, 0.9 and 1.1 m for the powders calcined at 800, 1000, 1200, 1250, 1300 and
1350 oC, respectively.

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(a)

(b)

Figure 5. SEM photomicrographs of BZT powders calcined at (a) 1000 oC and (b) 1300 oC.

Summary
It has been shown that the pure perovskite phase of Ba(Ti0.75Zr0.25)O3 powders can be formed
through the reaction of barium carbonate, titanium (IV) oxide and zirconium (IV) oxide with
calcined temperatures at 1300 oC. Evidence of the formations of minor phases of BaZrO3, BaTiO3
and Ba2ZrO4, which coexists with the perovskite phase, is found at calcinations temperatures
ranging from 1000-1250 oC. The calcination temperatures have a strong influence on the crystal
structure, homogeneity and the unit cell volume of the calcined powders. The resulting
microstructure of the BZT powders were more agglomerated as the calcination temperatures
increased.
Acknowledgments
This work was supported financially by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), and Naresuan University. Thanks also to the Uttaradit Rajabphat University and
King Mongkuts Institute of technology, Ladkrabang (KMITL) for supporting facilities.
Acknowledgement is also given to Mr. Don Hindle, for his helpful comments and correction of the
manuscript.
References
[1]
[2]
[3]
[4]
[5]
[6]

W.S. Clabaugh, R. Swiggard and R.Gilchrist: J. Res. Nat. Bur. Stds. Vol. 56 (1956), p. 289.
Y. Sakabe, K. Minai and K.Wakino: Jpn. J. Appl. Phys. Suppl. Vol. 20 (1981), p.147.
B. Jaffe, J. Cook and H. Jaffe: Piezoelectric Ceramics (Academic Press, London, U.K., 1997).
E. J. Brajer: U.S. Patent 2, 708, 243. (1955).
F. Kulscar: U.S. Patent 2, 735, 024. (1956).
W. Ulrich, G. Georg B. Ulrich, W. Sophie, H. Detlev and W. Rainer: J. Am. Ceram. Soc. Vol.
84 (2001), p. 759.
[7] D. Hennings, A. Schnell and G. Simon: J. Am. Ceram. Soc. Vol. 65 (1982), p. 539.
[8] X.G. Tang, K.H. Chew and H.L.W. Chan: Acta Mater. Vol. 52 (2004) , p. 5177.
[9] R. Liang, X. Dong, Y. Chen, F. Cao and Y. Wang: Ceram. Int. Vol. 33 (2007), p. 957.
[10] A. S. Seveyrat, A. Hajjaji, Y. Emziane, B. Guiffard and D. Guyomar: Ceram. Int. Vol 35
(2007), p. 35.

Advanced Materials Research Vols. 55-57 (2008) pp 209-212


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.209

Fabrication of Lead Barium Titanate Ceramics via Conventional


Solid-State Mixed Oxide Technique
T. Bongkarna* and P. Panyab
Department of Physics, Faculty of Science, Naresuan University, Phitsanulok, 65000, Thailand
a

researchcmu@yahoo.com, bnothingll@hotmail.com

Keywords: Phase Formation, Morphology, Tetragonality, Calcination

Abstract. (Pb0.925Ba0.075)TiO3 (PBT) ceramics have been prepared using a mixed oxide technique.
The phase formation and morphology were studied in detail via X-ray diffraction (XRD) and
scanning electron microscopy (SEM). The pure tetragonal perovskite structure was discovered with
calcination temperatures above 800 oC. The percentage of perovskite phase and particle size tends
to increase with the increasing of calcination temperatures. The PBT ceramics sintered at various
temperatures belonged to a pure tetragonal perovskite phase. The average grain sizes increased from
0.90 to 6.44 m with the increase of sintering temperatures from 1100 to 1200 oC. The highest
density was obtained from the sample that sintered at 1150 and 1200 oC.
Introduction
Lead titanate or PT, one of the important compounds in the family of perovskite ferroelectrics, are
very attractive for high frequency and high temperature applications such as SAW (Surface
Acoustic Wave) devices and piezoelectric transducers, owning to their high Curie temperature (Tc
490 oC) and low dielectric constant of about 200 [1-3]. At room temperature, a PT ceramic has a
tetragonal structure and belongs to the space group P4mm (Z=1). According to the published data,
the unit cell parameters a and c for PT range from 3.895 to 3.94 and from 4.063 to 4.171 ,
respectively. Correspondingly, the ratio c/a varies from 1.0312 to 1.0709 [4-6].
The PT ceramics prepared by conventional technique are too fragile to be sintered as dense
material. However, modified dense PT ceramics were obtained by substituting lead with a small
amount of dopant, such as Ca2+, Ba2+, Sr2+, Nd3+ and La3+. The lattice anisotropy is reduced, making
it possible to produce hard, dense ceramics with a high mechanical strength [7, 8].
Much of the work concerning the (Pb1-xBax)TiO3 (PBT) compound has been directed toward
determining the phase formation and microstructure [9,10]. Xing et al. [9] reported that the structure
of (Pb0.5Ba0.5)TiO3 prepared by a solid-state reaction is tetragonal and Arya et al. [10] showed that
the average grain size of (Pb0.25Ba0.75)TiO3 fabricated via a polymeric citrate precursor route
occurred around 54 nm. However, the effects of firing the temperatures for the preparation of
(Pb0.925Ba0.075)TiO3 are not clear. Consequently, in this work, we reported how the fabrication of
(Pb0.925Ba0.075)TiO3, was affected by firing conditions.
Experimental
Samples were synthesized via a mixed oxide technique at high temperatures. The raw materials
were commercially available lead (II) oxide (PbO), barium carbonate (BaCO3) and titanium (IV)
oxide (TiO2). Stoichiometric quantities were weighed to form PBT. The mixed powders were
milled in ethyl alcohol with zirconia balls for 24 h. After the slurry was dried and pulverized the
powder was calcined with calcination temperatures ranging from 400 to 900 oC. The calcined
powder was calcinated at 800 oC, was pressed into pellets. The pellets were then sintered in a
covered alumina crucible at temperatures ranging from 1100 to 1225 oC for 2 h. The calcined
powders and sintered ceramics were analyzed by X-ray diffraction (XRD) to check the reflections
of the phases. Microstructures were investigated via a scanning electron microscope (SEM). The
density of the sintered pellets was measured by the Archimedes method.

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Results and Discussion


The XRD patterns of PBT powders calcined at 400-800 oC for 4 h are shown in Fig. 1. For the
powders calcined at below 800 oC, X-ray peaks of precursors and impurities, TiO, TiO2, BaCO3,
PbO and PbO2, appeared, while the high purity of the tetragonal perovskite phase was discovered in
powders calcined above 800 oC, which could
be matched with JCPDS file numbers 060452 [11]. A solid-state reaction between
PbO, BaCO3 and TiO2 was obtained above
800 oC. Table 1 shows the dependence of the
cell parameters on the calcination
temperatures. It was found that the c axis
decreased, and the a axis increased, while
the
unit
cell
volume
stabilized,
approximately 62.2 3, with an increase of
calcination temperature. The c/a ratio
contracted with a rising temperature
signifying the decrease in the tetragonal
distortion. There was also evidence that Badoped in PT could reduce the c/a ratio from
1.064 to around 1.059.
Figure 1. XRD patterns of PBT powders calcined for
4 h at various temperatures: () TiO, (+) TiO2,
(*) BaCO3, () PbO2 and () PbO.
The percentage of the perovskite phase can be estimated by the following equations

I perov
%perovskite phase =
I perov + I PbO + I BaCO + I TiO + I PbO + I TiO
2
2
3

100

Where I perov , I PbO , I BaCO3 , I TiO2 , I PbO2 and ITiO are the intensities of the (101) perovskite peak, and PbO,
BaCO3, TiO2, PbO2 and TiO, represent all impurities. The percent perovskite phase of PBT
compounds were calculated and are listed in Table 1. The purity of the perovskite phase rose with
the increasing of temperature. 100% of the perovskite phase was found above 800 oC.

(a)

(b)

Figure 2. SEM micrographs of the PBT powders calcined at: (a) 700 oC and (b) 900 oC, for 4 h.

Advanced Materials Research Vols. 55-57

211

The SEM images of the PBT powders calcined at 1100 oC and 1225 oC for 4 h are illustrated in Fig.
2. It reveals that the particle size of PBT powders is increased as the calcination temperatures
increased. In general, the particles are highly agglomerated and basically irregular in shape, with a
substantial variation in particle size. The average particle size was discovered to be approximately
0.14, 0.20, 0.25, 0.33, 0.44, 0.59 and 0.65 m for the samples calcined at 600, 700, 750, 800, 850
and 900 oC for 4 h. The results indicate that the averaged particle size and degree of agglomeration
tend to increase with increasing temperature as expected.
The XRD patterns of PBT ceramics sintered at various sintering temperatures (1100-1225 oC)
for 2 h dwell time are demonstrated in Fig. 3. From the patterns, a single perovskite tetragonal
phase PBT could be obtained by the conventional solid-state mixed oxide technique. This indicates
that the conventional solid-state mixed oxide technique is a simple and effective method to produce
PBT ceramics. The maximum value of
density can be discovered in ceramics
sintered at 1150 and 1200 oC. This proved
that high-density PBT ceramics could be
produce by conventional solid-state mixed
oxide technique.
The SEM photographs of as-fried PBT
ceramics sintered at 1100 and 1200 oC for 2
h are shown in Fig. 4. Porous pellets were
formed at 1100 oC and the pores
disappeared above 1150 oC. Grain size
expanded with the increase of sintering
temperature as expected. The mean grain
size was discovered to be about 0.90, 3.05,
6.44 and 5.71 m for the samples sintered
at 1100, 1150, 1200 and 1225 oC for 2 h.
Figure 3. XRD patterns of PBT ceramics sintered for
2 h at various temperatures.

(a)

(b)

Figure 4. SEM micrographs of the PBT ceramics sintered at: (a) 1100 oC and (b) 1200 oC, for 2 h.

Summary
Perovskite (Pb0.925Ba0.075)TiO3 powders and ceramics could be gained successfully by a
conventional solid-state mixed oxide technique. The c/a ratio of powders reduced when calcination
temperatures increased. The 100% of the perovskite tetragonal phase was discovered at calcination
temperatures above 800 oC. The particle size tends to spherical agglomerate and leads to expansion
with rising temperatures. The resulting (Pb0.925Ba0.075)TiO3 ceramics consist of a variety of

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agglomerated grain sizes, depending on the sintering temperatures. The sintering temperatures have
a strong influence on the density of the sintered ceramics.
Table 1. The percentage of perovskite phase, lattice parameter (a, c), unit cell volume and c/a ratio
of PBT powders calcined at various temperatures
Calcination
Temperatures
(oC)
400
600
700
750
800
850
900

% perovskite
phase (%)
8.39
93.16
95.12
96.90
100.00
100.00
100.00

Lattice Parameter ()
c

4.115
4.114
4.111
4.110
4.108
4.108

3.887
3.887
3.888
3.891
3.891
3.894

Unit cell
volume
(3)
62.2
62.2
62.1
62.2
62.2
62.3

c/a ratio
1.509
1.058
1.057
1.056
1.056
1.055

Acknowledgments
This work was financially supported by the Thailand Research Fun (TRF), Commission on Higher
Education (CHE) and the Science Lab Center, Faculty of Science, Naresuan University for
supporting facilities. Thanks also to Mr. Don Hindle for his help in editing this manuscript.

References
[1]
[2]
[3]
[4]
[5]

S. Ikegami, I. Udea and T. Nagata: J. Acoust. Soc. Am. Vol. 50 (1971), p. 1060.
T. Takahashi: Ceram. Bull. Vol. 69 (1990), p 691.
T.Y. Chen and S.Y. Chu: J. Eur. Ceram. Soc. Vol. 23 (2003), p. 2171.
S.A. Mabud and A.M. Glazer: J. Appl. Crystallogr. Vol. 12 (1979), p. 49.
M. Kupriyanov, D. Kovtun, A. Zakharov, G. Kushlyan, S. Yagunov, R. Kolesova and K.
Abdulvakhidov: Phase Transit. Vol. 64 (1998), p. 145.
[6] J. Joseph, T.M. Vimala, V, Sivasubramanian and V.R.K. Murthy: J. Mater. Sci. Vol. 35
(2000), p. 1571.
[7] J. Shenglin, Z. Xuli, W. Xiaozhen and W. Xianghong: Piezoelect. Acoust. Vol. 17 (1995), p.
26.
[8] I. Ueda and S. Ikegami: Jap. J. Appl. Phys. Vol. 7 (1968), p. 236.
[9] X. Xing, J. Deng, Z. Zhu and G. Lui: J. Alloy. Comp. Vol. 353 (2003), p. 1.
[10] P.R. Arya, P. Jha, G.N. Subbanna and A.K. Ganguli: Mater. Res. Bull. Vol. 38 (2003), p. 617.
[11] Powder Diffraction File No. 06-0452, International Center for Diffraction Data, Newton
Square, PA, 2003.

Advanced Materials Research Vols. 55-57 (2008) pp 213-216


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.213

Fabrication of Barium Zirconium Titanate Ceramics Using


Ultrasonic Ball Milling Technique
W. Thamjaree, W. Nhuapeng* and T. Tunkasiri
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
*nhuapeng@yahoo.com
Keywords: BZT, milling time, ultrasonic ball milling

Abstract. In this work, barium zirconium titanate (BZT) ceramics were fabricated by using a
ultrasonic ball milling technique. BZT with the ratio of BaCO3:ZrO2:TiO2 was 1:0.05:0.95 was
mixed in ultrasonic ball milling for 1, 3 and 4.5 hr and calcined at temperature of 1000 C. Phase
formation of BZT powder was investigated using XRD technique. Moreover, physical and
electrical properties were examined. It was found that the tetragonal structure of BZT can be
observed. Particle size of sample powder obtained from new milling technique is smaller than that
of powder obtained from conventional mixed oxide method. Moreover, this new technique also
requires the less time fabrication. Furthermore, the dielectric properties are increased with milling
time and sintering temperature.
Introduction
In the past, innovations in many applications for example, actuators, sensors, hydrophones and
ultrasonic transducers have been the driving force for new developments in piezoelectric ceramics
[1]. Leadcontaining materials including mainly lead zirconate titanate (PZT) and lead-based
perovskite compositions have been the mainstay for high performance applications due to their
excellent dielectric, piezoelectric and electromechanical coupling coefficients [1,2]. However, from
the sustainable development point of view, the toxicity of lead oxide and its high vapor pressure
during materials processing may bring serious problems and the growing of concerning on health
and safety worldwide have drawn the attention owing to the need for environmental protection
[2,3]. In recent years, lead-free ferroelectric and piezoelectric materials have received much
attention to produce the electronic products to protect the environment and human health.
Therefore, it is necessary and urgent to develop lead-free materials with excellent properties for
replacing the lead-based materials. One of the most important and promising lead-free materials is
barium titanate (BT) and its solid solutions for example, barium zirconium titanate (BZT) [4].
Normally, the fine, high purity and uniform BT and its solid solution powder which is advantages in
many engineering applications can be synthesized by such chemical methods for example, sol-gel,
co-precipitation, hydrothermal, the poly vinyl alcohol evaporation route, spray dry technique and
spray pyrolysis technique,..etc [5]. However, the chemical synthesis is not suitable for mass
production due to low yield and high cost of powder. Therefore, the solid-state reaction process
using oxides as the starting materials are more favorite to prepare BT and its solid solution powder
because this technique is very simple, low cost and can be prepared for mass product [6].
Unfortunately, the conventional method requires a high calcinations temperature to synthesize the
designed BT compound, making the fabrication of BT ceramics very complicated and timeconsuming [7]. Therefore, in this work the authors attempt to prepare the BZT powder by using
ultra-ball milling technique. The effect of time on formation and morphology of powder was
studied. Furthermore, the physical and electrical properties of samples were also examined.

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Experimental
BZT with the mole ratio of BaCO3:ZrO2:TiO2 was 1:0.05:0.95 was prepared via the ultrasonic ballmilling technique (Figure 1). BaCO3 (99%, Fluka), ZrO2 (99%, Fluka) and TiO2, (99%, Reidel)
were employed as precursors. The starting powders were weighed according to appropriate molar
fractions, mixed and wet milled (in ethanol) for different time (1, 3 and 4.5 hr) in the zirconia
grinding media. The mixtures were dried, calcined in closed alumina crucible at temperature of
1000 -1250 C for 2 hr with heating and cooling rate of 3 C/min. Moreover, the calcined powder
was sieved and sintered in closed alumina crucible at temperature of 1300 C and 1350 C for 2 hr
with heating and cooling rate of 3 C/min., respectively. An X-ray diffractometer (XRD, Philips)
and a scanning electron microscope (SEM, Philips XL 30 ESEM) were employed to study phase
evolution and microstructure of the samples, respectively.

Figture 1. Fabrication of BZT powder using the ultrasonic ball-milling technique.


Results and Discussion
The phase identification of calcined and sintered BZT ceramics were conducted by X-ray
diffraction (XRD) technique. Figure 2 show the XRD pattern of BZT powder which milled for 4.5
hr and calcined as different temperature. From Fig. 2, the series of peak can be matched with the
JCPDS file no. 83-1880. It can be seen that the uncompleted perovskite-like BZT phase was found
in powder with a milling time of 1 hr and the single BZT phase was obtained from a milling time of
3 hr and 4.5 hr (Figure 3). It can be seen that the ultrasonic ball-milling technique take the less time
consuming when compare with the conventional method which normally take 24 hr for milling
time. This may be due to that the ultrasonic processing may promote the ability of grinding,
breaking down the agglomeration of powder. Next, effect of milling on particle size of BZT
powder was examined by particle size analyzer (Mastersizer S ver 2.19, Malven Instrument, Ltd.) as
show in Table 1. It can be seen that average particle size of uncalcine powder and calcined powder
are in the range of 0.83-0.16 m and 0.72-0.22 m, respectively. Besides, it is also found that there
is a significantly change in size of particle with the further milling time of ultrasonic ball mill.
Table 2 exhibits the density, dielectric properties and Curie temperature of BZT ceramics. It can be
found that density and dielectric constant of BZT ceramics is increasing with the milling time which
effect from the decreasing of particle size when the milling time is increased. The optimum values
of density and dielectric constant (77.67% and 1555) obtain from ceramics sintered at 1350 C with
the milling time of 4.5 hr. It has been observed that density of samples is not extremely high which
may be due to its sintering behavior of the oxide mixture which shows the volumetric expansion
[7]. Moreover, there is a significantly change in Curie temperature of BZT ceramics sintered at
1350 C which may be due to the density of sample and the Zr concentration from the media. The
relationship between dielectric constant of BZT ceramics and temperature is shown in Figure 4.

Advanced Materials Research Vols. 55-57

215

(101)

(211)

(210)

(200)

(001)

(111)

(101)

The normal curve of dielectric shows that higher dielectric constant values obtain from ceramics
which sintered higher temperature.

(211)

(210)

(200)

(111)

1200 C

(001)

1250 C

1150 C

4.5 hr

1100 C
1050 C

3 hr

1000 C
1 hr

uncalcine

2 (degree)

2 (degree)

Figure 2. XRD pattern of BZT powder


Milled for of 4.5 hr and calcined
different temperatures.

Figure 3. XRD pattern of BZT powder


calcined at 1000 C which mixed for
different of milling times.

Dielectric constant

1 hr/1300 C
3 hr/1300 C
4.5 hr/1300 C
1 hr/1350 C
3 hr/1350 C
4.5 hr/1350 C

Temperature (C)

Figure 4. Relationship between dielectric constant of BZT ceramics and temperature.

(a)
Figure 5. SEM micrographs of BZT samples sintered at 1350 C (a) as received surface and (b)
fracture surface.

(b)

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Table 1. Average particle size of uncalcine and calcined BZT powders


Milling Time (hr)
1
3
4.5

Mean diameter (m)


Uncalcine powder
Calcined at 1000 C
0.83
0.72
0.18
0.23
0.16
0.22

Table 2. Density, dielectric properties and Curie temperature of BZT ceramics


Sintering
Temperature
(oC)

1300

1350

Milling Time
(hr)

Density
(%)

1
3
4.5
1
3
4.5

67.62
71.69
73.08
74.72
75.16
77.67

866
970
1308
1128
1193
1555

Frequency
(1 kHz)
tan

0.38
0.35
0.60
0.19
0.13
0.25

Curie
Temperature
(C)

130
130
129
123
126
134

The SEM micrographs of as receive surface and fracture surface of BZT ceramics sintered at 1350
C are shown in Figure 5. There is many pores appear in the bulk which may be due to the effect of
low density of the samples. However, this problem can be improved by using higher sintering
temperature. The time employed in the ball milled method has the effect on the porosity in the bulk
(not show here). The grains agglomerate in irregular shape. Furthermore, the average grain size of
sintered ceramics is about 1.2 m. Therefore, it could be concluded that the ultrasonic ball milling
technique could produce fine powder but consuming less milling time when compared to the
conventional technique.
Summary
It can be concluded that homogeneous and fine powder can be obtained by using the ultrasonic ballmilling technique which could be fabricated in mass product and low cost. The most significant
change occurs in the size of the particles. Moreover, the ultrasonic ball-milling technique results in
smaller particle size and less milling time than the powder processed via the conventional ball
milling method.
Acknowledgement
The authors would like to express their sincere thanks to the Thailand Research Fund (TRF) and
Department of Physics, Faculty of Science, Chiang Mai University for supporting this research.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

T.R. Shrout and S.J. Zhang: J. Electroceram Vol. 19 (2007), p. 111.


J. Wu, D. Xiao, Y. Wang, J. Zu and P. Yu: J. Appl. Phys. Vol. 103 (2008), p. 1.
H. Yan, D. Xiao, P. Yu, J. Zhu, D. Lin and G. Li: Mats Design Vol. 26 (2005), p. 474.
Z. Yu, R. Guo and A.S. Bhalla: Mats. Lett. Vol. 57 (2002), p. 349.
J. Lappalainen and V.Lantto: App. Surf. Sci. Vol. 154-155 (2000), p. 118.
Shirane, K. Suziki and A. Takeda: J. Phys. Soc. Jpn. Vol. 7 (1952), p. 12.
L.B. Kong, J. Ma, H.T. Huang, W. Zhu and O.K. Tan: Mater. Lett. Vol. 50 (2001), p. 129.

Advanced Materials Research Vols. 55-57 (2008) pp 217-220


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.217

Ferroelectric and Mechanical Properties


of PZT-PZN-PNN Ceramics
S. Nabunmee, N. Vittayakorn, D. P. Cann and G. Rujijanagul*
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
*rujijanagul@yahoo.com

Keywords: Dielectric permittivity, Phase transition, PZT-PZN-PNN ceramics


Abstract. Ceramics in the system 0.05(Pb(Zn1/3Nb2/3)O3-0.15Pb(Ni1/3Nb2/3)O3-0.8Pb(Zr1/2Ti1/2)O3
(0.05PZN-0.15PNN-0.8PZT) were synthesized via the columbite method. Ferroelectric properties
of the samples prepared by different sintering conditions were investigated. The mechanical
property of the ceramics was also determined. The best ferroelectric properties were observed for
the sample sintered at 1250C.
Introduction
In the last decade, normal ferroelectric such as lead zirconate titanate [PbZr1xTixO3, PZT] has
become an important commercially produced piezoelectric materials.[1-3] Excellent piezoelectric
properties of PZT have been observed in compositions close to the morphotropic phase
boundary(MPB Zr:Ti ,52:48). [1-3] Locating the MPB for the ferroelectric materials is very
important for making the phase diagram and for obtaining excellent electrical properties. Therefore,
most commercial PZT and other ferroelectric ceramics are thus designed in the vicinity of the MPB
with various dopings in order to achieve high properties.
Lead-based relaxor perovskites, such as Pb(Zn1/3Nb2/3)O3 (PZN) and Pb(Ni1/3Nb2/3)O3 (PNN),
having the general formula Pb(BB)O3 have received significant attention since the 1970s because
of their peculiar dielectric and piezoelectric behavior. These materials have been applied in many
areas such as electrostrictive actuators, transducers, and multilayer ceramic capacitors. [4-9]
Recently, binary or ternary systems containing a combination of relaxor ferroelectrics with
rhombohedral symmetry and normal ferroelectric tetragonal symmetry near the MPB have attracted
particular attention owing to their high dielectric and piezoelectric properties. The excellent
electrical properties can be applied to many areas such as multilayer ceramic capacitors,
electrostrictive transducers, sensors, and actuators. [10-12] In the present work, solid solution of
0.05PZN-0.15PNN-0.8PZT ternary system was synthesized via a columbite method. Various
sintering temperature were carried out, to find out the optimum processing condition.
Experimental
The ternary system of 0.05PZN-0.15PNN-0.8PZT was synthesized by a columbite method. The
wolframite precursor ZrTiO4 was formed by reaction between ZrO2 with TiO2 at 1400 C for 4 h.
The columbite precursor ZnNb2O6 was prepared from the reaction between ZnO and Nb2O5 at
975 C for 4 h. The precursors ZrTiO4, ZnNb2O6 were then mixed with PbO (99.9%) according to
the stoichiometric ratio for the desired compositions with 2 mol% excess PbO added. The mixed
powders were calcined at temperatures ranging, 900C at a dwell time of 2 h in a double crucible
configuration with a heating rate of 20 C/min. The calcined powders were isostatically cold
pressed into pellets at a pressure of 100 MPa. Sintering occurred between 1100 and 1350 C with a
dwell time of 2 h at 500C with heating rate 1C/min and 2 h at 1250C with heating rate 5C/min.
The perovskite phase was examined by x-ray diffraction (XRD). The density of the sintered
samples was measured by Archimedes method with distilled water as the fluid medium. The
polarization-Electric field (P-E) property and mechanical property of the sintered samples were
measurement.

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Results and Discussion


The perovskite and pyrochlore phase formation at different sintering temperatures in 0.05PZN0.15PNN-0.8PZT ceramics were studied and analyzed by XRD.
o

1300 C

(Intensity)(a.u.)

1250 C

1200 C

20

30

40

50

60

70

2-theta

Figure 1. XRD patterns at room temperature of 0.05PZN-0.15PNN-0.8PZT ceramics.


Fig. 1 illustrates XRD patterns from this system. The pyrochlore-type structure was found in the
sample sintered at 1200 and 1300C, as indicated by . In the other hand, pure peroskite was
observed for the 1250 C sintered sample. The formation of pyrochlore phase may be due to
reaction between PbO and the columbite precursors or due to lead lose at high temperature.

Density(g/cm )

7.85

7.80

7.75

7.70

7.65

1200

1250

1300
o

Sintering temperature( c)

Figure 2. Density as a function of sintering temperature of 0.05PZN-0.15PNN-0.8PZT ceramics.

Fig. 2 shows the typical sintered densities of 0.05PZN-0.15PNN-0.8PZT ceramics for various
sintering temperature. Although the pure perovskite phase was found at 1250C, the density of the
sample was observed to decrease with increasing sintering temperature. The decreasing in density
may be due to the PbO evaporation at high temperature.

Advanced Materials Research Vols. 55-57

219

50
o

1250 c

40

1300 c
o
1200 c

Polarization(C/cm )

30
20
10
0
-10
-20
-30
-40
-50

-20

-10

10

20

Electric Field(KV/cm)

Figure 3. Polarization vs. electrical field for 0.05PZN-0.15PNN-0.8PZT ceramics.


The result of polarization-field (P-E) measurements for the ceramics sintered at various
temperatures is shown in Fig. 3. All samples showed normal ferroelectric behavior with a
rectangular loop. High polarization was observed for all samples. The optimum ferroelectric with
higher remanent polarization (Pr) of 40 C/cm2 was observed for the sample sintered at 1250C, as
expected. The lower remanent polarization in other sintering conditions may due to the formation of
pyrochlore phase in the samples which made the ceramics have lower ferroelectric behavior.
However, coercive field (Ec) was ~ 7.2 kV/cm for all sintering conditions.
6.8

Hardness(GPa)

6.6

6.4

6.2

6.0

5.8
1200

1250

1300
o

Temperature( c)

Figure 4. The 1250C sintered sample displayed a higher hardness than the other samples.

The results of hardness measurements are shown in Fig. 4. The higher hardness value was 6.7 GPa.
In the present work, the grain size of the system was found to increase with increasing the sintering
temperature. Therefore, the existent of pyrochlore phase may result in the lower mechanical
property of the samples.

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Summary
In this work, 0.05PZN-0.15PNN-0.8PZT ceramics were synthesized via a columbite method. The
sintering temperature of 1250C was selected as the optimum sintering condition for preparation of
the 0.05PZN-0.15PNN-0.8PZT ceramics. Pyrochlore phase was found to effect on the ferroelectric
and mechanical properties of the ceramics.
Acknowledgements
This work was supported by The Thailand Research Fund (TRF), National Metal and Materials
Technology Center (MTEC), Faculty of Science and Graduate School Chiang Mai University, and
Commission on Higher Education (CHE) Thailand. The authors would like to thank Prof. Dr.
Tawee Tunkasiri for his help in many facilities.
References
[1]
[2]

K. Uchino: Ferroelectric Devices (Marcel Dekker, New York, 2000).


A. J. Moulson and J. M. Herbert : Electroceramics Materials Properties and Applications
(Chapman and Hall, New York, 1990).
[3] K. Uchino: Solid State Ionics Vol. 108 (1998), p. 43.
[4] L.E. Cross: Ferroelectrics Vol.76 (1987), p. 241.
[5] T.R. Shrout and A. Halliyal: Journal of American Ceramics Society Bull. (1987).
[7] K. Uchino: Ferroelectrics Vol.151 (1994), p. 321.
[8] K. Uchino: Solid State Ionics Vol.108 (1998), p. 43.
[9] K. Uchino: Piezoelectric Actuators and Ultrasonic Motors (Kluwer Academic Publishers,
Boston, MA, 1996).
[10] N. Vittayakorn, C. Puchmark, G. Rujijanagul, X. Tan, and D. P. Cann: J. Appl. Phys. Vol.6
(2006), p. 303.
[11] N. Vittayakorn, G. Rujijanagul, X. Tan, M. A. Marquardt, and D. P. Cann: J. Appl. Phys. Vol.
96 (2004), p. 5103.
[12] S. Nabunmee, G. Rujijanagul, N. Vittayakorn, D. P. Cann: J. Appl. Phys. Vol.102 (2007), p.
094108.

Advanced Materials Research Vols. 55-57 (2008) pp 221-224


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.221

Antiferroelectric Lead Zirconate Ceramics with Nanoparticle Alumina


Additions
C. Puchmark1,a, S. J. Milne2,b and G. Rujijanagul3,c*
1

Department of Physics, Faculty of Science, Naresuan University, Phitsanulok 65000, Thailand


2

Institute for Materials Research, University of Leeds, Leeds, LS2 9JT, UK

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
a

kungmic2002@yahoo.com, bcer6sjm@leeds.ac.uk, c*rujijanagul@yahoo.com

Keywords: Antiferroelectric, Phase transitions, Lead zirconate

Abstract. The effects of alumina nanoparticles on the properties of PbZrO3 ceramics were
investigated. The samples were prepared by a simple conventional mixed oxide method involving
calcination and sintering temperatures of 800 oC and 1200 oC, respectively. Single-phase lead
zirconate was observed in X-ray powder diffraction patterns for all the samples. The relationship
between the Al2O3 content, the dielectric properties and Knoop hardness were determined. The results
indicate that the additive affects Curie temperatures and the shape of the Curie peak, implying a
chemical reaction takes place with the matrix during high-temperature processing. Hardness values
increase for additions up to 1 vol % Al2O3.
Introduction
PbZrO3 (PZ) has an antiferroelectric phase (AFE) which exhibits an orthorhombic structure at room
temperature. An anti-pararell shift of Pb ions along the [110] a direction is the origin of the
antiferoelectricity [1-4]. A paraelectric phase (PE) of PZ occurs at the temperature above Tc 236 oC.
A sharp permittivity peak with relative permittivity around 4000 at 1 kHz is observed at this
temperature [1]. It was reported that there exists an intermediate ferroelectric phase (FE) over a very
narrow temperature range (5 oC) below the Tc [3]. The temperature range over which the FE phase is
stable can be extended by application of an electric field or by chemical substitution, such as Ba2+ on
the Pb2+ sites to form (Pb1-xBax)ZrO3 solid solutions [5-13]. The AFEFE phase transition produces a
large volume expansion. This makes the material potentially useful for high displacement
electromechanical actuator applications [14]. It was reported that the mechanical properties of
structural ceramics can be improved by the addition of second phase nanoparticles such as SiC and
Al2O3 [15]. The term nanocomposites was used for such materials. In recent years, some
consideration has been given to the ferroelectric properties of the nanocomposites. However, there is
little information available on the properties of nanocomposites of antiferroelectric materials, such
as PbZr2O3. In the present work, we prepared PZ/Al2O3 composites by a simple solid-state method.
The effect of Al2O3 nanoparticles on the dielectric behaviour and mechanical hardness are present.
Experimental
Monolithic PZ and PZ/Al2O3 nanocomposites were prepared by a simple solid-state mixed oxide
method. The starting powders of PbO, ZrO2 and TiO2 were mixed in isopropanol using zirconia balls
as the grinding media. The mixed powders were calcined at 800 oC for 3 h. In order to study the effect
of Al2O3 (0.5, 1, 3 vol% Al2O3) on the properties of PZ, an Al2O3 powder, with average primary
particle size 40 nm, was blended with the calcined PZ powder, and 1% PVA binder added. The mixed
powders were uniaxially pressed into pellets at a pressure of 100 MPa. The PVA binder was burnt out
at 550 oC using a heating rate of 1 oC /min. Finally, the pellets were sintered at 1200 oC for 2 h with a
heating rate of 5 oC /min. In order to minimize the loss of lead due to vaporization, a PbO atmosphere

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was maintained during sintering using PZ as the spacer powder. X-ray diffraction analysis (XRD) was
used to identify phase formation of calcined powders and sintered samples. Relative
permittivity-temperature measurements were carried out using an impedance analyzer in conjunction
with a non-inductively wound tube furnace. The effect of Al2O3 nanopowder on the mechanical
properties of the ceramics was studied by using a Knoop microhardness tester. Indentations were applied
on the polished surfaces of PZ ceramics.
Results and Discussion
XRD patterns of the monolithic PZ and PZ/Al2O3 nanocomposite ceramics are shown in Fig. 1. Only
PZ phase was found for all samples. The analysis was carried out based on the basis of Joint
Committee on Powder Diffraction Standard (JCPDS) data [16]. No trace of the Al2O3 phase was
detected.

Figure 1. XRD patterns of monolithic PZ and PZ/Al2O3 nonocomposite sintered at 1200 oC


Plots of relative permittivity versus temperature are shown in Fig. 2. The trend of the relative
permittivity at the Tc was found to increase from 4900 for pure PZ to 6100 for the 0.5 vol% Al2O3
sample and 5800 for 1 vol% Al2O3, but decreased to 4800 for the 3 vol% Al2O3 sample.

Figure 2. Relative permittivity, r (at 1 kHz) vs. temperature for samples of differing Al2O3 content
sintered at 1200 oC.

Advanced Materials Research Vols. 55-57

223

The variation of the Tc with Al2O3 content is shown in Fig. 3. The Tc of the monolithic sample (i.e.
without Al2O3) was 239 oC, but it decreased to 233 oC for the nanocomposite samples. Furthermore,
the permittivity curves of the PZ/Al2O3 samples exhibited a broad shoulder below the Curie
temperature, which suggests a change in the antiferroelectric to ferroelectric phase transition. The
data suggests that a reaction occurs between the additive and matrix during processing, and that Al ion
doping of PbZrO3 may be responsible for the changes in dielectric properties [17].

Figure 3. Plot of Tc vs.volume fraction of Al2O3 nanoparticles.


The results of Knoop hardness measurements are shown in Fig. 4. The PZ/Al2O3 nanocomposites
displayed 28% higher hardness than the monolithic PZT. The maximum value of hardness of 3.1 GPa
was found for the samples containing 1 vol% Al2O3. This value is close to the value reported by
Tajima et al., in PZT [18, 19]. The improved mechanical properties in PZT were proposed to be due to
Al2O3 nanoparticles reinforcing the grain boundaries and acting as effective pins against microcrack
propagation [18, 19]. It can be pointed out here that the hardness of the PZ samples could be improved
at only some concentrations of nanoparticle additions, up to 1 vol%. The slight decrease in hardness
on moving from 1 to 3 vol% Al2O3 may be due to the higher porosity of the PZ containing 3 vol %
Al2O3.

Figure 4. Knoop hardness and porosity vs. volume fraction of Al2O3 nanoparticles.

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Summary
Dielectric and mechanical property measurements of PbZrO3/Al2O3 nanocomposites were
investigated. Dielectric results infer a chemical reaction between the additive and matrix occurs
during ceramic processing. There was a marked increase in peak permittivity, from 4900 for pure PZ,
to ~6100 for 0.5 vol% Al2O3. All PbZrO3/Al2O3 samples exhibited a 6 C reduction in Curie
temperature relative to PbZrO3. A low-temperature shoulder to the Curie peak appeared in the
modified samples which imply that chemical reaction with the matrix also affects the
antiferroelectrifc-ferroelectric phase transition. The optimum hardness of the nanocomposites was
found for the sample with 1 vol% Al2O3 addition.
Acknowledgments
This work was supported by The Thailand Research Fund (TRF), Commission on Higher Education
(CHE) and Faculty of Science Naresuan University. The authors would like to thank Prof. Dr. Tawee
Tunkasiri for his help in many facilities.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

G. Shirane, E. Sawaguchi and Y. Takagi: Phys. Rev. Vol.84 (1951), p. 476.


R.W. Whatmore and A.M. Glazer: J. Phys. C: Solid State Phys. Vol.12 (1979), p. 1505.
S. Teslic and T. Egami: Acta Crystallogr. B Vol.54 (1998), p. 750.
X. Dai, J. Li and D. Viehland: Phys. Rev. B Vol.51 (1995), p. 2651.
G. Shirane: Phys. Rev. Vol.86 (1952), p. 219.
G. Shirane and S. Hoshino: Acta Crystallogr. Vol.7 (1954), p. 203.
I.H. Ismailzade and O.A. Samedov: Phys. Statatus Solidi A Vol.90 (1985), p. 445.
Z. Ujma, J. Handerek, M. Pawelczyk and D. Dmytrow: Ferroelectrics Vol.129 (1992), p. 127.
K.H. Yoon and S.C. Hwang: J. Mater. Sci. Vol.32 (1997), p. 17.
B.P. Pokharel, M.K. Datta and D. Pandey: J. Mater. Sci. Vol.34 (1999), p. 691.
B.P. Pokharel and D. Pandey: J. Appl. Phys. Vol.86 (1999), p. 3327.
B.P. Pokharel and D. Pandey: J. Appl. Phys. Vol.88 (2000), p. 5364.
B.P. Pokharel and D. Pandey: J. Appl. Phys. Vol.90 (2001), p. 2985.
E.E. Oren, E. Taspinar and A.C. Tas: J. Am. Ceram. Soc. Vol.80 (1997), p. 2714.
M. Sternitzke: J. Eur. Ceram. Soc. Vol.17 (1997), p 1061.
Powder Diffraction File, Card No.35-0739. Joint Committee on Powder Diffraction Standards
(JCPDS) PDF-4, Internation Centre for Diffraction Data (ICDD), (2000).
[17] C. Puchmark, S. Jiansirisomboon, G. Rujijanagul, T. Comyn, J.Y. He and S. J. Milne: Materials
Research Bulletin Vol.42 (2007), p. 1269.
[18] K. Tajima, H. Hwang, M. Sando and K. Niihara, J. Eur. Ceram. Soc. Vol.19 (1999), p. 1179.
[19] K. Tajima, H. Hwang, M. Sando and K. Niihara: J. Ceram. Soc. Jpn. Vol.108 (2000), p. 607.

Advanced Materials Research Vols. 55-57 (2008) pp 225-228


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.225

Morphotropic Phase Boundary of Lead-Free Piezoelectric Ceramics


from BNT- KN System
N. Pisitpipathsina,1, W. Koontasingb,1, S. Eitssayeamc,1, U. Intathad,2,
G. Rujijanagule,1, K. Pengpatf,1 and T. Tunkasirig,1
1

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50202, Thailand
2

School of Science, Mae Fah Luang University, Chiang Rai 57100, Thailand

bom_sep@hotmail.com, bfon_worralak@hotmail.com, csukum99@yahoo.com,


d
i_uraiwan@yahoo.com, ekpengpat@gmail.com, frujijanagul@yahoo.com and
g
tawee@chiangmai.ac.th

Keywords: BNT, KN, Lead -free piezoelectric ceramic, Two-step mixed oxide method

Abstract. In this research work, the investigation of the morphotropic phase boundary, physical
properties and electrical properties of lead- free piezoelectric materials of bismuth sodium titanium
oxide: (Bi0.5Na0.5)TiO3 (BNT) and potassium niobium oxide : KNbO3 (KN) in the ceramic system
of (1-x)BNT- xKN where x= 0.00, 0.03, 0.05, 0.08, 0.10 and 0.15 by modified mixed oxide method
was carried out. The BNT and KN powders were prepared separately using calcination technique
with optimum calcination temperature for producing both BNT and KN powders of about 800C.
XRD results revealed that the BNT-KN ceramics with low KN content of x less than 0.05 contain
ferroelectric perovskite phase with rhombohedral symmetries while the higher KN content ceramics
have mixed symmetries between rhombohedral and orthorhombic. From the evidences including
phases, microstructures and dielectric data of the BNT-KN ceramics, it may be assumed that the
morphotropic phase boundary may be at around the composition of x = 0.05.
Introduction
Lead-free piezoelectric ceramics have recently attracted interest among most scientists in the field
of electroceramics because of the control-free atmosphere and pollution-free sintering process.
Among piezoelectric materials, (Bi0.5Na0.5)TiO3(BNT) and KNbO3(KN) are of interest and have
perovskite structures. The BNT crystal was first discovered by Smolensky et al. [1], having crystal
structure of rhombohedral at room temperature. The first phase transition occurs at 200oC (Tp)
where the ferroelectric rhombohedral changes to antiferroelectric tetragonal phase [2-4]. Potassium
niobate, KNbO3 (KN), has an orthorhombic symmetry at room temperature. Moreover KN has low
dielectric constants and high electromechanical coupling factors which could be obtained over a
wide compositional range [5]. The study of bismuth sodium titanate (BNT)-based solid solution
with KN were reported by Pengpat et. al.[6], who studied the wide composition range of up to 50
mol% KN. However, there was no report on the morphotropic phase boundary from their work.
In this research work, the narrow region of (1-x)BNT - xKN where x = 0.00, 0.03, 0.05, 0.08,
0.10 and 0.15 was investigated by two-step mixed oxide method. The BNT and KN powders were
prepared separately using calcination method. X-ray diffraction (XRD) was used for phase
identification and scanning electron microscopy (SEM) was employed for microstructural study of
the prepared ceramics. The dielectric properties of the prepared ceramics were also measured.
Experimental
The conventional ceramic fabrication technique was used to prepare BNT-KN ceramics of
composition (1-x)(Bi0.5Na0.5)TiO3-xKNbO3 where x = 0.00, 0.03, 0.05, 0.08, 0.10 and 0.15.
Reagent-grade metal oxide or carbonate powders with 99%+ purity of Bi2O3, Na2CO3, TiO2,
K2CO3 and Nb2O5 were used as the starting raw materials. The batch composition of BNT and KN

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were weighed and mixed via ball-milling with acetone as a medium for 24 hours. Then both
mixture of BNT and KN were dried and calcined separately at 800C for two hours. The batch
compositions corresponding to the above formula were prepared and mixed using ball-milling
method with ethanol as a medium for 24 hours. After drying and sieving the mixtures, the powders
were made into pellets of 15 mm in diameter and about 1.7 mm in thickness. The pressed-disc
samples were sintered between 1050-1150C in an electric furnace and air atmosphere under
controlled heating/cooling rate of 3C /min with 2 hours dwell time. The phase identification of
prepared powders and the sintered ceramics were investigated using the X-ray diffraction technique.
The density of sintered ceramic sample was investigated using Archemedes method. The dielectric
constant at room temperature (r) of all ceramic samples was measured using an LCZ-meter (Model
4276A, Hewlett Packard).
Results and Discussion
The XRD patterns of the ceramics are shown in Fig. 1. It can be seen that all peaks in the XRD
pattern of the BNT (x = 0) ceramic correspond to the BNT phase of the JCPDS file No. 34-0360
with rhombohedral structure. The addition of KN phase at low content of about x = 0.03 affected
no change on structure of the ceramic, however, the XRD patterns of higher KN content reveal
noticeable change in crystal symmetries as can be clearly seen in Fig. 1(b) of extended XRD
patterns, where orthorhombic structures may start to superimposed into the rhombohedral structure,
indicating the mixing between two phases at this composition. This may be assumed that the x =
0.05 composition is a morphotropic phase boundary of this BNT-KN system.
(a)

(b)

Figure 1. XRD patterns of (1-x)BNT-xKN ceramics with 2 ranging from (a) 10 -60 and (b) 20-45.
In order to obtain highly dense ceramics for further investigation of both microstructures and
dielectric properties, the optimum sintering temperatures should be chosen carefully. Fig. 2 shows
the density of the BNT-KN ceramics sintered at different temperatures. It was found that the
optimum sintering temperature of these ceramics can lie between 1050 and 1075C, depending on
each composition. The dielectric constant of the dense ceramics was then measured and the result is
shown in Fig. 3. It is clearly seen that the addition of KN content enhances the dielectric constant of
the ceramics as well as suppresses their dielectric loss. The dielectric constant was found to increase
up to the composition of x = 0.05 and then drop down and then increase again where the amount of
KN is increased to x = 0.15. This may be implied that orthorhombic structure starts to occur at the
composition of x = 0.05.
The SEM micrographs of these BNT-KN ceramics (Fig. 4) reveals the evidence of structural
change at x = 0.08, as the morphology of grains changed from equiaxed to rectangular shape,
indicating the existence of orthorhombic KN. This agrees pretty well with the XRD and dielectric

Advanced Materials Research Vols. 55-57

227

results. At this point, the obtained data may help to assume the morphotropic phase boundary of
BNT-KN system which should be existed at x = 0.05. However, the increase in dielectric constant
at higher content of KN (x = 0.15) may be another evidence of some structural change, however, the
difficulty occurs where the XRD results showed no change in the XRD pattern of this composition
comparing with that of lower KN content. However, the SEM micrographs of this x = 0.15 sample
contain rectangular grains with the size smaller than that of lower KN content (x = 0.08), which
may cause the enhance in dielectric constant of this ceramic.

Figure 2. Density of BNT- KN ceramics as a function of sintering temperature.

Figure 3. Dielectric constant (r) and loss (tan ) at room temperature and 1 kHz of the BNT-KN
ceramics as a function of KN content.

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B!T

x = 0.05

x = 0.08

x = 0.15

Figure 4. SEM micrographs of the selected BNT-KN ceramics at their surfaces.


Summary
The two-step mixed oxide method was employed in order to prepare the ceramics from the BNTKN system. This method involves the separate calcination of pure BNT and KN powders at 800 C,
then mixed in various compositions (with x values between 0.0 and 0.15), pressed into pellets and
sintered to form dense ceramics. The results show that the sintering temperatures for obtaining
maximum densities of the ceramics are in a range of 1050 to 1075 and at higher temperature the
density starts dropping as a result of porosity. It was found that the addition of KN enhances the
dielectric properties of the (1-x)BNT-xKN ceramics. The morphotropic phase boundary is assumed
to be at the composition of 5 mol% KN by consideration of the data from XRD, microstructures and
dielectric properties. This may be useful in future development of the lead-free materials for
electronic applications.
Acknowledgment
The authors would like to thank the Thailand Research Fund, National Metal and Materials
Technology Center (MTEC), and Faculty of Science, Chiang Mai University for financial support.
References
[1]
[2]
[3]
[4]
[5]
[6]

G.A. Smolenskii, V.A. Isupov, A.I. Agranovskaya, N.N. Kraink: Sov. Phys.Solid State. Vol. 2
(1961), p. 2651.
K. Sakata and Y. Masuda: Ferroelectrics. Vol. 95 (1974), p. 347.
T. Takenaka, K. Maruyama, and K. Sakata: Jpn. J. Appl. Phys. Vol. 30 (1991), p. 2246.
T. Takenaka, H. Nagata: Applications of Ferroelectrics, 1998. ISAF 98. Proceedings of the
Eleventh IEEE International Symposium on 24-27 Aug., (1998), p. 559.
T. Wada, K. Toyoike, Y. Imanaka and Y. Matsuo: Jpn. J. Appl. Phys. Vol. 40 (2001), p. 5703.
K. Pengpat, P. Jarupoom, P. Kantha, S. Eitssayeam, U. Intatha, G. Rujijanagul and T.
Tunkasiri: Curr. Appl. Phys. Vol. 8 (2008), p. 241.

Advanced Materials Research Vols. 55-57 (2008) pp 229-232


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.229

Formation of NaNbO3 Crystals in Dielectric Glass and Glass-Ceramics


of a Na2O-Nb2O5-Al2O3-SiO2 System
S. Thongsaeng1, A. Niyompan1, a, R. Tipakontitikul1, b, and K. Pengpat 2
1

Department of Physics, Faculty of Science, Ubon Ratchathani University, Ubon Ratchathani 34190,
Thailand
2

Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50202, Thailand
a

scanusni@ubu.ac.th, rungnapa@rocketmail.com

Keywords: Sodium niobate, dielectric glass, heat treatment, transparent ferroelectric glassceramics

Abstract. Dielectric glass and glass-ceramics were derived from Na2O-Nb2O5-Al2O3-SiO2 system.
Small amount of TiO2 were also introduced into glass compositions to study crystallization
behavior of the glass with present of this nucleating agent. Conventional melt-quenching technique
was employed for a glass production and the selected bulk glass samples were subjected to the heattreatment process at appropriate temperature. After six different glass compositions were produced,
and by observation with necked eyes, all obtained glass samples are in light brown color and some
samples were opaque due to crystallization took place during quenching. Phase identification
through XRD patterns show that there were 3 phases, NaNbO3, NaNbO8 and a sodium aluminum
silicate compound, found in those opaque glass samples. NaNbO3 is a predominant phase in all
samples. Fortunately, clear transparent glass was obtained from the composition with no TiO2
addition. Heat treatment of this glass did not induce phase change, three aforementioned phases
still present. Increasing heat treatment time promoted a higher of observed intensity of NaNbO3.
But the NaNbO3 crystalline size was not significantly developed with time. The dielectric response
of the NaNbO3 crystals in the glass-ceramics samples are influenced by presence of other crystalline
phases.
Introduction
Crystals of alkali niobate compounds (LiNbO3, NaNbO3 or KNbO3) are important ferroelectric
materials for applications in optics and electronics because they have large electro-optics,
photorefractive and holographic effect [1]. Large intensive investigations in these particular
materials have resulted in development of many different techniques of alkali niobate preparation
and characterization schemes. Practically, nano-size alkali niobate crystals can be grown and
embedded in a glass matrix by the controlled glass crystallization process and the resulting
materials known as ferroelectric glass-ceramics [2]. In this case, growing crystal to a size lower
than that of visible light wavelength can be achieved if desired condition is applied and the
transparent ferroelectric glass-ceramic will be obtained [3]. The major potential applications of this
materials are in microwave, pyroelectric and piezoelectric devices. It has been also clear that
preparing dielectric materials with classical sintering method can give out a structural defect which
diminishes dielectric properties [4]. While, preparing materials in a glass-ceramics form as
proposed in this work can overcome such problem and it also give a material with a combination of
physical properties which are otherwise difficult to achieve from other preparation techniques. In
this work, dielectric glass-ceramics containing NaNbO3 crystals were derived from the Na2ONb2O5-Al2O3-SiO2 glass forming system. Small amount of TiO2 were also introduced into glass
compositions to study crystallization behavior with present of this nucleating agent. Heat treatment
duration is varied to observe the effect on crystalline size and concentration.

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Experimental
Batch mixtures of various compositions, detailed in Table 1, in amount of 30 g, were prepared from
reagent grade NaCO3, Nb2O5, SiO2 and Al2O3. Conventional melt-quenching technique was
employed for parent glass production. Batch mixtures were melted in an electrical furnace at
1450oC for 3 h. Glass melt were then quenched onto steel plate which was pre-heated at 300oC or
cooled by liquid nitrogen. The obtained glass samples were then subsequently annealed at
appropriate temperature to remove the internal stress. Only the transparent bulk glass sample noted
in Table 1, was subjected to the heat-treatment process at appropriate temperature. To observe
progress of crystal growth, the treatment time were varied from 0.2 to 2 h. Phase formation and
crystalline size were examined using XRD technique. Dielectric properties of the glass-ceramics
were studied using LRC meter.
Table 1. Glass batch compositions, given names, quenching conditions and result of observation
with necked eye.
Sample

Glass composition ( mol%)

Mold*

Appearance**

C
C
C

G-1
G-2

Na2O
21
21

Nb2O5
21
21

SiO2
53
53

Al2O3
5
5

TiO2
5
-

H
H

G-3
G-4

21
21

16
16

58
58

5
5

H
LN

G-5

21

16

58

LN

T
TL

G-6

21

16

58

LN

TL

* H = preheat mould at 300oC, LN = cooled with liquid nitrogen


** C = crystallize, T = Transparent and TL = Translucent
Results and Discussion
In order to determine the glass-forming region in the investigated system, batch mixtures of various
oxide compositions, as detailed in Table. 1, were prepared and obtained glasses were observed with
necked eye to classify glass into three characteristics, crystallized (C) transparent (T) and
translucent glass (TL). The results show that the preheated mould did not give a clear transparent
glass but rather it caused the melt crystallized to form crystallized glasses which were seen as
opaque bulk glasses. However, soaking the mould into a bath of liquid nitrogen led transparent
glass be able to form, glass G-4 was in this case. This was because glass compositions in the
present work contained a lower content of the network former which formed a very fluid forming
melt and the phase separation may also took place which could give rise to a rapid crystallization
during cooling. Similar observation was also reported in ref. [3]. Thus, a high cooling rate and high
temperature gradient are required for obtaining transparent glass in this particular system. Addition
of TiO2 into the compositions (G-5 and G-6) also shows the same effect but give slightly different
crystals characteristic. As observed with necked eye, these latter two glass samples seemed not to
show completely opaque. This confirms the fact that TiO2 content form nuclei which are ready to
induce devitrification to occur rapidly [5].
X-ray diffraction analysis (Fig.1(a)) revealed that the glass for all compositions contained three
crystalline phases, NaNbO3, NaNbO8 and a sodium alumino silicate compounds. NaNbO3 is a
predominant phase. Crystalline size calculation based on line broadening of the strongest peak of
NaNbO3 gave values of 354.00, 231.33, 293.00, 181.00, 221.00 and 270.33 nm for the G-1, G-2, G3, G-4, G-5 and G-6, respectively. The crystalline size values and phases concentration (determined

Advanced Materials Research Vols. 55-57

231

from relative peak intensity) of NaNbO3 are the key of transparency. As found in G-4, it contained
smallest NaNbO3 crystalline size and has higher NaNbO3 phase concentration compared to other
samples, as a result, the obtained G-4 exhibited as a transparent glass while other samples are
opaque due to larger crystalline size and higher concentration of the secondary phases.

(a)

G-6

G-5

(b)

Intensity (a.u.)

G-4

G-3

2h

1h

0.5 h

0.2 h

Intensity (a.u.)

G-2

20

30

40

G-1

50

2 (degree)

60

20

30

40
2 (degree)

parent glass G-4

50

60

Figure 1. XRD powder patterns of (a) glass samples, rapid crystallization lead to formation of three
crystalline phases and (b) heat treated glass samples at 700oC for various treatment times, the
pattern of parent glass G-4 is also shown. Three crystalline phases, NaNbO3 (), NaNbO8 () and
) are found in all samples.
sodium alumino silicate compound (
Parent glass G-4 was selected for crystallization study and subjected to heat treatment at
different times from 0.2 to 2.0 h. The XRD results in Fig. 1(b) suggest that phase transformation
was not occurred for NaNbO3 and others two secondary phases still be found. For increasing of
treatment time, there was no significant growth of the NaNbO3 crystal as the observed crystalline
sizes are just in range 181-188 nm for the glass-ceramics heat treated for approximately 0.2-2.0 h.
However, development of NaNbO3 phases concentration or volume fraction with increasing
treatment time is clearly seen from relative integrated peak intensity. Fig. 2 is the plot of Ix/(Ic1+Ic2)
as a function of treatment time, where Ix, Ic1 and Ic2 are integrated intensity of the strongest
diffracted peaks of NaNbO3, NaNbO8 and the sodium alumino silicate phases, respectively.
Increasing of NaNbO3 volume fraction to a certain level also reduced transparency of the glassceramics because it increased degree of heterogeneity [6]. Decolorization was also observed as the
sample was originally seen in light brown then it is visible as cloudy-like white (Fig. 3) after treated
for 2 h. This is consistent with formation of NaNbO3 at a higher degree as suggested by Graca et al
[7] coupled with development of other phases.
2.2
2.0

Ix/(Ic1+Ic2)

1.8
1.6
1.4
1.2
1.0
0.8
0.0

0.5

1.0

1.5

2.0

Treatment Time (h.)

Figure 2. Plot of NaNbO3 relative intensity


ratio as a function of heat treatment

Figure 3. Transparency of the parent glass G-4


and corresponding glass ceramics G-4/A-G-4/D
heat treated for 0.2 to 2.0 h.

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3200
2800

0.2 hr.
0.3 hr.
0.5 hr.
1.0 hr.
2.0 hr.

Dielectric constant

2400
2000
1600

Figure 4. Dielectric constant as a function of


temperature for glass-ceramics heat treated for
different period of times.

1200
800
400
0

50

100

150

200

250

300

350

Temperature ( C)

Fig. 4 show variation of dielectric constant versus temperature for glass-ceramic samples heat
treated at various times. It can be seen that dielectric respond of the NaNbO3 content for all samples
show the same tendency. The dielectric constant seemed to rise to a maximum point at somewhat
outside the temperature range performed in this work. At that point, orthorhombic-tetragonal phase
transition will be undergone. This observation is consistent with previous report [8] about transition
temperature of NaNbO3. Phase transition range reported for Na1-xLixNbO3 polycrystalline system is
also located at temperature range above 350oC [9]. At room temperature and at frequency 1 kHz,
there is no exact relationship between measured dielectric constants and volume fraction of
NaNbO3 as they are varied from 22.11 to 43.50, 35.95, 37.05 and 46.08 for samples treated at 0.2,
0.3, 0.5, 1.0 and 2 h, respectively. However, at higher temperature, this relationship is more
substantially important, as the higher dielectric constant is found in the glass-ceramics sample with
the higher volume fraction of NaNbO3 crystals.
Summary
The transparent ferroelectric glass-ceramics containing nano-size NaNbO3 crystals were
successfully prepared by controlling crystallization of the glass in the Na2O-Nb2O5-Al2O3-SiO2
system. Heat treatments were performed at temperature 700oC for various times. The results of
present study show that only NaNbO3 phase concentration increased with treatment time while their
crystalline size had no significant change. It should also be noted that NaNbO3 phase was not
crystallized alone but NaNbO8 and a phase of sodium alumino silicate compound were also found.
Dielectric measurement reveals that tetragonal-orthorhombic phase transition took place at
temperature above 350oC.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

M. Todorovi and Lj. Radonji: Ceram. Int. Vol. 23 (1997), p. 55.


Y. Hu and C.-L. Huang: J. Non-Cryst. Solids. Vol. 278 (2000), p. 170.
L. Radonji, M. Todorovi and J. Miladinovi: Mater. Chem. Phys. Vol. 88 (2004), p. 427.
S. Lanfredi, L. Dessemond and A.C. martins Rodrigues: J. Eur. Ceram. Soc. Vol. 20 (2000),
p. 983.
X. Guo, H. Yang, C. Han and F. Song: Thermochim. Acta Vol. 444 (2006), p. 201.
L. Radonji, M. Todorovi and J. Miladinovi: Mat. Sci. Eng. B-Solid Vol. 121 (2005), p. 64.
M.P.F. Graca, M.G. Ferreira da Silva, A.S.B. Sombra and M.A. Valente: Physica B Vol. 396
(2007), p. 62.
C.N.W. Darlington and K.S. Knight: Physica B Vol. 226 (1999), p. 368.
M.A.L. Nobre and S. Lanfredi: J. Phys. Chem. Solids Vol. 62 (2001), p. 1999.

Advanced Materials Research Vols. 55-57 (2008) pp 233-236


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.233

Ferroelectric and Dielectric Aging Effects of Fe3+/Nb5+ Hybrid-Doped


Barium Titanate Ceramics
S. Prasertpalichatr, M. Unruan, J. Tungsritrakul and R. Yimniruna
Department of Physics, Faculty of Science, ChiangMai University, Chiang Mai 50200, Thailand.
a

rattikornyimnirun@yahoo.com

Keywords : Ferroelectric Aging effect, Hybrid doping , Donor dopant , acceptor dopant

Abstract. It is well known that acceptor and donor doping results in opposite ferroelectric aging
effects; however, the aging effects in hybrid-doped (acceptor+donor) has remained unclear. Thus,
the aging effect of dielectric and ferroelectric properties in Fe3+/Nb5+ hybrid-doped BaTiO3
ceramics was investigated in this research. The concentration of acceptor dopant (Fe3+) was fixed
at 1 mol% while that of donor dopant (Nb5+) was varied from 0.5-2.0 mol%. XRD technique was
used to study the phase morphology. Before measuring dielectric and ferroelectric aging effect, all
samples were deaged at 250 C for 1 hour. The results showed that the dielectric properties of all
deaged samples have decreased exponentially with time. The deaged samples with 0.5 and 1.0
mol% of Nb5+ obviously showed double hysteresis loop while that with higher concentration of
Nb5+ (1.5-2.0 mol%) showed the rectangular (normal) hysteresis loop. The explanations based on
the effect of defect dipole were discussed.
Introduction
Due to its high permittivity and environmentally friendly applications, barium titanate has been
used widely during the last fifty years. Besides, by adding dopants, very interesting characteristics
for various applications such as capacitor, transducer and transmitter can be obtained as well.[1]
However, there is still some undesirable effect called aging effect ; the spontaneous change of
ferroelectric, dielectric and piezoelectric with time[2-5]. This results in opposite ferroelectric aging
effect between acceptor-doped ferroelectrics and donor-doped ferroelectrics. In other words,
hysteresis loop of acceptor-doped ferroelectric becomes an interesting double (constricted) loop
after aging while that of donor-doped ferroelectric remains normal (rectangular) shape. However,
the results of aging effect in hybrid-doped ferroelectrics has remained unclear and lead to many
interesting questions : what will happen in an aging effect when a ferroelectric is hybrid-doped?
Does donor doping cancel the aging effect of acceptor doping? [6]
Experimental
Ba(Ti0.99xFe0.01Nbx)O3 powder, x = 0.005-0.020 , was prepared by convention mixed-oxide. The
raw materials TiO2, BaCO3 , Fe2O3 and Nb2O5 were mixed by vibro-milled in ethyl alcohol for 1 h
and then dried by oven at 120 C. After drying, the powders were calcined at 1250C for 2 h [7].
The calcined powders were pressed into disk-shaped compacts by using uniaxial pressure of 0.5
tons/cm2 for 20 second. The pellets were heated at 500 C for 1 h in order to eliminate the PVA and
then followed by sintering at 1450 C for 2 h with a heating rate of 5 C/min. Phase identification
and microstructure of Ba(Ti0.99xFe0.01Nbx)O3 ceramics were performed by x-ray diffraction (XRD)
and SEM. Prior to aging, all samples were deaged by heating at 250 C for 1 h and then cooled to
the room temperature immediately. By using LCR meter, the dielectric aging was measured by
using frequency at 5,10,20 and 50 kHz. P-E hysteresis loop aging were measured by using
modified Sawyer-Tower circuits with electric field of 5 kV/cm.

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Results and Discussion


The XRD patterns of Ba(Ti0.99xFe0.01Nbx)O3 ceramics, x = 0.005-0.020 , are shown in Figure 1.
The results indicate that the peaks of all compositions correspond to the tetragonal barium titanate
peaks (JCPDS files number 89-1428).

Fig. 1 XRD patterns of Ba(Ti0.99xFe0.01Nbx)O3 ceramics, x = 0.005-0.020 compared with JCPDS


files number 89-1428
Figure 2 shows the changes of dielectric permittivity for the hybrid-doped samples with different
Nb concentrations (0.5, 1.0, 1.5 and 2.0 %mol). It is clearly evident that all hybrid-doped ceramics
shows the exponential decays of the dielectric permittivity with time. These observations indicate
that the dielectric aging effect exists in all hybrid-doped ceramics, whether the concentrations of
donor dopant (Nb) or acceptor dopant (Fe) dominates. Moreover, its obviously seen that the aging
effect decreased rapidly in the former and gradually decrease in the latter.

(a)

(b)

(c)

(d)

Fig. 2 Dielectric aging of Ba(Ti0.99xFe0.01Nbx)O3 ceramics when (a) x = 0.005 (b) x=0.010
(c) x=0.015 (d) x=0.020

Advanced Materials Research Vols. 55-57

235

Figure 3 shows the evolution of the P-E hysteresis loops for hybrid-doped Ba(Ti0.99xFe0.01Nbx)O3
ceramics , x = 0.005-0.020 samples where x=0.5, 1.0, 1.5, and 2.0. It can be clearly seen that the
pinched type hysteresis loops are observed for the compositions with 0.5% and 1.0% mol Nb, and
the polarization values also decreases with time. On the other hand, the P-E hysteresis loops of the
other compositions remain relatively the same. Therefore, it can be stated that strong ferroelectric
aging effect is only observed in the compositions with larger Fe concentrations.

(a)

(b)

(c)

(d)

Fig. 3 P-E hysterysis aging of Ba(Ti0.99xFe0.01Nbx)O3 ceramics when (a) x = 0.005 (b) x=0.010
(c) x=0.015 (d) x=0.020
To explain the aging effect in hybrid-doped BaTiO3, one needs to analyze its defect structure, as
aging is believed to be controlled by the migration of mobile oxygen vacancies. Since in this study
the concentration of acceptor dopant, Fe, was fixed at 1 %mol, the explanation has to be divided
into two limiting cases: first being the ceramics with lower donor Nb concentration of 0.5 % and
1% mol, and second being the ceramics with higher donor Nb concentration of 1.5 % and 2.0%
mol. It should first be mentioned that when for every two Fe3+ ions substitution in Ti4+, one oxygen
vacancy is likely to be created to neutralize the excess negative charges. On the other hand, A-site
vacancies (Ba2+) are created for the charge balance of every two Nb5+ substitution for Ti4+. Let us
now consider the controlling factor in each limiting case. With lower donor Nb concentration,
oxygen vacancies obtained from the substitution of Fe dopant form the defect-dipoles with other
charges which in turn create the built-in defect field. This built-in field makes the pinched P-E
loops, and causes the polarization switching more difficult, hence decrease in the polarization
values. On the other hand, for other compositions (1.5% mol and 2.0% mol), the hysteresis loop
remained the same due to the increasing of donor dopants (Nb). In this case with the donor Nb
concentration higher than the acceptor Fe dopant, the more A-site vacancies are created. The less
mobility of A-site vacancy results in less moveable domain walls, hence no pinched P-E loops are
observed. In the same way, the dielectric permittivity decreases with time due to the mobility of

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oxygen vacancies is decreased. Thus, the dielectric permittivity significantly decreases in the former
and gradually decreases in the latter.
Summary
In this research, the dielectric and ferroelectric aging effects in hybrid doped BaTiO3 ceramics were
investigated. The concentration of acceptor dopant (Fe3+) was fixed at 1 mol% while that of donor
dopant (Nb5+) was varied from 0.5-2.0 mol%. XRD technique was used to study the phase
morphology. The results showed that the dielectric properties of all deaged samples have decreased
exponentially with time. The deaged samples with 0.5 and 1.0 mol% of Nb5+ obviously showed
double hysteresis loop while that with higher concentration of Nb5+ (1.5-2.0 mol%) showed the
rectangular (normal) hysteresis loop.
In summary, this current study intuitively points out that only acceptor-dominant hybrid-doped
BT ceramics result in ferroelectric aging effect. It should be pointed out that in a previous
investigation on Mn-Nb-doped BT ceramics [6] the ferroelectric aging effect is still observed in
donor-dominant compositions. The explanation for this difference is still unknown, and requires
further investigations. However, this study shows the different controlling influence between
various acceptor dopants, i.e. Fe and Mn for this case.
Acknowledgments
This work was supported jointly by the Thailand Research Fund (TRF), Commission on Higher
Education (CHE), the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science
and Technology, Thailand, through its program of Center of Excellent Network, Graduate School
and Faculty of Science, Chiang Mai University. Thanks are also extended to Promotion of Science
and Technology Talent Project for undergraduate scholarship.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

B.D. Stojanovic, M.A. Zaghete, C.R. Foschini, F.O.S. Voeora, J.A. Varela: Ferroelectrics
Vol. 16 (2002), p. 270.
P. V. Lambeek and G. H. Jonker: J. Phys. Chem. Solids Vol 47 (1986), p. 453.
W. A. Schulze and K. Ogino: Ferroelectrics Vol. 87 (1988), p. 361.
U. Robels and G. Arlt: J. Appl. Phys. Vol. 73 (1993), p. 3454.
L. X. Zhang and X. Ren: Phys. Rev. B Vol. 73 (2006), p. 094121.
Wenfeng Liu, Wei Chen, Liu Yang, Lixue Zhang, Yu Wang, Chao Zhou, Shengtao Li, and
Xiaobing Ren: J. Appl. Phys. Vol. 89 (2006), p. 172908.
Abdelkafi, N. Abdelmoula , H. KhemaKhem, R. Von Der Muhll, and L. Bih: J. Alloy.
Compd. Vol. 427 (2007), p. 260.

Advanced Materials Research Vols. 55-57 (2008) pp 237-240


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.237

Effect of Calcination Conditions on Phase Formation and Characterization


of BiFeO3 Powders Synthesized By a Solid-State Reaction
C. Silawongsawat*,a, S. Chandaraka, T. Sareeina, A. Ngamjarurojanaa,
S. Maensirib, P. Laoratanakulc, S. Anantaa and R. Yimniruna
a

Department of Physics, Faculty of Science, Chiang Mai University, 50200, Thailand.

Department of Physics, Faculty of Science, Khon Kaen University, 40002, Thailand.

National Metal and Materials Technology Center (MTEC), Pathumthani 12120, Thailand
*pensila@gmail.com

Keywords: Bismuth ferrite; Crystal structure; Calcination; Phase formation; Powder synthesis

Abstract. A perovskite-type phase of Bismuth Ferrite, BiFeO3, powder was synthesized by a solidstate reaction via a rapid vibro-milling technique. The effect of calcination condition on the phase
formation, and characterization of BiFeO3 powder was investigated. The formation of the BiFeO3
phase investigated as a function of calcination conditions by TGDTA and XRD. Morphology,
particle size and chemical composition have been determined via a combination of SEM and EDX
techniques and vibrating sample magnetometer (VSM) were used to characterize the structures and
magnetic properties of prepared samples. The rapid vibro-milling is employed for the first time in
this work as a significant time-saving method to obtain single-phase BiFeO3 powders.
Introduction
Bismuth ferrite, one of the very few multiferroics with a simultaneous coexistence of ferroelectric
and antiferromagnetic order parameters in perovskite structure, has attracted much attention for
many decades since 1960. BiFeO3 (BFO) has a ferroelectric Curie temperature Tc of 850oC and an
antiferromagnetic Neel temperature of 370 oC [1,2]. However, potential applications of BFO in the
memory devices, sensors, satellite communications, optical filters and smart devices were greatly
limited due to its low insulation resistance caused by the reduction of Fe3+ species to Fe2+ and
oxygen vacancies for charge compensation [3,4]. It was hard to avoid generating impurity phases by
the conventional solid-state reaction in bulk materials. BFO perovskites could only stabilize within
a narrow ranged temperature.
In this work, BiFeO3 powder was synthesized by a solid-state reaction via a rapid vibro-milling
technique. The conventional mixed oxide synthetic route via a rapid vibro-milling has been
developed with a one-step reaction of all starting materials. The rapid vibro-milling is employed for
the first time in this work as a significant time-saving method to obtain highly-phase BiFeO3
powders.
Experimental
BiFeO3 powder was synthesized by the solid-state reaction of thoroughly ground mixtures of Bi2O3
and Fe2O3 powders that were milled in the required stoichiometric ratio. Instead of employing a
ball-milling procedure (ZrO2 media under acetone for 24 h), use was made of a McCrone vibromilling. In order to improve the reactivity of the constituents, the milling process was carried for 30
min. with corundum media in isopropyl alcohol (IPA). Although the use of IPA in place of acetone
was dictated by the use of the McCrone mill, an associated benefit is the avoidance of unpleasant
vapours associated with the use of acetone. Drying was carried out at 120C for 2h, prior to sieving
through a 100-m mesh. After sieving, various calcination conditions, i.e., temperatures ranging
from 600 to 900C, dwell times ranging from 2 to 12 h. with heating/cooling rates 5 C/min were
applied in order to investigate the formation of BiFO3. The reactions of the uncalcined BFO

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powders taking place during heat treatment were investigated by thermogravimetric and differential
thermal analysis (TG-DTA, Shimadzu), using a heating rate of 10 C/min in air from room
temperature up to 1100 C. Calcined powders were subsequently examined by room temperature Xray diffraction (XRD; Philips PW 1729 diffractometer), using Ni-filtered CuK radiation to identify
the phases formed and optimum calcination conditions for the manufacture of BFO powder. Powder
morphologies and particle sizes were directly imaged, using scanning electron microscopy (SEM;
JEOL JSM-840A). The chemical compositions of the phases formed were elucidated by an energydispersive X-ray (EDX) analyzer with an ultra-thin window. EDX spectra were quantified with the
virtual standard peaks supplied with the Oxford Instruments eXL software. The magnetic properties
of the calcined powders were examined at room temperature (293 K) using a vibrating sample
magnetometer (VSM) (VSM 7403, Lake Shore, USA).
Results and Discussion
The TG-DTA simultaneous analysis of a powder mixed in the stoichiometric proportions of Bi2O3
and Fe2O3 powders are shown in Fig. 1. The TG curve shows two distinct weight losses. In the
temperature range from room temperature to ~150 C, both large exothermic and endothermic
peaks are observed in the DTA curve in consistent with the first weight loss. These observations can
be attributed to the decomposition of the organic species from the milling process. Increasing the
temperature up to ~1000 C, the solid-state reaction occurred between Bi2O3 and Fe2O3. The broad
exotherm in the DTA curve represents that reaction, which has a maximum at ~600 C. This is
supported by a second peak in sample weight over the same temperature range. No further
significant weight loss was observed for the temperatures above 600C in the TG-curve, indicating
that the minimum firing temperature to get Bi2O3-Fe2O3 compounds is in good agreement with
XRD result (Fig. 2,3) and those of other workers. However, the DTA curve shows that there are
other peaks at ~800 and 850C. It is to be noted that there is no obvious interpretation of these
peaks. These data were used to define the range of temperatures for XRD investigation to between
600 and 850C.

Figure 1. TG-DTA curves for the mixture of Bi2O3- Fe2O3 powder.


Powder XRD patterns of the calcined BFO powders at different calcination temperatures are shown
in Fig. 2. The XRD results show that the pyrochlore phase Bi24FeO40 (JCPDS No.46-0416) is
dominant at the calcination temperature above 650C for the powders. It was decreased when
increasing calcined temperature. It can be noticed that in highly pure perovskite phase is formed
suddenly above 750C, in which more perovskite phase was found with increasing calcination
temperature. The difference could be attributed to nano-sized mixed powders obtained from a rapid
vibro-milling technique. Fig. 3 shows that the Bi24FeO40 phase (JCPDS No.46-0416) is dominant at
the various dwell time from 2-12 h. for the powders.

Advanced Materials Research Vols. 55-57

239

Figure 2. XRD patterns of BFO powder for various calcined temperature dwell times of 2h. with
heating/cooling rates of 5 C/min.

Figure 3. XRD patterns of BFO powder calcined at 850 C for various dwell times with
heating/cooling rates of 5 C/min.
The morphological changes in the BFO powders formed by a mixed oxide method are illustrated in
Fig. 4 In general, the particles are agglomerated and basically irregular in shape, with a substantial
variation in particle size. Generally, particle size of all compositions can be estimated from SEM
micrographs to be in range of 0.2-2 m.

calcined at 800 C 2h
calcined at 850 C 2h
calcined at 850 C 6h
Figure 4. SEM micrographs of BFO powders calcined at temperature
Fig. 5 shows the field dependence of specific magnetization (MH curve) of the different calcined
condition on BFO samples measured at 293 K. the observation of small remanent magnetization in

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air cooled samples could be attributed to a canted spin structure although BFO is known to be
antiferromagnetic having a G-type magnetic structure. As the XRD results suggested the phase
obtained was not BiFeO3 but a mixture of unreacted Fe2O3, possessing canted antiferromagnetic
structure and another unidentified phase showing a significant degree of ferromagnetic ordering[5].

Figure 5. Specific magnetizations of BFO powder for various calcined temperature as a function of
field, measured at 293 K.
Summary
In this study, an approach to synthesize highly pure-phase BiFeO3 powders by a solid-state reaction
via a rapid vibro-milling technique is instigated. The rapid vibro-milling is employed for the first
time in significant time-saving method. The effect of calcination condition on the phase formation,
and characterization of BiFeO3 powder was investigated. The potential of a vibro-milling technique
as a significant time-saving method to obtain highly pure-phase BiFeO3 is also discussed. The
results indicated that for 2h of 850oC calcination, with a heating/cooling rates of 10oC/min. the
highly pure-phase BiFeO3 powder can be obtained.
Acknowledgments
This work was supported by the Thailand Research Fund (TRF), Commission on Higher Education
(CHE) and National Synchrotron Research Center (NSRC), National Nanotechnology Center
(NANOTEC), NSTDA, Ministry of Science and Technology, Thailand, through its program of
Center of Excellent Network, Faculty of Science, Chiang Mai University. Thanks are also extended
to Young Scientist and Technologist Program of the National Science and Technology
Development Agency for undergraduate scholarship.
References
[1]
[2]
[3]
[4]
[5]

J.G. Ismilzade: Phys. Status Solidi (b) Vol. 46 (1971), p. K39.


G.A. Smolenskii and V.M. Yudin: Sov. Phys. JETP Vol. 16 (1963), p. 622.
Y.P. Wang, L. Zhou, M.F. Zhang, X.Y. Chen, J.M. Liu and Z.G. Liu: Appl. Phys. Lett. Vol.
84 (2004), p. 1731.
V.R. Palkar, R. Pinto and Pramana: J. Phys. Vol. 58 (2002), p. 1003.
A.Garg, H. K. Thota, B. Pandey, and H. C. Verma: Mater. Res. Soc. Symp. Proc. Vol. 997
(2007), p. 0997.

Advanced Materials Research Vols. 55-57 (2008) pp 241-244


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.241

Effect of Calcination Conditions on Phase Formation and Characterization


of BiFeO3-BaTiO3 Powders Synthesized By a Solid-State Reaction
S. Chandarak*,a , T. Sareeina, A. Ngamjarurojanaa, S. Maensiri b,
P. Laoratanakulc, S. Ananta a and R. Yimnirun a

Department of Physics, Faculty of Science, Chiang Mai University, 50200, Thailand.

Department of Physics, Faculty of Science, Khon Kaen University, 40002, Thailand.

National Metal and Materials Technology Center (MTEC), Pathumthani 12120, Thailand
Pinky_pure58@hotmail.com

Keywords: Bismuth ferrite; Barium titanate; Calcination; Phase formation; Powder synthesis

Abstract. A perovskite-type phase of solid solution of BiFeO3-BaTiO3 powders were synthesized


by a solid-state reaction via a rapid vibro-milling technique. The effect of calcination condition on
the phase formation, and characterization of BiFeO3-BaTiO3 powders were investigated. The
formation of the BiFeO3-BaTiO3 phase investigated as a function of calcination conditions by TG
DTA and XRD. Morphology, particle size and chemical composition have been determined via a
combination of SEM and EDX techniques and vibrating sample magnetometer (VSM) was used to
characterize the structures and magnetic properties of prepared samples. The rapid vibro-milling is
employed for the first time in this work as a significant time-saving method to obtain single-phase
BiFeO3-BaTiO3 powders.
Introduction
Bismuth ferrite, one of the very few multiferroics with a simultaneous coexistence of ferroelectric
and antiferromagnetic order parameters in perovskite structure, has attracted much attention for
many decades since 1960. BiFeO3 (BF) has a ferroelectric Curie temperature Tc of 850oC and an
antiferromagnetic Neel temperature of 370 oC [1,2]. However, potential applications of BFO in the
memory devices, sensors, satellite communications, optical filters and smart devices were greatly
limited due to its low insulation resistance caused by the reduction of Fe3+ species to Fe2+ and
oxygen vacancies for charge compensation [3,4]. It was hard to avoid generating impurity phases by
the conventional solid-state reaction in bulk materials. The addition of other perovskite materials,
such as lead titanate (PbTiO3) has been found to be effective in stabilizing BF in the perovskite
structure.
The present work is aimed at synthesizing pyrochlore-free bismuth ferrite-barium titanate
powders. The conventional mixed oxide synthetic route via a rapid vibro-milling has been
developed with a one-step reaction of all starting materials. The rapid vibro-milling is employed for
the first time in this work as a significant time-saving method to obtain single-phase BF-BT.
Experimental
Regent grade oxides of Bi2O3, Fe2O3, BaCO3 and TiO2 were used as starting materials. BF-BT
powders were synthesized by the solid-state reaction of these raw materials. Ground mixtures of
the powders were required with stoichiometric ratios for the general composition (1-x)BiFeO3 xBaTiO3 where x = 0.1, 0.2, 0.3, 0.4, and 0.5. A McCrone vibro-milling technique was employed in
order to combine mixing capacity with a significant time saving. The milling operation was carried
out in isopropanal. High purity corundum cylindrical media were used as the milling media. After
vibro-milling for 30 minutes and drying at 120oC, the reaction of the uncalcined powders taking
place during heat treatment was investigated by themogravimetric and differential thermal analysis
(TG-DTA, Shimadzu) in air from room temperature up to 1300oC. Based on the TG-DTA results,
the mixture was calcined at temperatures between 650 to 950oC for 2 hours in alumina crucible to

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examine the phase formation behavior of BF-BT powders. A heating/cooling rate of 5oC/min was
selected for all of the compositions in this system. Calcined powders were subsequently examined
by room temperature X-ray diffraction (XRD; Siemens-D500 diffractrometer) using Ni-filtered
CuK radiation to identify the phases formed for the BF-BT powders. The relative amounts of
perovskite and pyrochlore phases were approximated by calculating the ratio of the major XRD
peak intensities of the perovskite and pyrochlore phases via the following equation:

I perov
(1)
Perovskite % =
100
I
perov + I pyro
where Iperov and Ipyro, refer to the intensity of the (110) perovskite peak and (222) pyrochlore peak,
respectively. Powder morphologies and particle sizes were directly imaged using scanning electron
microscopy (SEM; JEOL JSM-840A). EDX spectra were quantified with the virtual standards
peaks supplied with the Oxford Instruments eXL software. The magnetic properties of the calcined
powders were examined at room temperature (293 K) using a vibrating sample magnetometer
(VSM) (VSM 7403, Lake Shore, USA). Diagram of experimental procedure is shown in Fig. 1.

Figure 1 Diagram of experimental procedure.

Results and Discussion


TG-DTA curves obtained for powders mixed in the stoichiometric proportions of BF and BT
powders are displayed in Fig. 2. In the temperature range 50200oC, the sample shows several large
exothermic peaks in the DTA curve. These DTA peaks can be attributed to the decomposition of the
organic species from the milling process. The different temperature, intensities, and shapes of the
thermal peaks probably are related to the different natures of the organic species and, consequently,
caused by the removal of species differently bounded in the network. In the temperature range 650
1050oC, both exothermic and endothermic peaks are observed in the DTA curve. The DTA curve
shows that the endothermic peak centered at ~800oC may result from perovskite phase
crystallization, and the last exothermic peak centered at ~ 850oC may be caused by the
decomposition of bismuth oxide. Above 1000oC, TG curve indicates that higher weight loss of
substance occurs. This TG result implies the upper limit of the calcination temperature for the
mixed powders. Therefore, these temperatures are used to define the ranges of calcination
temperatures (650 to 950oC) used in subsequent powder processing steps.
Powder XRD patterns of the calcined 0.7BF-0.3BT powders at different calcination
temperatures are shown in Fig. 3. The XRD results show that the pyrochlore phase Bi4Ti3O12
(JCPDS No.80-2143) is dominant at the calcination temperature below 750C for the powders. The
precursor phases Bi2O3, Fe2O3, BaCO3 and TiO2 are also detected in the powders by XRD when
calcined below 700oC. Other compositions also show a similar trend.

Advanced Materials Research Vols. 55-57

243

Figure 2. TG-DTA curves for the mixture of Bi2O3- Fe2O3- BaO TiO2 powders.

Figure 3. XRD patterns of 0.7BF-0.3BT


powders for various calcined temperature.

Figure 4. XRD patterns of xBF-(1-x)BT powder


calcined at optimum conditions

As listed in Table 1, all the compositions in the present work exhibit pyrochlore-free XRD scans at
calcination temperatures above 950C. It can be noticed that in most compositions the perovskite
phase is formed more perovskite phase with increasing calcination temperature. The difference
could be attributed to nano-sized mixed powders obtained from a rapid vibro-milling technique. The
perovskite phase formation behavior for (1-x)BF - xBT powders at the calcination temperature of
950C is shown in Fig. 4. The percentage of perovskite phase in BF-BT powders is summarized in
Table 1 as a function of calcination temperature. These experimental results indicate that when the
concentration of the BT phase increases the calcination temperature must be increased to obtain
phase-pure perovskite BF-BT powders. More importantly, this study suggests that the conventional
mixed oxide method helps to stabilize the perovskite phase and the calcination temperature can be
futher reduced by a vibro-milling technique.
Table 1 Percentage of perovskite phase of (1-x)BF - xBT; x = 0.1-0.5.

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The morphological changes in the BF-BT powders formed by a mixed oxide method are illustrated
in Fig. 5. In general, the particles are agglomerated and basically irregular in shape, with a
substantial variation in particle size, particularly in samples with more BT contents. Generally,
particle size of all compositions can be estimated from SEM micrographs to be in range of 0.4-2 m.

x=0.1

x=0.2

x=0.3

x=0.4

x=0.5

Figure 5. micrographs of the (1-x)BF - xBT powders


Figure 6 shows the field dependence of specific magnetization (MH curve) of the different
calcined condition on (1-x)BF - xBT samples measured at 293 K. the observation of larger
remanent magnetization when increasing BT content .

Summary
In this study, an approach to synthesize pyrochlore-free
lead zinc niobate lead zirconate titanate powders with a
formula (1-x)BF - xBT (when x = 0.1-0.5) by a mixed
oxide synthetic route via a rapid vibro-milling has been
developed. The formation of perovskite phase in calcined
BF-BT powders has been investigated as a function of
calcination temperature by TG-DTA and XRD
techniques. Powder morphology and chemical
Figure 6. Specific magnetizations of (1-x)
composition have been determined with SEM and
BF - xBT powders as a function of field.
EDX techniques. The potential of a vibro-milling
technique as a significant time-saving method to obtain single-phase BF-BT powders at low
calcination temperature is also discussed. The results indicated that at calcination condition of
950oC for 2h, with heating/cooling rates of 5oC/min single-phase BF-BT powders can be obtained
for every composition ratio between x = 0.1-0.5.
Acknowledgments
This work was supported by the Thailand Research Fund (TRF), Commission on Higher Education
(CHE) and National Synchrotron Research Center (NSRC), National Nanotechnology Center
(NANOTEC), NSTDA, Ministry of Science and Technology, Thailand, through its program of
Center of Excellent Network, Faculty of Science, Chiang Mai University. Thanks are also extended
to Young Scientist and Technologist Program of the National Science and Technology
Development Agency for undergraduate scholarship.
References
[1]
[2]
[3]
[4]

J.G. Ismilzade: Phys. Status Solidi (b) Vol. 46 (1971), p. K39.


G.A. Smolenskii and V.M. Yudin: Sov. Phys. JETP Vol. 16 (1963), p. 622.
Y.P. Wang, L. Zhou, M.F. Zhang, X.Y. Chen, J.M. Liu and Z.G. Liu: Appl. Phys. Lett. Vol.
84 (2004), p. 1731.
V.R. Palkar, R. Pinto and Pramana: J. Phys. Vol. 58 (2002), p. 1003.

Advanced Materials Research Vols. 55-57 (2008) pp 245-248


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.245

Assessment of Mechanical Properties and Transformation Behavior of


Locally-made Ni-Ti Alloys Used in Orthodontics
N. Chiranavanit1,a, A. Khantachawana2,b, N. Anuwongnukroh1,c and
S. Dechkunakorn1,d,*
1

Department of Orthodontics, Faculty of Dentistry, Mahidol University, Bangkok 10400 Thailand


2

Biological Engineering Program and Department of Mechanical Engineering, Faculty of


Engineering, King Mongkuts University of Technology Thonburi, Bangkok 10140 Thailand
kulni@hotmail.com, banak.kha@kmutt.ac.th, cdtnan@mahidol.ac.th, d dtsdh@mahidol.ac.th

*Corresponding Author: dtsdh@mahidol.ac.th


Keywords: Mechanical
Orthodontics

properties,

Transformation

behavior,

Locally-made

Ni-Ti

alloys,

Abstract. Ni-Ti alloy wires have been widely used in clinical orthodontics because of their
properties of superelasticity (SE) and shape memory effect (SME). The purpose of this study was to
assess the mechanical properties and phase transformation of 50.7Ni-49.3 Ti (at%) alloy (NT) and
45.2Ni-49.8Ti-5.0Cu (at%) alloy (NTC), cold-rolled with various percent reductions. To investigate
SE and SME, heat-treatment was performed at 400C and 600C for 1 h. The specimens were
examined using an Energy-Dispersive X-ray Spectroscope (EDS), Differential Scanning
Calorimeter (DSC), Universal Testing Machine (Instron), Vickers Hardness Tester and Optical
Microscope (OM). On the three-point bending test, the superelastic load-deflection curve was seen
in NTC heat-treated at 400C. Furthermore, NT heat-treated at 400C with 30% reduction produced
a partial superelastic curve. For SME, no conditions revealed superelasticity at the oral temperature.
Micro-hardness value increased with greater percentage reduction. The average grain size for all
specimens was typically 55-80 m. The results showed that locally-made Ni-Ti alloys have various
transformation behaviors and mechanical properties depending on three principal factors: chemical
composition, work-hardening (the percent reduction) and heat-treatment temperature.
Introduction
In orthodontics, the ideal arch wire should provide light, continuous forces [1]. Such forces may
reduce the potential discomfort, tissue hyalinization, and undermine resorption [2]. Ni-Ti alloy wire
is widely used in clinical orthodontics due to its superelasticity and ability to provide light and
continuous forces transmitted to the dentition over a long activation period resulting in a desirable
biological response [3]. Moreover, superelasticity is manifested by a considerable range of
deflection without permanent deformation (Fig.1). This phenomenon means that an arch wire would
exert constant force whether it were deflected a relatively small or a large distance, which is a
unique and extremely desirable characteristic especially for leveling and aligning severely
malpositioned teeth [1]. Many companies in Thailand import Ni-Ti alloy wires from foreign
countries. In addition, no nickel-titanium orthodontic arch wire producer exists in Thailand.
Therefore, this study will be a preliminary work to fabricate and evaluate the effect of different
degrees of cold-working and heat treatment temperatures on the properties of Ni-Ti alloys.

(a) Beginning treatment

(b) After 3 months

Figure 1. (a) At the beginning of


treatment, NiTi alloy wire was
used for leveling the crowded
teeth. (b) After treatment for 3
months, the teeth were aligned.

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Experimental
A conventional vacuum arc re-melting technique was employed to prepare two systems of the
equiatomic Ni-Ti alloys: 50.7Ni-49.3 Ti (at%) alloy (NT) and 45.2Ni-49.8Ti-5.0Cu (at%) alloy
(NTC). Titanium, nickel and copper (purity, 99.9%) were cleaned in hydrofluoric and nitric
solutions to remove surface grease and oxide before melting together in argon atmosphere. The
ingot was turned over and re-melted five times to ensure chemical homogeneity. Further, the asmelted ingots were sliced into small plates (1.5 mm. in thickness) using a CNC wire cutting
machine (Sodick: Linear Servo Controller LN1W) and followed by cold-rolling process. The final
thicknesses of the cold-rolled plates were 1.35, 1.20 and 1.05 mm. with reductions of 10%, 20% and
30 %, respectively. The received plates were cut into specific shaped specimens by a CNC wire
cutting machine. Specimens for phase-transformation temperature analysis by Differential Scanning
Calorimeter (DSC) were 3.0 X 3.0 mm. Specimens for chemical composition analysis by X-ray
Energy-Dispersive Spectroscope (EDS), for micro-indentation hardness test by Vickers
Microhardness Tester and for grain structure analysis by optical microscope were 3.0 X 7.0 mm.
Lastly, specimens for three-point bending test by Instron Universal Testing Machine were 30.0 X
1.0 mm. After removing any oxide layers and surface contaminants by mechanical polishing, the
specimens were annealed at 400C and 600C in a vacuum heat treatment furnace for 1 hour in
order to study the influence of recrystallzation on the mechanical properties and transformation
behavior of the alloys.
Results and Discussion
The chemical compositions analyzed by EDS were 47.65at%Ni, 52.01at%Ti, 0.24at%Si for NT,
and 41.94at%Ni, 50.21at%Ti, 7.56at%Cu, 0.29at%Si for NTC. Transformation temperature ranges
determined by DSC are listed in Table 1.
Table 1. Transformation temperatures and enthalpy changes (H) for all conditions of nickeltitanium alloy specimens
Heating
Cooling
Ni-Ti alloy
Heat
Temperature
%
specimens
treatment
hysteresis
As
Af
Ms
Mf
Reduction
[at%]
temp.[C] [C] [C] [C]
[C]
[C]
400
26
55
34
10
23
10
600
54
70
48
34
25
400
22
52
31
5
21
NT
20
600
59
72
52
38
24
400
18
49
29
0
19
30
600
59
71
49
40
23
400
25
56
52*
23**
5
10
600
-2
28
0
-31
25
31**
4
400
34
55
53*
NTC
20
600
11
30
3
-16
20
400
34
55
53*
32**
3
30
600
-1
26
0
-26
24
* Rs, ** Rf (Rhombohedral phase)
Superelasticity (SE) was observed in NTC heat-treated at 400C (Fig.1). No significant difference
of the transformation temperature ranges was found among the 10%, 20% and 30% reductions. All
peaks were broad and showed narrow temperature hysteresis, approximately 5C. This phenomenon
confirmed that the peak on cooling path was not the martensitic transformation but the R-phase
transformation, which can occur in nickel-rich Ti-Ni alloys aged at an appropriate temperature and
in ternary Ti-Ni-Fe and Ti-Ni-Al alloys [4,5]. The R-phase is thought to be caused by the

Advanced Materials Research Vols. 55-57

247

introduction of dislocation and precipitations and also provided very small stress hysteresis [6]. The
average peak of heating and cooling curves was located approximately at the oral temperature.
Thus, the superelastic property should be present in this alloy. The load-deflection curves of the
specimens in all percent reductions were almost identical and showed superelastic curves (Fig.2b)
with small stress hysteresis. This result corresponded with the thermograph (Fig.2a).
0.18
0.13

10% reduction
20% reduction

13500

30% reduction

12000

20% Reduction
30% Reduction

10500

0.08

9000

0.03

Load (gf)

Heat flow (W/g)

10% Reduction

-0.02

7500
6000
4500

-0.07

3000

-0.12
1500

-0.17

-60

-40

-20

20

40

60

Temperature ( C)

80

100

120

Figure 2a. Thermograph of NTC with 10%, 20%


and 30% reductions heat-treated at 400C

0.5

1.5

Deflection (mm.)

Figure 2b. Load-deflection curves of NTC


with 10%, 20% and 30% reductions heattreated at 400C

Partial superelasticity was obtained in NT, cold-rolled at 30% reduction and heat-treated at 400C
for 1 hour. The differences among the peaks of phase transformation with 10%, 20% and 30%
reductions were observed. The transformation temperature ranges of both heating and cooling paths
decreased and the peaks broadened when the percent reduction increased. This signified that the
percentage reduction has an impact on phase transformation. On the other hand, the dislocation that
occured from work-hardening suppressed the phase transformation [7]. For the specimens of 10%
and 20% reductions, similar load-deflection curves were found. Interestingly, when the percent
reduction increased to 30%, the recovery stress could be noticed on the unloading curve. Moreover,
the load-deflection curve showed greater superelasticity than that of 10% and 20% reductions.
For shape memory effect (SME), no conditions revealed superelasticity at the oral temperature.
Interestingly, NTC heat-treated at 600C should represent the superelasticity at the oral temperature
because Af was set between 26C-30C. On the other hand, clinical use was not a stress-free
condition. The applied stress from the three-point bending test may induce the transformation
temperature range to shift higher according to the Clausius-Clapeyron relationship [6], which gives
the relationships of shape memory and superelastic behavior to stress and temperature. From this
theory, the transformation temperature ranges, especially Af, may shift over the oral temperature
and cause the reverse transformation to disappear or partially occur. The transformation peaks were
sharper than that of NiTiCu heat-treated at 400C because of the recrystalization at the 600C heat
treatment (Fig.1). Temperature hysteresis was also larger. These characteristics indicated that the
peak was the martensitic transformation, not the R phase transformation. In addition, the difference
between the peak positions of 10%, 20% and 30% reductions indicated that cold-working had an
influence on transformation temperature range. Nevertheless, heat treatment at 600C caused the
transformation temperature range of martensite to shift higher and approach the oral temperature.
This means the probability of obtaining superelasticity at the oral temperature was decreased. On
the three-point bending test, significant differences of load-deflection curves were clearly seen
within three cycles of each percent reduction. The deflection did not completely recover.

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Micro-hardness values of Ni-Ti alloys heat-treated at 400C tended to increase when the
percentage reduction increased. At 600C heat treatment temperature, the hardness values
decreased with no significant difference of microhardness values found among the percentage
reductions. Figs.3(a) and 3(b) show the optical micrograph of NTC with 20% reduction and 400C
heat treatment. Grain strutures of the Ni-Ti alloys on the longitudinal section were elongated
parallel to the cold-rolling direction. The average grain sizes measured on the cross section were 5580m. No significant difference of the grain sizes was found among the reductions of 10%, 20%
and 30%.

Figures 3a and 3b. Optical micrograph


(20X) showing grain structure of NTC
with 20% reduction and 400C heat
treatment

(a) Longitudinal section

(b) Cross section

Summary
The principal factors affecting the transformation behavior and mechanical properties of Ni-Ti
alloys are chemical compositions, working history and heat treatment temperature. SEwas observed
in NTC with 10%, 20% and 30% reductions and heat-treated at 400C for 1 h. In addition, partial
SE was found in NT with 30% reduction and heat-treated at 400C for 1 h. On the other hand, SME
was not obtained in any conditions of all specimens. To improve SE and SME, transformation
temperature range should be reduced by increasing the percentage reduction over 30% or by
increasing Ni/Cu content. This information is valuable as baseline data for further development of
locally-made nickel-titanium alloy wires used in orthodontics.
References
[1] W. Proffit, Fields and H. Jr: Contemporary orthodontics (3rd ed, St. Louis, Mosby, 2000).
[2] R.P. Kusy: Angle Orthod., Vol. 67 (1997), p. 197.
[3] F.J. Gil, E. Solano, J. Pena, E. Engel, A. Mendoza and J.A. Planell: J. Mater. Sci. Mater. Med.,
Vol. 15 (2004), p. 1181.
[4] K. Otsuka and Wayman: Shape memory materials, (United Kingdom, Cambridge University
Press, 1998).
[5] P.C. Su and S.K. Wu: Acta. Materialia., Vol. 52 (2004), p. 1117.
[6] M. Iijima, H. Ohno, I. Kawashima, K. Endo, W.A. Brantley and I. Mizoguchi: Biomaterials., Vol.
23 (2002), p. 1769.
[7] T. Kurita, H. Matsumoto and H. Abe: J. Alloys Compd., Vol. 381 (2004), p. 158.

Advanced Materials Research Vols. 55-57 (2008) pp 249-252


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.249

Effect of Direct Electric Resistance Heat Treatment on


Mechanical Properties of NiTi Orthodontic Arch Wires
W. Kiattiwongse1,a, A. Khantachawana2,b, P. Santiwong1,c,*
1

Department of Orthodontics, Faculty of Dentistry, Mahidol University, Bangkok 10400, Thailand


2

Department of Mechanical Engineering, Faculty of Engineering,

King Mongkuts University of Technology Thonburi, Bangkok 10140, Thailand


a

redwing7724@hotmail.com, b anak.kha@kmutt.ac.th , *, cdtpsg@mahidol.ac.th

Keywords: Nickel titanium alloy, orthodontic archwire, heat treatment, surface hardness, threepoint bending test

Abstract. Two types of rectangular orthodontic archwires; NiTiTM and 40oCuNiTi, were heat
treated by Direct Electric Resistance Heat Treatment (DERHT) using different electric currents for
4 s. Their mechanical properties were then evaluated by micro hardness and three-point bending
tests. After applying 4.5-5.5 A current, the hardness of NiTiTM increased with the increased current,
whereas the change in hardness of 40oCuNiTi was slight. When 6 A current was applied, the
hardness of the midspan of both wires significantly decreased. From the three-point bending test,
unloading forces of NiTiTM increased after treating with 5.5 A current, while those of 40oCuNiTi
decreased. However, both specimens lost their superelasticity when applied with 6 A current. In
conclusion, after DERHT, various changes in mechanical properties can be noted in the different
types of nickel titanium archwire.
Introduction
Nickel Titanium [NiTi] alloy has been widely used as an orthodontic archwire for more than two
decades. It is generally accepted that light and continuous forces applied to the dentoalveolar
structures provide optimal tooth movement. The superelasticity of NiTi archwires allows the
clinician to apply a light continuous force with larger activations making them popular as the initial
archwires for levelling and alignment [1, 2]. Some heat treatment methods have been used to
control the level of force delivered from NiTi archwire [3, 4]. Direct Electric Resistance Heat
Treatment [DERHT], first introduced by Miura et al, is considered to be one of the most suitable
methods for heat treating the wire for clinical use [5]. Little is known about the physical and
mechanical properties of various commercial orthodontic archwires after DERHT. This study aimed
to investigate the effect of DERHT on mechanical properties of two NiTi orthodontic archwires.

A.

B.

(A)
(B)
Figure 1. (A) An orthodontic archwire (B) Orthodontic treatment with NiTi archwires placed
intraorally

250

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Materials and Methods


The straightest part of preformed rectangular archwires, 0.0160.022 inches2, for two types; NiTiTM
and 40oCuNiTi [Ormco,USA], were cut into 30 mm. segments. The heat treatment processes were
carried out for 4 s using the electric current of 4.5, 5, 5.5 and 6 A. After heat treatment, mechanical
properties were evaluated by micro hardness test and three-point bending test. For the hardness test,
three archwire segments from each group were embedded in epoxy resin. The specimens were
polished with water coolant silicon carbide paper from 400 to 2000 grit and washed with acetone.
Each specimen surface was subjected to Vickers Hardness Test by using a microhardness tester
[Future-Tech Corporation, Tokyo, Japan] applying a load of 50 g for 15 s at three specific regions
[4 mm, 10 mm, and 15 mm from one end of the wire]. For the three-point bending test, the
apparatus and test conditions were set according to ISO 15841:2006 [6]. Briefly, the wire specimen
was supported by two pulleys, located 10 mm apart. Each wire was loaded to a deflection of 3 mm
and then unloaded at constant temperature 37oC. The loads measured at a deflection of 1.5 mm
during the unloading process were statistically compared.
Results and Discussion
The mean comparison of surface hardness values among different areas and currents of both wires
were analyzed by two-way ANOVA at a P-value of 0.05 [Table 1]. A statistically significant
difference was found in the different levels of current but not in different areas. The hardness
values of NiTiTM were greater than those of the 40oCuNiTi in all conditions. For the heat treated
NiTiTM wires, the hardness increased when compared with those of the as-received wires, except for
the wires heated with 6 A for 4 s. For this heating condition, the highest hardness value was at the
end region of the wire and the lowest hardness value was in the midspan of the wire. On the other
hand, a correlation between hardness and increased current could not be found in the 40oCuNiTi
group except for the wire heated with 6 A for 4 s, in which case, the correlation was the same as
NiTiTM.
Table 1. The hardness measurements of NiTiTM and 40oCuNiTi in different heat-treating conditions.
Type of

iTiTM

40 CuiTi

5 A for 4s 5.5 A for 4s

6 A for 4s

As-received

4.5 A for 4s

4 mm

3457

36523

3448

40521

42011

10 mm

34011

3676

39231

38528

34715

15 mm

35215

34624

40825

41824

31121

4 mm

3088

3143

31313

3134

32612

10 mm

3250

3259.64

3434

32311

28110

15 mm

31010

3257

34412

3364

2587

wire/Current(A)

The results from the three-point bending test are shown in Table 2. The mean comparison of
unloading forces among as-received wire and heat-treated wires were analyzed by Pair T-test for
data with normal distribution or by Mann-Witney Rank Sum Test for data without normal
distribution. When heated with 4.5 A and 5 A, the unloading forces showed no statistically
significant difference from the control. However, the unloading force significantly increased in
NiTiTM and decreased in 40oCuNiTi after heat treatment with 5.5 A. With 6 A current, the
unloading force of both wires significantly decreased. Moreover, permanent deformation occurred

Advanced Materials Research Vols. 55-57

251

in the NiTiTM and the 40oCuNiTi wires lost their superelasticity after heat treatment at these
conditions [Figure 2].
Table 2. Means standard deviations of forces measured when as-received and heat-treated
orthodontic archwires were deflected 1.5 mm during the unloading process at 37oC (gram)
Type of wires

As-received 4.5 A

iTiTM

31511.15

31411.47 31112.33 41510.03 26768.47

40oCuiTi

8114.31

8713.16

5.5A

5.5 A

766.99

6A

4731.01

6A

2.12.76

As-received

700
600
500
400
300
200
100
0

5.5A

6A

300
250

Load (gf)

Load (gf)

As-received

5A

200
150
100
50
0

0.5

1.5

Deflection (mm.)

2.5

0.5

1.5

2.5

Deflection (mm.)

(A)
(B)
o
Figure 2. Load-deflection curves from three-point bending test at 37 C of the as-received and heattreated wires, (A) NiTiTM and (B) 40oCuNiTi
From the phase diagram of NiTi alloy, the system approaches equilibrium by precipitation in order
to make the Ni/Ti ratio within the matrix equal to 1. This process is activated by heat treatment
because precipitation occurs with rising temperature. The precipitation causes an important
variation in the chemical composition because the quantity of Ni in the matrix of the alloy is
changed to create the precipitate resulting in a hardening of the alloy [7]. The properties of NiTi
alloy are sensitive to the Ni-content in the matrix, so the transition temperatures and unloading force
are affected.
Heat treatment effects on surface hardness did not appear when Cu was present because the
hardness was slightly constant when applied with different currents. This fact was due to the
substitution of nickel atoms by copper atoms, producing a decrease of the nickel content, which is
the chemical content limit needed for the precipitation process. However, during heat treatment,
deformation rearranged and decreased leading to a decreased unloading force of 40oCuNiTi [8,9].
In our study, permanent deformation occurred in the NiTiTM wires, when heated with 6 A current
for 4 s. Moreover, by the same condition, the 40oCuNiTi wires lost their superelasticity. These
results indicate that DERHT using 6 A current for 4 s resulted in over heating for both NiTiTM and
40oCuNiTi wires, and are not appropriate for clinical use. After DERHT, the unloading forces of
different nickel titanium archwires would be changed in various ways. Increasing the magnitude of
force raises the possibility of tissue destruction, such as root resorption. On the other hand,
decreasing force to sub-optimal level lead to the ineffective and slow tooth movement. Therefore,
the effects of DERHT on the mechanical properties of any archwires, especially the unloading
force, should be thoroughly studied before clinical application.

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Summary
1. The hardness of NiTiTM increased with increasing current, whereas the hardness of 40oCuNiTi
was changed slightly.
2. The unloading forces of both wires showed no statistically significant difference after DERHT
at 4.5 and 5 A for 4 s.
3. After DERHT at 5.5 A for 4 s, the unloading forces of NiTiTM increased but those of 40oCuNiTi
decreased.
4. DERHT at 6 A for 4 s produced over heating for the NiTiTM and 40oCuNiTi.
5. Considering the various changes in the mechanical properties of different NiTi archwires after
DERHT, the effect of DERHT on the mechanical properties of any archwires, especially the
unloading force, should be thoroughly studied before clinical application.
Acknowledgement
This study was supported by a grant from the Faculty of Dentistry, Mahidol University.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

William A. Brantley and E.Theodore: Orthodontic Materials (New York, 2001)


R.P.Kusy: Am J Orthod Dentofacial Orthop Vol. 100(3) (1991), p. 25.
F.Miura, M.Mogi, Y.Ohura and H.Hamanaka: Am J Orthod Dentofacial Orthop Vol. 27(3)
(1986), p. 1.
T.Yoneyama, H.Doi, H.Hamanaka, M.Yamamoto and T.Kuroda: J Biomed Mater Res Vol.
27(3) (1993), p. 399.
F.Miura, M.Mogi and Y.Ohura: Eur J Orthod Vol. 10(3) (1988), p. 187.
Standardization. Dentistry-Wires for use in orthodontics. In: Metallic material bending test.
(2006), p. 1-9.
F.J.Gil, E.Solano, A.Campos, F.Boccio, I.Saez and N.V.Alfonso: Biomed Mater Eng Vol.8(56) (1998), p. 335.
F.J.Gil and J.A.Planell: J Biomed Mater Res Vol.48(5) (1999), p. 682.
M.Iijima, K.Endo, H.Ohno and I.Mizoguchi: Dent Mater J Vol.17(1) (1998), p. 31.

Advanced Materials Research Vols. 55-57 (2008) pp 253-256


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.253

Materials of Nanocrystalline Sr1-xBaxBi4Ti4O15 for Piezoelectric Sensor


N. A. A. Manafa, M. M. Salleha and M. Yahayab
a

Institute of Microengineering and Nanoelectronic (IMEN), Universiti Kebangsaan Malaysia,


43600 UKM, Bangi, Selangor, Malaysia;

School of Applied Physics, Faculty of Science & Technology, Universiti Kebangsaan Malaysia
43600 UKM, Bangi, Selangor, Malaysia
a

azlianmanaf@yahoo.com, mms@ukm.my, myahya@ukm.my

Keywords: Nanocrystalline thin films; sol-gel; strontium barium bismuth titanate; piezoelectric
pressure sensor.

Abstract. The nanocrystalline Strontium Barium Bismuth Titanate (SBBT) thin films with structure
of Al/TiO2/SBBT/TiO2/RuO2/SiO2/Si were fabricated using sol-gel technique. The source materials
are bismuth acetate Bi(CH3COO)2, barium acetate Bi(CH3COO)2, strontium acetate Sr(CH3COO)2
and titanium butoxide (Ti(OC4H9 )4). Different nanostructures of the films were prepared with
un-annealed condition as well as after annealing at three different temperatures of 400, 500 and
6000C, in air for 2 minutes. The structure of SBBT thin films have been systematically studied by
XRD, AFM, SEM and dielectric constant measurement. For the sensor device measurement, the
SBBT thin film pressure sensors were tested by pneumatic loading method at pressure range between
0 to 450 kPa. It was found that the sensing properties of the films were affected by the crystalline
nature of the films. It is shown that there is a linear relationship between the crystallization, grains
size and dielectric properties with the sensing response of the film towards pressure.
Introduction
Pressure sensors are one of the most common micro-sensors devices used in various industries such as
automotive, medical, military, aeronautical, hydraulics, instrumentation, process and industrial
control [1]. Pressure or stress sensing materials, that is piezoelectric material is the most frequently
used material in pressure gauge because of its special capabilities such as fast response, ruggedness,
high stiffness, ability to measure the quasi-static pressure and good thermal stability.
At present, in commercial sector, lead zirconate titanate (PZT) based ceramic are most widely
used as a sensing material. However the evaporation of toxic lead during the fabrication of their
ceramic causes an environmental problem. Therefore, there is an increasing interest of investigating
lead free of piezoelectric materials to replace PZT based piezoelectric ceramics. In the previous
research we choose bismuth titanate (BTO) to replace PZT since it has a large piezoelectric
coefficient. BTO is one of the family called Aurivillius phase, generally formulated as Am-1BmO3m-1
[2]. However, the most problem found in the performance of BTO pressure sensor are slow recovery
time, low repeatability and raising current leakage at high annealing temperature. Several approaches
have been made to solve these well known problems. One critical approach is altering the previous
BTO solution by doping strontium and barium in proper molar composition. Strontium and barium
have been identified as potential stabilizing materials in BTO ceramics. Strontium barium bismuth
titanate (SBBT) Sr(1-x)Ba(x)(Bi4Ti4O15 ) based ceramics is chosen because of its high Curie
temperature (Tc= 6200C), good piezoelectricity and thermal stability [3]. In this paper, we report the
fabrication and characterization of Sr(1-x)Ba(x)(Bi4Ti4O15) thin films pressure sensors with various
annealing temperature.

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Experimental
The solution of Sr(1-x)Ba(x)(Bi4Ti4O15) was prepared by sol gel technique. The raw starting materials
were bismuth acetate Bi(CH3COO)2, barium acetate Bi(CH3COO)2, strontium acetate Sr(CH3COO)2
and titanium butoxide (Ti(OC4H9 )4). Initially, the powder of bismuth, barium and strontium were
dissolved with a proper molar in 4 ml acetic acid containing 20% volume of deionize water at room
temperature.
The SBBT films were spin coated on silicon wafer at 400 rpm for 30 second followed by heating
process at 300 0C in air for 15 minutes. The films were then annealed at temperature of 400, 500, 600
and 700 0C. The crystal structure of the SBBT thin films were examined using X-ray diffractometer
(XRD). Dielectric measurements were carried out using impedance spectroscopy
Solarton-Schlumberger, while the homogeneities and grains size of the samples were characterized by
Scanning Electron Microscope (SEM).
The SBBT pressure sensors were fabricated with the structure of Al/TiO2/SBT/TiO2/SiO2/Si. The
raw material is silicon wafer and the silicon oxides were deposited by electron beam evaporation with
thickness of 1500 . Ruthenium Oxide as bottom electrode was deposited using RF magnetron
sputtering for 2 hours. In order to reduce the crystallization temperature for the formation of SBBT
ferroelectric phase, the buffer layer, TiO2 was then deposited on these thin films.
Results and Discussion
Thin film characterization
Typical XRD patterns SBBT thin films annealed at various temperatures are shown in figure 1. It is
shown that the films were in amorphous phase and it began to converse to crystalline phase after
annealing at 600 0C. Figure. 2 shows SEM micrographs of SBBT thin films. The images indicated that
annealed films were in orderly forms, where the nano sized grains were formed with a clear grain
boundary. This feature is very important, since the electromechanical responds can be arose from the
orderly oriented grains. The electrical behavior of SBBT thin films measured in terms of the dielectric
constant. The value of the dielectric constant was calculated from the capacitance of the film using
Debye distribution formula, measured at 1 kHz at 20 mV. Dielectric constant of un-anneal SBBT film
was 72.81 and increased to 187.4 at annealing temperature 700 0C. The higher dielectric constant is
due to the increasing number of domain population and its wall motion [4] hence improved
crystallization process of the thin film after annealing.

Figure 1. XRD patterns of x = 2 with different annealing temperature.

Advanced Materials Research Vols. 55-57

255

Figure 2. SEM images of surface morphology of Sr(1-x)Ba(x)(Bi4Ti4O15) thin film for un-anneal and
anneal at 4000 C, 5000 C, 6000 C, 7000 C.
Piezoelectric pressure sensor measurement
The piezoelectric measurement system was designed using the concept of direct piezoelectric effect.
When pressure is applied to piezoelectric materials, it create a strain or deformation in the materials,
due to the deflection of the lattice in a naturally piezoelectric quartz crystal [5]. The response
repeatability of SBBT sensor is shown in figure 3. The measurements were made by seven cycles at
450 kPa. The graph indicated that the 600 0C anneal sensor showed the best repeatability compared to
others since the similar respond was maintained until the seventh cycles. The SBBT pressure sensor
achieved a linear characteristic response between 50 kPa to 450 kPa pressure load. It was found that
the performance of sensors could be influence by internal structure of SBBT films. This structure is
applicable for better electromechanical responds in the ferroelectrics materials. The small dielectric
constant for low annealed sensor gave low capacitance that would present poor repeatability during
continuous high pressure measurement. The 700 0C annealed sensor presents poor repeatability.
Based on the SEM result, it is suggests that nanostructure of the films would play an important role to
generate the high voltage and stable electromechanical response. When the grain size increase, the
domain that carrying the dipoles will be increased as well [6].

Figure 3. The piezoelectric response SBBT pressure sensors measured at 450 kPa pressure load for
un-annealed and annealed at 400, 500, 600 and 700 0C.

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Figure 4. Graph of linearity for pressure sensor performance for un-anneal and anneal at 4000 C,
5000 C, 6000 C, 7000 C
The figure of merit of this sensor that is the sensitivity of 20-4010-3 mV/Pa is slightly higher
compared to that of PbTiO3PVDF(TeFE) piezoelectric composites which is greater than 1 mV/Pa
[7]
Summary
The microstructure and piezoelectric responds of SrBi4Ti4O15 thin films pressure sensors have been
systematically studied in as-prepared condition as well as after annealing at 400, 500, 600 and 700 0C.
The XRD results indicated that the SBBT film starts to converse from amorphous phase to crystalline
after annealing at 600 0C. The dielectric constant and grain size were found to increase with annealing
temperature.
Acknowledgement
The authors would like to thank the Malaysia Ministry of Science, Technology and Innovation for the
grant Science Fund project.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

D. Tandaske: Pressure sensors: selection and application (Marcel Dekker, New York, 1984).
Y. Xu: Ferroelectric materials and their application (Elsevier, North-Holland, 1991)
Xie, W.Pan and H. Shi: Mater. Sci. Eng. B Vol. 99 (2003), p. 1.
T.L Jordan and Z. Ounaies: Piezoelectric ceramics characterization (ICASE, NASA
Langley Research Center, Hampton, Virgina, 2001).
S.B Ren, C.J Lu, J.S Liu, H.M Shen and Y. N Wang: Phys. Rev. B Vol. 54 (1996), p. 14337.
C. J Lu, S. B. Ren, J.S Liu, H.M Shen and Y. N Wang: J. Phys. Matter Vol. 8 (1996), p. 8011.
L. Wang, J. Zhu, X.Zou and F. Zhang: Sensor. and Actuat. B Vol. 66 (2000), p. 266.

Advanced Materials Research Vols. 55-57 (2008) pp 257-260


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.257

Electrical Conductivity of Poly(3,4-ethylenedioxythiophene)Poly(styrenesulfonate) Coatings on Polyacrylonitrile Nanofibers for


Sensor Applications
M. Panapoya, N. Saengsilb and B. Ksapabutrc
Department of Materials Science and Engineering, Faculty of Engineering and Industrial
Technology, Silpakorn University, Nakhon Pathom 73000, Thailand
a

mpanapoy@hotmail.com, bms_petro@hotmail.com, ckbussarin@hotmail.com

Keywords: Polyacrylonitrile, PEDOT/PSS, Electrospinning, Nanofibers, Sensor

Abstract. Conducting polyacrylonitrile (PAN) nanofiber mats were prepared by dipping nonwoven nanofiber mats of PAN in the solution of poly(3,4-ethylenedioxythiophene)/poly(4styrenesulfonate) (PEDOT/PSS). PAN nanofiber mats were fabricated via the electrospinning
process. The solvent used for PEDOT/PSS was ethylene glycol and isopropanol. The morphology
of the resulting PAN nanofibers and the coating layers was investigated using SEM analysis. The
electrical conductivity of PEDOT/PSS coated PAN nanofiber mats was measured by the four-point
probe method, for different concentrations of solvent in the PEDOT/PSS solution. An addition of
ethylene glycol resulted in higher electrical conductivity of the coated mats than that of isopropanol.
The resistive humidity sensing properties were also investigated. The device reproducibility was
presented by vapor adsorption/desorption dynamic cycles. The reproducibility of the PEDOT/PSS
coated mats was superior to that of neat PEDOT/PSS films. The response sensitivity of coated mats
using isopropanol as solvent was higher than that using ethylene glycol.
Introduction
The growing attention has been dedicated to intrinsically conducting polymers (ICPs) during the
last decade due to their availability of a diverse range of monomer analogues, possible
modifications of basic polymer and dopant systems, and formation of film coating on various
substrates These properties may be useful in the realization of a number of devices, such as
electronic circuit components, light-emitting diodes, and sensors [1]. There are various interesting
candidates, i.e. polyacetylene, polypyrroles, polythiophenes, and polyanilines that can be used in
different applications where electrical conductivity is required. Among them, poly(3,4ethylenedioxythiophene) (PEDOT) doped with poly (4-styrenesulfonate) (PSS) has gained a
considerable momentum due to its interesting electrical, electrochemical and optical properties. Its
excellent thermal and environmental stability, high quality film formation, high electrical
conductivity, and high transparency in the visible range make PEDOT/PSS useful for potential
applications in electronic devices, such as sensors, hole injection layer, antistatic coating,
supercapacitors, transistors, electrochromic displays and flexible electrodes [2]. In recent years, the
studies on PEDOT/PSS as sensor materials have been reported, in various applications such as
biosensor and biological receptors [3]. With the rapid economic growth, the living standards of
human beings have greatly improved. Humidity sensors have become increasingly important and
are widely used in many fields, such as improving quality of life and enhancing industrial
processes.
In this study, we further extend the efforts for the application of PEDOT/PSS to polymeric
nanofibers so as to be used for sensor applications. PEDOT/PSS coated PAN nanofibers were
prepared via an electrospinning method of PAN solution followed by dipping PAN nanofiber mats
in the solution of PEDOT/PSS. The electrical conductivity and the humidity sensing properties of
PEDOT/PSS coated PAN nanofiber mats were addressed. An emphasis will be made on the effects
of coating and solvent on the sensing performance of this system.

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Experimental
Commercial PAN powders (Aldrich) were dissolved in 99.5 % ,-dimethylformamide (DMF) to
produce a homogeneous PAN solution with a concentration of 7 wt% for electrospinning. The
polymer solution was electrospun at room temperature in ambient air atmosphere under an applied
voltage of 19 kV. The flow rate of the polymer solution was controlled at 0.25 ml h-1. The
positively charged syringe used in this work had a capillary tip diameter of 0.711 mm. A grounded
metal screen covered by an aluminum foil was used as the counter electrode and was placed 15 cm
from the tip of the capillary. Continuous PAN nanofibers were deposited on the aluminum foil and
collected in the form of fibrous nonwoven mats. The electrospun PAN nanofiber mesh was
carefully peeled off from the aluminum foil. As-electrospun PAN fibers were examined using SEM
carried out on a Hitachi S3400N electron microscope.
PEDOT/PSS coated PAN nanofiber mats were prepared by dissolving PEDOT/PSS (SigmaAldrich in the form of water suspension (1.3 wt%)) in solvent at different concentrations ranged
from 3 to 50 % (v/v). The solvents used were isopropanol (99.8 %) and ethylene glycol (EG). The
as-spun PAN nanofiber mats obtained were immersed into the mixed solution of PEDOT/PSS and
organic solvent for 30 min, and subsequently dried in a vacuum oven at 40oC for 3 h. Neat
PEDOT/PSS films were prepared using only commercial PEDOT/PSS in the form of water
suspension (1.3 wt%) via tape casting technique. The morphology of PEDOT/PSS coated PAN
nanofiber mats was examined by SEM analysis. The electrical conductivity of specimens was
measured at room temperature using four-point probe (Lucas Labs, 302Resistivity Probe). The
current-voltage characteristics were measured using a Keithly 6517A digital electrometer and
stabilized power supply. The resistance was recorded by two-probe method (a Hioki 3801 Hitester).
Measurement of moisture sensing responses was performed by enclosing samples in a closed
chamber over several materials for several days. The materials employed were dried silica gel,
substantive 55.01% H2SO4 solution, NaCl saturated solution, yielding relative humidity (RH) about
0 %, 25 %, 75 % and 100 %, respectively.
Results and Discussion
SEM micrographs of as-electrospun PAN fibers are demonstrated
in Fig. 1 PAN nanofibers with an average diameter of
approximately 330 nm were obtained. Fig. 2 presents the electrical
conductivity of PEDOT/PSS coated PAN nanofiber mats prepared
from two different solvents as a function of solvent concentration.

Conductivity (log (s/cm))

2 um

Figure 1. SEM image of PAN nanofibers (Inset is low


magnification).
The electrical conductivity of coated PAN nanofiber
mats prepared using isopropanol as solvent increased
with rising solvent concentration. The screening effect
between the positively charged PEDOT chains and
negatively charged PSS chains may be induced,
resulting in an enhancement of hopping rate. A similar
trend was observed in case of EG solvent by Ashizawa
et al. [4]. At higher EG concentration, the electrical
conductivity decreased owing to a reduction of
PEDOT/PSS concentration, which lowers the density of
connections between the grains.

-.5
Isopropanol
EG

-1.0
-1.5
-2.0
-2.5
-3.0
-3.5
0

10

20

30

40

50

Concentration (%v/v)

60

Figure 2. Dependence of solvent concentration on


conductivity of coated nanofiber mats.

Advanced Materials Research Vols. 55-57

259

The coated nanofiber mats prepared from EG (9 % (v/v)) and isopropanol (50 % (v/v)) show the
highest conductivity. Therefore, the highest conductivity of each solvent was chosen for further
studying the humidity sensor properties for practical use.

)
Resistance (k

The reproducibility, response and recovery time and sensitivity of neat PEDOT/PSS film were
tested through carrying out adsorption/desorption dynamic cycles, with RH being interchanged
between 0 and 100 % repeatedly at 25oC. The device responsetime curves of three typical cycles are illustrated in Fig. 3.
140
When the sensor was exposed to the 100%RH, the stepwise
120
increase in resistance was observed in two ranges, possibly
100
due to the adsorption and diffusion of water molecules into the
layer leading to the film swelling which increased the
80
resistance of PEDOT/PSS film. The water molecules
60
contribute to the reduction in effective conductivity of
40
PEDOT/PSS in the presence of humidity [5]. Afterwards, the
20
resistance gradually decreased and reached a plateau. When
the sensor was switched to 0 % RH again, the resistance
0
0
100
200
300
400 drastically decreased and rapidly reached an original value,
Time (s)
indicating the interaction between water vapor and the
polymer surface dominated by physisorption.

280
260
240
220
200
180
160
140
120
100

The time taken to finish 90 %


of its total resistance change
in a RH increasing and RH
decreasing step was defined
as device response time and
recovery time, respectively
[6]. The response time and
recovery time were about 40
and 15 s, respectively.

60

)
Resistance (k

)
Resistance (k

Figure 3. Resistance response of neat PEDOT/PSS film to dynamic switches between 0 and
100 %RH.

50
40
30
20
10
0

0 100 200 300 400 500 600 700

Time (s)

100 200 300 400 500

Time (s)

Figure 4. Resistance response of coated mats to dynamic switches between 0 and 100 %RH in (a)
EG and (b) Isopropanol.
Nevertheless, the neat PEDOT/PSS based humidity sensor had low reproducibility after three cycles
of humidity switch between 0 and 100 % RH. Fig. 4 demonstrates the resistance response of sensor
using PEDOT/PSS coated PAN nanofiber mats prepared from two different solvents. The measured
recovery times in different RH dynamic cycles for coated mats using EG and isopropanol were
about 27 and 13 s, respectively. The response time of coated mats prepared from EG (19 s) was
lower than that prepared from isopropanol (50 s). It can be explained by inhomogeneity of coating,
as shown in Fig. 5. The coating of PEDOT/PSS on PAN nanofiber mats using isopropanol was not
uniform, leading to the slow diffusion of water vapor into the bottom layer of PEDOT/PSS.
However, by defining 100(R RH R0% RH ) / R0% RH as response sensitivity (where RRH and R0%RH are
the film resistances of coated mats at a measuring RH level and at RH of 0%, respectively) [7], the
response sensitivity of coated mats using isopropanol (58%) was higher than that using EG (14%).
Hence, the coated mats from isopropanol were further investigated on the response sensitivity at
various RH levels. Fig. 6 exhibits the resistance of coated mats from isopropanol upon exposure at

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different RH values. The response sensitivities of coated mats were about 10, 42 and 58 %,
corresponding to RH of 25, 75 and 100 %, respectively.
70

10 um
(b)

)
Resistance (k

(a)

25 % RH
75 %RH
100 %RH

60
50
40
30
20
0

10 um
Figure 5. SEM images of coated mats
from (a) EG and (b) Isopropanol.

100 200

300

400 500

Time (s)

Figure 6. Resistance response of coated


mats from isopropanol to dynamic
switches between 0 and different %RH.

Summary
PEDOT/PSS coated PAN nanofiber mats were prepared by coating PAN nanofibers obtained by an
electrospinning process with PEDOT/PSS solution. The electrical conductivity of coated mats
prepared using EG as solvent was higher than that using isopropanol. The effect of testing chamber
humidity on PEDOT/PSS coated PAN nanofiber sensors prepared using ethylene glycol and
isopropanol as solvent was investigated by measuring the resistance. From vapor
adsorption/desorption dynamic cycles, the reproducibility of coated PAN nanofibers was superior to
that of neat PEDOT/PSS films. By combining the use of electronically conducting polymers with
polymeric nanofibers, it is possible to develop the application for other sensing materials.
Acknowledgment
This work was supported by Department of Materials Science and Engineering, Faculty of
Engineering and Industrial Technology, Silpakorn University and the National Excellence Center
for Petroleum, Petrochemicals, and Advanced Materials.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

J.D.S. Smith: Prog. Polym. Sci. Vol. 23 (1998), p. 57.


D.L. Carroll, R. Czerw and S. Webster: Synth. Met. Vol. 155 (2005), p. 694.
U. Lange, N.V. Roznyatovskaya and V.M. Mirsky: Analytica Chimica Acta. Vol. 614 (2008),
p. 1.
S. Ashizawa, R. Horikawa and H. Okuzaki: Synth. Met. Vol. 153 (2005), p. 5.
J. Liu, M. Agarwal, K. Varhramyan, E.S.Berney IV and W.D. Hodo: Sensor Actuat. B. Vol.
129 (2008), p. 599.
Q. Kuang, C. Lao, Z.L. Wang, Z. Xie and L. Zheng: J. Am. Chem. Soc. Vol. 129 (2007), p.
6070.
W.F. Jiang, S.H. Xiao, C.Y. Feng, H.Y. Li and X.J. Li: Sensor Actuat. B. Vol. 125 (2007), p.
651.

Advanced Materials Research Vols. 55-57 (2008) pp 261-264


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.261

SiO2-Multiwalled Carbon Nanotube Base Gas Sensor


S. Jesena, S. Ruangphet and S. Cheirsirikul
Electronics Research Center, Faculty of Engineering, King Mongkuts Institute of Technology
Ladkrabang, Chalongkrung Rd., Ladkrabang,Bangkok, 10520 Thailand
a

wm_nhoinnoi@yahoo.com

Keywords: Carbon nanotube, ammonia, ethyl alcohol, oxygen, gas sensor.

Abstract. The gas sensors are fabricated from multiwalled carbon nanotube-based. The electrode is
constructed from platinum (Pt) and titanium (Ti). The gas sensors are used for detecting oxygen
(O2), ethyl alcohol (C2H5OH) and ammonia (NH3) by measuring the charge of their electrical
capacitance. In the ratio silicon dioxide (SiO2) : carbon nanotube (MWCNTs) = 100:1 by weight,
the electrical capacitance of the film layer has changed at the highest rate. The response of oxygen
with concentration of 10,000 ppm, 20% of ethyl alcohol and 20% of ammonia, it is found that the
electrical capacitance of thin layer has change about 34%, 60% and 70%.
Introduction
Carbon nanotubes have been found application as field emission devices [1], electronic switches [2]
and actuators [3]. Recently, application of carbon nanotubes as oxygen [4] and methane [5] gas
sensors has been reported. Since nanotubes are essentially all surface, they offer the possibility of
excellent sensitivity and rapid response times. Gas sensors are used in many industrial, medical, and
commercial applications. For example, oxygen sensors are used in the monitoring of combustion
engine environment to increase engine performance and reduce emission of green house gases [6].
In addition to controlling industrial processes [7] and monitoring air quality [8]. Most gas sensors
available on the market today operate by measuring the impedance of a capacitor coated with a gasresponsive polymer(s) or ceramic such as heteropolysiloxane [9] etc. In this paper, we report the
application of multiwall carbon nanotubes (MWNTs) for detection of oxygen, ethyl alcohol and
ammonia based upon the measured changes in MWNT permittivity and conductivity with gas
exposure.
Experimental
The gas sensors have been fabricated from multiwalled carbon nanotube-based. The gas sensors
6,500
consist of multiwalled carbon nanotube
W
(MWCNTs) and silicon dioxide (SiO2)
prepared from silicon dioxide sol-gel solution
on silicon dioxide layer of silicon substrate by
spin coat method. The electrode is constructed
3,500
6,500
from platinum (Pt) and titanium (Ti) by coating
D
using dc-sputtering system. The titanium (Ti)
L
layer functions to adhere between platinum (Pt)
and silicon dioxide (SiO2). Oxygen (O2) gas
2000
measure at the concentrations 500 to 10,000
2000
ppm. Whereas the concentrations of ethyl
L = 6230, W = 60, D = 30
alcohol (C2H5OH) and ammonia (NH3) content
in
DI water 0.1-20% by volume. The structure
120
6,260
120
of sensor show in Fig 1 and Fig 2.
Figure 1. Schematic drawing (m) of the SiO2multiwalled carbon nanotube base gas sensor.

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Capacitor
Electrode

Capacitor
Electrode
Pt

0.50 m

SiO2-MWNTs

0.45 m

SiO2

350  m

Si

Ti

Figure 2. Cross-sectional view (m) of SiO2- multiwalled carbon nanotube base gas sensor.
Results and Discussion

Change rate of electrical capacitance (%)

For the response of oxygen (O2) gas in Fig. 3, at the concentration = 10,000 ppm, the change rate of
electrical capacitance in the ratio silicon
-10
dioxide (SiO2):carbon nanotube (MWCNTs)
100:1 by weight
80:1 by weight
= 100:1 by weight is the most highest rate
60:1 by weight
about 34% and much more than silicon
40:1 by weight
-20
dioxide pure (SiO2) about 7%.
20:1 by weight
SiO2 pure
When the sensors detected oxygen (O2)
gas, the conductivity of SiO2-MWCNTs film
-30
layer would be increased. Since, SiO2MWCNTs film layer oxidize with oxygen
(O2), the electron are hold and hole would be
-40
increased, thus dielectric constant would be
500
1000
5000 10000
increased and depend on concentration of
Concentration of gas (ppm)
gas. The change rate of electrical capacitance
Figure 3. The change rate of electrical capacitance would be increased together wtih the
with concentration of gas, while detecting oxygen increasing of electrical capacitance of film
layer as shown in Fig. 3.
at room temperature.

Change rate of electrical capacitance(%)

For the response of ethyl alcohol (C2H5OH) in Fig. 4, at the concentration = 20%, the change rate of
electrical capacitance in the ratio silicon
dioxide (SiO2):carbon nanotube (MWCNTs)
65
100:1 by weight
= 100:1 by weight is the most highest rate
60
80:1 by weight
about 60% and much more than silicon
60:1 by weight
55
40:1 by weight
dioxide pure (SiO2) about 8%.
50
20:1 by weight
When the sensors detect ethyl alcohol
SiO2 pure
45
(C2H5OH), the conductivity of SiO240
MWCNTs film layer would be increased.
35
Since, SiO2-MWCNTs film layer are
30
reducing agent with (H) ethyl alcohol
25
(C2H5OH), the electron are injected in SiO20.1
1
10
20
MWCNTs
film layer and hole would be
Concentration of gas (% )
decreased [2]. thus, the dielectric constant
Figure 4. The change rate of electrical capacitance would be increased and depend on
with concentration of gas, while detecting ethyl concentration of gas. The change rate of
electrical capacitance would be increased
alcohol at room temperature.
together wtih the increasing of electrical

Change rate of electrical capacitance (%)

Advanced Materials Research Vols. 55-57

75
100:1 by weight
80:1 by weight
60:1 by weight
40:1 by weight
20:1 by weight
SiO2 pure

70
65
60
55
50
45
40
0.1

10

20

263

capacitance of film layer.


For the response of ammonia (NH3) in
Fig. 5, at the concentration = 20%, the
change rate of electrical capacitance in the
ratio silicon dioxide (SiO2):carbon nanotube
(MWCNTs) = 100:1 by weight is the most
highest rate about 70% and much more than
silicon dioxide pure (SiO2) about 10%.
When the sensors detected ammonia
(NH3), the reaction like the ethyl alcohol
(C2H5OH), but the change rate of electrical
capacitance of ammonia (NH3) much more
than ethyl alcohol (C2H5OH),

Concentration of gas (% )

Figure 5. The change rate of electrical capacitance


with concentration of gas, while detecting ammonia
at room temperature.

Change rate of Capacitor (%)

For the result of film thickness in Fig. 6, the film thickness increase from 2,000 to 5,000 , so the
change rate of electrical capacitance are decreased. At the concentration = 10,000 ppm of Oxygen
(O2) gas, the change rate of electrical capacitance is 1.5%. At the concentration = 20% of ethyl
alcohol (C2H5OH), the change rate of electrical capacitance is 2%. At the concentration = 20% of
ammonia (NH3), the change rate of
80
electrical capacitance is 3.5%. The best
Oxygen
ethyl
alcohol
response is ammonia (NH3).
60
ammonia
Because, difference of film thickness
40
in between air level (atmosphere 30C)
20
and gas. If the film thickness is
increased, area (A) would be increase
0
and electrical capacitance would be
-20
increased (C=A/l, C = electrical
-40
capacitance, =dielectric constant, A=
2000
3000
4000
5000
area,
l=length between electrode). But
Thickness (Angstrom)
the change rate of electrical capacitance
is decreased, while film thickness
Figure 6. The change rate of electrical capacitance
increase from 2,000 to 5,000 in air
with concentration of gas, when film thickness are
level (atmosphere 30C)
change at room temperature.
For the result of temperature in Fig. 7, the temperature of film increase from 10C to 90C. So, the
change rate of electrical capacitance is increased. At the concentration = 10,000 ppm of Oxygen
(O2) gas, the change rate of electrical capacitance is 2%. At the concentration = 20% of ethyl
alcohol (C2H5OH), the change rate of electrical capacitance is 7%. At the concentration = 20% of
ammonia (NH3), the change rate of electrical capacitance is 7.5%. The best response is ammonia
(NH3).
When the temperature is increased, dielectric constant would be decrease and electrical
capacitance is decreased, so the change rate of electrical capacitance is increased.

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Change rate of Capacitor (%)

100

Oxygen
ethyl alcohol
ammonia

80
60
40
20
0
-20
-40
-60
10

30

50

70

90

Temperature (degree Celsius)

Figure 7. The change rate of electrical capacitance with concentration of gas, when temperature are
change at the concentration = 10,000 ppm of Oxygen, 20% of ethyl alcohol, 20% of ammonia
Summary
For this experiment, in the ratio silicon dioxide (SiO2) : carbon nanotube (MWCNTs) = 100:1 by
weight, the thickness of film at 2,000A and the temperature of film at 90C, they have the change
rate of electrical capacitance at the highest rate.
Acknowledgment
The author would like to thank Electronics Research Center, National Science and Technology
Development Agency (NSTDA) and National Electronics and Computer Technology Center
(NECTEC) support in research. Finally, this work might not have been possible the Thailand
Graduate Institute of Science and Technology (TGIST) support in Scholarship.
References
[1]
[2]
[3]

[4]
[5]
[6]
[7]
[8]
[9]

W. A. de Heer, A. Chatelain, and D. Ugarte: Science Vol. 270 (1995), p. 1179.


R. Martel, T. Schmidt, H. R. Shea, T. Hertel, and Ph. Avouris: Appl. Phys. Lett. Vol. 73
(1998), p. 2447.
R. H. Baughman, C. Cui, A. A. Zakhidov, Z. Iqbal, J. N. Barasci, G. M. Spinks, G. G.
Wallace, A. Mazzoldi, D. de Rossi, A. G. Rinzler, O. Jaschinski, S. Roth, and M. Kertesz:
Science Vol. 284 (1999), p. 1340.
J. Kong, N. R. Franklin, C. Zhou, M. G. Chapline, S. Peng, K. Cho, and H. Dai: Science Vol.
287 (2000), p. 622.
M. Bienfait, B. Asmussen, M. Johnson, and P. Zeppenfeld: Surf. Sci. Vol. 460 (2000), p. 243.
E. Ivers-Tiffee, K. H. Hardtl, W. Menesklou, and J. Riegel: Electrochim. Acta. Vol. 47
(2001), p. 807.
S. L. Well and J. DeSimone: Angew. Chem. Int. Ed. Vol. 40 (2001), p. 518.
T. Lindgren, D. Norback, K. Anderson, and B. Dammstrom: Aviation, Space, Environ. Med.
Vol. 71(8) (2000), p. 774.
H.-E. Endres, R. Hartinger, M. Schwaiger, G. Gmelch, and M. Roth: Sens. Actuators B Vol.
57 (1999), p. 83.

Advanced Materials Research Vols. 55-57 (2008) pp 265-268


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.265

Application of the PEGDE Modified Silk Fibroin Membrane to


an Amperometric Glucose Biosensor
P. Moonsri1,a, S. Watanesk1,b, R. Watanesk1, H. Niamsup1,Q. Cheng2
and R. L. Deming3
1

Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
2
Department of Chemistry, University of California Riverside, Riverside, CA 92521, USA.

Department of Chemistry and Biochemistry, California State University Fullerton, Fullerton, CA 92834, USA.
a
piyarutto@hotmail.com, bswatanes@chiangmai.ac.th

Keywords: Silk fibroin; PEGDE; Glucose oxidase; Prussian blue; Amperometric biosensor
Abstract. Stable silk fibroin (SF) membranes were prepared by modifying SF with polyethylene glycol
diglycidyl ether (PEGDE) for use as enzyme immobilizing matrix. Morphology, structure, and water
solubility of the modified silk fibroin (MSF) membrane were investigated. SEM images revealed greater
porosity in the MSF membranes. IR spectra confirmed the predominant -sheet conformation when the
PEGDE was greater than 4%. In addition, the MSF membranes were highly insoluble within the pH
range 4 10. An amperometric glucose biosensor was initially constructed using glucose oxidase (GOx)
immobilized on the MSF membrane, coupled to a Prussian Blue (PB) deposited Au electrode. The
response characteristics of the biosensors based on the GOx immobilized onto the 4% and 8% PEGDE
modified SF membranes (4P-MSF and 8P-MSF) and the methanol treated SF membrane (MT-SF) were
investigated. Amperometric measurements at the applied potential of 0.0 V demonstrated that the
glucose biosensor based on the GOx immobilized onto the 4P-MSF membrane exhibited high sensitivity
to glucose with a short response time, less than 3 s. Moreover, the stability of the biosensors based on
the 4P-MSF membranes was better than those based on the MT-SF membrane after 2 weeks of storage
in a phosphate buffer of pH 7.0 at 4 C. These fundamental electroanalytical features of the sensor are
therefore expected to be useful in biosensor application
Introduction
SF membrane prepared by dissolving silk fibers of silk worm, Bombyx Mori, exhibits numerous
advantages, including easy preparation, biocompatibility, high oxygen permeability, and increased
enzyme activity, over other biopolymers and some synthetic polymers for enzyme immobilization.
Enzymes i.e. glucose oxidase, peroxidase, and uricase have been immobilized onto SF membrane with
high sensitivity [1]. Generally, stabilization of the immobilized enzyme and the SF membrane can be
carried out by methanol treatment, but the membrane becomes rigid and brittle when exposed to
ambient air. To overcome this problem, improvement of its physical properties has been carried out by
modification with chemical agents such as polyvinyl alcohol, chitosan, and polyethylene glycol [2-3].
In this work, a low molecular weight PEGDE was used for SF membrane modification and its
morphology, structure, and water solubility were investigated. The GOx was immobilized on the MSF
membrane and then deposited onto the PB modified Au electrode. The glucose sensors characteristics,
current response and stability have been tested under a variety of conditions.
Experimental
Materials. Silk waste was obtained from Jun Mai Thai Co., Ltd, Thailand. Glucose oxidase (GOx,
E.C.1.1.3.4), type VII, from Aspergillus niger (198,000 units.g-1) and PEGDE were purchased from
Sigma-Aldrich Co. All chemicals were of reagent grade.
SF membrane preparation and modification. Silk waste was degummed by 0.5 % w/v Na2CO3
solution at 98-100 0C. SF solution was prepared by dissolving 10 g of the degummed silk waste in
100 ml of CaCl2-ethanol-water (1:2:8 of mole ratio) solution at 110 5 0C for 2 h. Then the solution

266

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was filtered and dialyzed against distilled water for 3 days [4]. The SF membrane was prepared by
pouring 20 ml of the SF solution into a polystyrene dish (54 cm2) and drying at 60 0C for 9 h. The
PEGDE modified SF membranes were prepared as described above, but using the mixed solution of
the SF solution and PEGDE in various composition of 4% and 8% w/v of PEGDE/SF instead.
Membrane investigation. Membrane morphology and structure were characterized by scanning
electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively.
Water solubility was determined spectroscopically in term of protein loss by measuring the
increment of its absorbance at 276 nm of 10 ml aqueous solution at pH 4-10 in contact with 250 mg
of the membranes after shaking for 60 min and standing for 24 h at room temperature.
Enzyme electrode preparation. A gold disk electrode (1.6 mm ) was modified with a PB film by
electrochemical deposition at +0.40 V of a solution containing 2 mM each of K3[Fe(CN)6] and FeCl3
in a mixture solvent of 0.1 M KCl and 0.01 M HCl [5] for 80 s. The electrode was then stabilized
by immersing in the mixture solvent, where the electrode potential was cycled between -0.1 and 0.9 V
at a scan rate of 50 mV s-1. The enzyme electrode prepared by mixing the PEGDE solution and the
SF solution at appropriate composition (4% or 8% PEGDE). Then 8 mg of GOx enzyme was
thoroughly mixed with 0.25 ml of the PEGDE/SF solution. After that 20 l aliquot of the mixture
was spreaded onto the surface of the PB modified Au electrode and dried under ambient conditions.
For the electrode of GOx immobilized onto the SF membrane without PEGDE, the electrode was
immersed in 75% ethanol for 5 min to stabilize the membrane [6]. The electrodes were stored at 4 0C
in a 0.1 M potassium phosphate buffer at pH 7.
Electrochemical measurements. All electrochemical measurements were carried out using a
workstation (CH Instrument, USA) fitted with a conventional three-electrode system. The GOx
immobilized membrane deposited onto the PB modified Au electrode was the working electrode,
Ag/AgCl in 3 M NaCl was the reference electrode and a Pt wire was the auxiliary electrode. All
measurements were carried out in 20 ml of 0.1 M phosphate buffer solution with gentle stirring.
Kinetic property of the glucose biosensor. The apparent Michaelis-Menten constant Kmapp and the
maximum current response value, Imax, were determined from the plot of 1/Is vs. 1/[S], for the raw
data fitted to the modified Michaelis-Menten Eq. 1 [7]:
(I [S])
(1)
I s = max
(K m + [S])
where Is is the steady-state catalytic current (A) and [S] refers to the molar substrate concentration.
Results and Discussion
Membrane investigation
Fig. 1 shows SEM images of the cross-section of the membranes. For the SF membrane, a dense surface and
some large pores are observed (Fig. 1a), whereas the 4P-MSF membrane possesses more porosity (Fig. 1b).
However, at higher composition of PEGDE up to 8%, the membrane exhibits a dense skin layer (Fig. 1c).

(c)
(a)
(b)
Figure 1. SEM images of the SF membrane (a), the 4P-MSF membrane (b) and the 8P-MSF membrane (c).
IR spectra of the membranes are shown in Fig. 2. The SF membrane shows absorption bands of amide I
(C=O stretching) at 1652 cm-1, amide II (N-H bending vibration) at 1542 cm-1 and amide III (C-N
stretching) at 1242 cm-1, respectively. These peaks are assigned to be Silk I structure (-helix and
random coil structure). Comparing to the SF membrane, all the amide peaks of MSF membranes

Advanced Materials Research Vols. 55-57

267

show the red-shift; amide I at 1627 cm-1, amide II at 1522 cm-1 and amide III at 1234 cm-1. These new
positions are assigned to be Silk II structure (-sheet structure) [3-4].
The water solubility of the membranes in the pH range of 4-10 were determined. Fig. 3, shows the
results after exposuring the membranes into aqueous solutions at room temperature for 24 h. The SF
membrane lost almost 10-13 % of its protein due to the existence of unstable structure I in the
membrane. Whilst for the MSF membranes, increasing amount of PEGDE further decreased this loss
down to about 2%. This due partially to the conversion of the protein structure from Silk I structure to
the less soluble Silk II structure [4]. The decreased solubility makes the membrane more suitable for the
biosensor applications involving aqueous solutions near pH 7.

Figure 2. IR spectra of SF and MSF membranes

Figure 3. Water solubility of the membranes vs pH.

The response characteristics of the glucose biosensor


The effect of pH of the glucose solution sample on the sensitivity (A mM-1 cm-2) of the glucose
biosensors based on GOx immobilized onto the membranes were studied at 0.0 V over the pH range of
GOx working (pH 6.4-7.6) in a 0.1 M phosphate buffer at 40 0C.

Figure 4. Sensitivity of glucose sensors vs pH.

Figure 5. Sensitivity of glucose sensors vs temperature.

As shown in Fig. 4, the sensitivity of all glucose sensors highly occurs at pH 7.0. Therefore, the
optimum pH for glucose measurement using the GOx immobilized is 7.0, similar to that of the free
enzyme. In addition, it is well documented that the PB film provides lower sensitivity at basic pH values
[8]. The effect of temperature on the sensitivity of the glucose sensors was also studied at 0.0 V using
the phosphate buffer pH 7.0 over the temperature range 25-45 0C (Fig. 5). Electrode sensitivity
gradually increases throughout the range of 25-40 0C. At above 40 0C the change of sensitivity is
insignificant. Therefore the optimum temperature for glucose determination was selected to be 40 0C.
The amperometric measurement of the glucose sensors were carried out under the optimal conditions.
Fig. 6 shows the reductive current response (GOx-4P-MSF membrane) that decreases with each
addition of the glucose. This current is stabilized to 95% of the steady state current within 3 s after
each addition. The current response shows its linearity up to 1.4 mM glucose for all of membranes
(Fig. 7), but the sensor with 4P-MSF membrane shows the steepest slope. A detection limit
calculated from signal-to noise ratio (S/N=3) found to be 10-2 mM for this system. Moreover the

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sensors stability based on the 4P-MSF membrane was better than those based on the MT-SF
membrane after 2 weeks of storage in phosphate buffer of pH 7.0 at 4 0C (Fig. 8).
Kinetic properties of the enzyme electrodes
The Kmapp and Imax were determined from the modified
Michaelis-Menten equation. The Kmapp was found to
be 3.51, 3.76, and 2.71 mM and the Imax was found to
be 4.31, 3.32, and 2.13 A for the glucose sensors
based on 4P-MSF membrane, MT-SF membrane,
and 8P-MSF membrane, respectively. The results
Figure 6. Amperometric responses obtained suggest that the 4P-MSF membrane may have a higher
glucose concentration inside the membrane compared
upon the addition of glucose solution.
to the others because the 4P-MSF membrane possesses
more open or more porous structure than the others
[7].
Summary
The MSF membrane prepared by modifying SF with
4% PEGDE is the most stable that can be noticed from
its low solubility. The glucose biosensor prepared by
immobilizing GOx in the MSF membrane coupled to
the PB coated gold electrode proved to provide high
sensitivity and long-term stability. The GOx
.
immobilized onto the 4P-MSF membrane performed
Figure 7. Response currents of the glucose
better in all respects compared to the sensors based on
sensors.
the GOx immobilized onto the MT-SF and the 8P-MSF
membranes. Under the optimal operating conditions,
the GOx immobilized onto the 4P-MSF membrane
sensor exhibited a linear response up to 1.4 mM, with
the detection limit of 10-2 mM with a response time of
less than 3 s. Thus, the sensor offers favorable
analytical features for the glucose determination.
Acknowledgement
This work was partially supported by the Graduate
School of Chiang Mai University; and the Center for
Figure 8. Stability of the glucose sensors of
Innovation in Chemistry: Postgraduate Education and
storage in a phosphate buffer solution pH 7.0 Research Program in Chemistry, Thailand. Thanks are
at 40 0C
also due to the Phetchabun Rajabhat University for
financial support to Mr. Moonsri.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

Y-Q. Zhang: Biotech. Adv. Vol. 16 (1998), p. 961.


G. Freddi, M. Romano, M. R. Massafra and M. Tsukada: J. Appl. Polym. Sci. Vol. 56 (1995), p.
1537.
M. Li, W. Tao, S. Lu and S. Kuga: Int. J. Biol. Macromol. Vol. 32 (2003), p. 159.
P. Moonsri, R. Watanesk, S. Watanesk, H. Niamsup and R. L. Deming: J. Appl. Polym. Sci. Vol. 108 (2008),
p. 1402.
M. Ferreira, P.A. Fiorito, O.N. Oliveira Jr and S.I. Crdoba de Torresi: Biosens. Biolectron. Vol.19 (2004),
p. 1611.
Y-Q. Zhang, W-D. Shen, R-A. Gu, J. Zhu and R-Y. Xue: Anal. Chim. Acta. Vol. 369 (1998),
p.123.
Y. Liu, X. Zhang, H. Liu, T. Yu and J. Deng: J. Biotech. Vol. 46 (1996), p. 131.
F. Ricci and G. Palleschi: Biosens. Bioelectron. Vol. 21 (2005), p. 389.

Advanced Materials Research Vols. 55-57 (2008) pp 269-272


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.269

Enhanced the Performance of Fluorescence Gas Sensor of Porphyrin


Dye By Using TiO2 Nanoparticles
N. H. Yusoffa, M. M. Sallehb and M. Yahayac
Institute of Microengineering and Nanoelectronics
Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
a

nhudayusoff@yahoo.com, mms@ukm.my, myahya@ukm.my

Keywords: porphyrin dye, TiO2 nanoparticles coated with dye, fluorescence gas sensor.

Abstract. Fluorescence gas sensor was developed to identify the presence of volatile organic
compounds by using porphyrin dye thin film. The porphyrin dye used was iron (III) mesotetraphenylporphine chloride. The porphyrin thin film was deposited on quartz substrate using selfassembly through dip coating technique. The sensing properties of the thin films toward volatile
organic compounds; ethanol, acetone and 2-propanol were studied using luminescence
spectrometer. In presence of air and volatile organic compounds, thin films produced different
emission spectra and ease for chemical identification process. To improved the sensing
performance, TiO2 nanoparticles colloid were prepared, coated with porphyrin dye and deposited as
thin film. It was found that the thin film of TiO2 nanoparticles coated with porphyrin dye has more
intensive interaction toward volatile organic compounds than porphyrin thin film, and improved the
selective property. This may be due to the nanostructured thin film provided more surface area for
dye molecules to react with VOCs.
Introduction
Volatile Organic Compounds (VOCs) are organic chemicals that easily vaporize at room
temperature. VOCs are emitted as gases by a wide array of products such in paints, cleaning
supplies, pesticides and building materials. Long exposure time to the VOCs cause bad health effect
and cancer for human. Hence, it is very important to have a sensor for identification of the
hazardous VOCs. Recently, sensor base on optical sensing technique has received growing interest
as an alternative to sensors based on electrical resistance that operates at high temperature. Various
techniques have been employed, which include fluorescence [1], UV-VIS absorption [2], refractive
index [3] and surface plasmon resonance (SPR) [4]. Fluorescence gas sensor offers several
advantages over other methods such as sensitivity, high efficiency and specificity. It has been sought
for huge potential applications in food quality control [5], medical [6] and environmental [7].
Chemical dyes made of porphyrins and their related compounds were among the most
prospective candidate for development of gas sensor system. These chemicals have shown good
sensitivity to most volatile compounds through optical sensing techniques. Their interesting features
in the interactions with the gaseous molecules have been widely described elsewhere [8]. Recently,
there have been many efforts carried out to improve the response properties of the sensing element
to the presence of the gaseous molecules. A most straightforward strategy is to modify the
nanostructure of the sensor surface. This procedure is believed to be able to directly adjust the
properties of the sensor surface, such as surface molecular density and surface roughness, which in
turn improve their sensing properties [9]. One of the techniques to modify the nanostructure of the
sensor surface is by incorporate nanoparticles such as TiO2 in the thin film sensing material.
This paper reports the performance of fluorescence gas sensor of porphyrin dye towards volatile
organic compounds, which are ethanol, acetone and 2-propanol. The sensing sensitivity was based
on the changes of photoluminescence spectra of thin film in presence of volatile organic
compounds. The effect of incorporate TiO2 nanoparticles in the porphyrin thin films was studied.

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Experimental
Porphyrin dye used for sensing material was iron (III) meso-tetraphenylporphine chloride. The
colloidal solution of dye in toluene was prepared at a concentration of 0.2 mg/ml. Meanwhile, TiO2
nanoparticles colloid was synthesized from titanium (IV) ethoxide in ethanol with addition of
kalium chloride (KCl) as stabilizer [10] with some modifications. Firstly, ethanol was mixed with
KCl and stirred for one hour to get a complete mixture. Then, titanium ethoxide was dropped wisely
to the admixture solution in glove box under nitrogen atmosphere and humidity at 15%.
Acetylaceton was dropped into the solution at room temperature and stirred for two hours to form a
clear, transparent yellowish solution. To prepare TiO2 nanoparticles coated with porphyrin dye, the
porphyrin solution was added drop wisely into the TiO2 solution and stirred for one hour to obtain a
complete mixture of porphyrin and TiO2 nanoparticles colloidal solution. The volume ratio of
porphyrin to TiO2 was 2 to 1.
The thin films of porphyrin dye and TiO2 nanoparticles coated with porphyrin were deposited
onto quartz substrate using self-assembly technique. The clean quartz substrate was immersed in
Poly-L-Lysine (PLL) solution for 30 minutes to charge the surface into positive charge. Then, the
substrate was rinse with deionized water. Using KSV Dip coating system, the substrate was dipped
into the colloidal. The substrate was kept in the colloid for 30 minutes and lifted up at a constant
speed of 15 mm/min. One bilayer of porphyrin dye and TiO2 nanoparticles coated with dye thin
films was formed on the substrate surface. The prepared thin films were characterized using
scanning electron microscopy (SEM) to study the formation of nanoparticles and measure the size
of nanoparticles. The surface morphology of thin film was recorded using atomic force microscopy
(AFM). Luminescence spectrophotometer was used to measure emission spectra of the thin films.
The sensing properties of the thin films toward volatile organic compounds; ethanol, acetone
and 2-propanol were studied using Perkin Elmer luminescence spectrophotometer. The
experimental set-up depicted in Fig. 1. Nitrogen flow is used to carrier gas bubbling through a glass
balloon flask containing 10 ml of VOCs in airflow at rate of 16 ml/min which was control by
Brooks mass flow meter controller. Then, the gases enter the analysis chamber and reach to the
thin films surface, where each thin film will produce photoluminescence spectra with a distinct
emission peaks.

Figure1. Fluorescence gas sensing system setup.


Results and Discussion
Fig. 2 and Fig. 3 show the SEM and AFM images of the porphyrin dye and TiO2 nanoparticles
coated with porphyrin thin films. The averages diameters of nanoparticles that have been
synthesized and surface roughnesses obtained from these images were 20.21 nm and 2.167 nm
respectively for porphyrin dye thin film, and 15.21 nm and 10.50 nm respectively for TiO2
nanoparticles coated with dye thin film. The grain size and surface roughness are important
parameters to determine the sensing sensitivity of the thin film towards VOCs.

Advanced Materials Research Vols. 55-57

(a)

271

(b)

Figure 2. SEM images of (a) porphyrin dye and (b) TiO2 nanoparticles coated porphyrin dye thin
films. Scale bar is 100 nm.

(a)

(b)
2

Figure 3. Three-dimensinal AFM images in the areas of 1x1 (m) of (a) porphyrin dye and (b) TiO2
nanoparticles coated porphyrin dye thin films.
Fig. 4 compares the emission spectra of porphyrin dye and TiO2 nanoparticles coated porphyrin dye
thin films. The emission spectrum of the thin film shifted to red with addition of TiO2 nanoparticles.
When exposed to VOCs, both of the thin films undergo change in their fluorescence emission
spectra (Fig. 5).

Figure 4. Emission spectra of porphyrin dye and TiO2 nanoparticles coated porphyrin dye thin films

(a)

(b)

Figure 5. Emission spectra of (a) porphyrin dye and (b) TiO2 nanoparticles coated porphyrin dye
thin films in presence of ethanol, 2-popanol and acetone.

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The changes of emission peak of the thin films from the original either to red shift and blue shift
depended on changes in electronic states between the ground state and excited state of the porphyrin
molecules. These changes could be due to the interaction of porphyrin molecules with volatile
organic compounds molecules that causes rearrangement of the electrical dipole in the porphyrin
compounds of the thin film [8]. A certain circumstance may be created by this activity is the
changes on the energy gap between highest occupied molecular orbital (HUMO) and lowest
unoccupied molecular orbital (LUMO). Thin films before interacting with VOCs molecules
possesses a gap between these two orbital that determines its initial emission upon the excitation
light due to the excited transition of the electrons to the ground state. When an excitation light
source absorbed by the thin films molecules, which interact with gas molecules, it may emits light at
different wavelength peaks.
It was found that, the thin film of TiO2 nanoparticles coated porphyrin dye shows more intensive
interaction with wide selectivity property than porphyrin dye thin film. This may be due to the
nanostructured thin film provided more surface area for dye molecules to react with VOCs. The
sensing experiments using the same thin films were repeated for many times. It was found that no
significant different of the results. This means that the sensor has repeatability property and suitable
to be use as sensing material for identify type of volatile organic compounds.
Summary
Thin films of porphyrin dye and TiO2 nanoparticles coated porphyrin dye were succsessfuly
fabricated using self-assembly technique. In presence of air and volatile organic compounds, the
thin films produced different emission spectra and ease for chemical identification process. The thin
film of TiO2 nanoparticles coated porphyrin produced more intensive interaction with wide
selectivity property than the porphyrin dye thin film. Hence, it is potentially be use as fluorescence
gas sensor.
Acknowledgements
The authors would like to thank the Malaysia Ministry of Science, Technology and Innovation for
the grant Science Fund 03-01-02-SF0359 project.
References
[1]
[2]
[3]

F. S. Mehamod, R. Daik and M. Ahmad: Sensor. and Actuat. B Vol. 96 (2003), p.537.
A.A. Umar, M. M. Salleh and M. Yahaya: Curr. Appl. Phys. Vol. 8 (2008), p. 53.
G. Z. Xiao, A. Adnet, Z. Zhang, F. G. Sun and C. P. Grover: Sensor. Actuat. A Vol. 118
(2005), p. 177.
[4] Rajan, S. Chand and B.D. Gupta: Sensor. Actuat. B. Vol. 123 (2007), p. 661.
[5] M.S. Kim, A.M. Lefcourt, and Y. R. Chen: Proceed. SPIE Vol. 5271 (2004), p. 62.
[6] M.Z.Krecicka, T. Krecicki, M. Fraczek, E.B. Pawlik and T.Zatonski: Otolaryngol Pol. Vol. 59
(2005), p. 195.
[7] S.W. Hong, K.H. Kim, J. Huh, C. H. Ahn, and W.H. Jo: Chem. Mater. Vol 17 (2005), p.
6213.
[8] Akrajas, M. M. Salleh and M. Yahaya: Sensor. Actuat. B Vol. 85, (2002) p. 191.
[9] A.Umar, M.M. Salleh and M. Yahaya: Eur. Phys. J. Appl. Phys. Vol. 29 (2005) p. 215.
[10] S. E. Assmann, J. Widoniak and G. Maret: Chem. Mater Vol. 16 (2004), p. 6.

Advanced Materials Research Vols. 55-57 (2008) pp 273-276


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.273

Determination of Mn Site in BaTiO3 by X-Ray Absorption Spectroscopy


R. Yimnirun1,a, J. Tangsritrakul1, S. Rujirawat2, and S. Limpijumnong2
1

Department of Physics, Faculty of Science, Chiang Mai University,


Chiang Mai 50200 Thailand

National Synchrotron Research Center, Nakhon Ratchasima 30000, Thailand, and School of
Physics, Suranaree University of Technology, Nakhon Ratchasima 30000, Thailand
a

rattikornyimnirun@yahoo.com

Keywords: X-Ray Absorption Spectroscopy, Mn-Doped BaTiO3

Abstract. In this work, an experimental X-ray Absorption Spectroscopy (XAS) measurement was
employed to determine the local structure of Mn in BaTiO3. Synchrotron X-ray absorption nearedge structure (XANES) experiments were performed on Mn-doped BaTiO3 samples. The
BaTi0.8Mn0.2O3 powders were used for the XAS experiment. XAS spectra at the Mn K-edge were
recorded in transmission mode. The spectra were collected at ambient temperature with a Ge(111)
double crystal monochromator and recorded after performing an energy calibration. The features of
the measured Mn K-edge XANES were consistent with Mn on the Ti site and inconsistent with Mn
on other sites. The clear agreement was the strongest evidence of Mn substituting for Ti in BaTiO3.
Introduction
Barium titanate (BaTiO3 or BT), which exhibits a perovskite structure and a Curie temperature ~
120 C, is a classical ferroelectric material that has been extensively exploited both for academic
and for technological utilizations over the past decades [1, 2]. Owing to its high dielectric constant,
large mechanical-quality factor, large pyroelectric coefficient, non-toxic handling and low cost of
manufacturing, compared to several lead-based perovskite ferroelectrics, ceramics based on BT
have been strong candidates for several electronic applications [3]. BaTiO3 has various polymorphs,
all of which are based on the perovskite structure (ABO3); however, due to its high permittivity,
ferroelectric t-BaTiO3-based materials have received the most attention. We have known very little
about the electrical properties and defect chemistry of the high temperature hexagonal (6H)
polymorph, h-BaTiO3, which is stable above ~1460 C in undoped BaTiO3 [4]. In part, this is due to
undoped hexagonal BaTiO3 being metastable at room temperature. The 6H-BaTiO3 structure has
been reported by Bourgeois in 1883 as space group P63/mmc with lattice parameters a = 5.723
and c = 13.9649 [5]. It is known that the addition of 3d transition metal (e.g. Mn, Fe, Co and Ni)
enhances the positive temperature coefficient of resistance of BaTiO3. With such transition metal
dopants, the hexagonal polymorph can be formed at room temperature. To date, the reason for
stabilization of doped 6H-BaTiO3 has not been concluded yet. Mn is found to be one of the most
effective dopants. Some researchers believed that Mn substitutes Ti site and acts as an acceptor.
Recent works have shown that the Mn valence states depend on the growth condition and are yet to
be understood. The valence states of Mn in BaTiO3 have been reported to varied from +4 to +2
depending on oxygen partial pressure during the formation of crystal. Since the valence state of Mn
plays an important role in determining the crystal structure and over all properties of Mn-doped
BaTiO3, therefore, it is important to identify the local structure of Mn in BaTiO3 lattice.
X-ray absorption spectroscopy (XAS) is proven to be a very powerful technique for resolving
the local structure surrounding a particular (absorbing) atom. Traditionally, XAS is divided into
two regions: (1) the low energy region, which covers photon energy up to about 40 eV above the
absorption edge, called the X-ray absorption near-edge structure (XANES) and (2) the higher
energy region from 40 eV up to ~1000 eV above the absorption edge, called the extended X-ray
absorption fine structure (EXAFS) [6]. While both regions of XAS contain information on the

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arrangement of the neighboring atoms surrounding the absorbing atom, the final states in the
absorption process for these two regions are fundamentally different. The XANES region
corresponds to the excitation of a core electron to unoccupied bound states or low lying continuum
states, and a simulation of XANES requires detailed knowledge of the local electronic state density
near the absorbing atom. The information on the arrangement of neighboring atoms contained in
XANES is no less extensive than that contained in EXAFS. It is also strongly sensitive to the
chemical and coordination of the neighbors. In this work, we propose to carry out an experimental
investigation of the XAS measurement (especially in the XANES region) to determine the local
structure of Mn in BaTiO3 ceramics.
Experimental
Ba(Ti1-xMnx)O3 powders with x = 0.01 to 0.2 were prepared by a conventional mixed-oxide method
raw materials BaCO3 (Fluka,99.0% purity), TiO2 (Riedel-de Han, 99.0% purity) and MnO2
(Sigma-Aldrich, Inc., 99.999%) were mixed and vibro-milled in ethyl alcohol for 1 hour and then
oven dried overnight at 120 C. After drying, the powders were calcined at 1250 C for 2 hours
with 5 C/min heating rate and cooling rate. The calcined powders were pressed into disk-shaped by
uniaxial hydraulic press at pressure of 0.5 tons to form the green pellet of 1 cm diameter. The green
pellets were placed on the alumina powder inside an alumina crucible then heat treated at 500 C
for 1 hour to eliminate the PVA, followed by sintering at temperatures between 1350 to 1450 C for
2 hours with 5 C/min heating rate and cooling rate. Phase identification of Ba(Ti1-xMnx)O3
ceramics was performed by X-ray diffraction (XRD). The BaTi1-xMnxO3 powder samples were used
for the XAS experiment. XAS spectra at the Mn K-edge were recorded in transmission mode using
the facility of BL-8 at SPL, as shown in Fig. 1. The spectra were collected at ambient temperature
with a Ge(111) double crystal monochromator and recorded after performing an energy calibration.
To increase the count rate, the ionization chamber was filled with Ar gas. The SPS storage ring was
running at an energy of 1.2 GeV with electron currents between 80 mA and 30 mA.

Figure 1. XAS experimental set-up.


Results and Discussion
The XRD patterns of Ba(Ti1-xMnx)O3 ceramics showed that the crystal structure at room
temperature changed from tetragonal to hexagonal as Mn concentration increased. The sample with
x = 0 shows the tetragonal phase, while x = 0.01, the amount of hexagonal phase and small amount
of Ba2Ti5O12 occurred. When x increased from 0.02 to 0.2, it was found that Ba2Ti5O12 disappeared
and the extent of hexagonal phase increased with increasing Mn substitution with complete
hexagonal phase when x reached 0.1, as shown in Fig. 2.

Advanced Materials Research Vols. 55-57

275

Figure 3 shows the experimental Mn K-edge XANES spectrum of BaTi0.8Mn0.2O3 taken at SPL
(solid line) compared with the spectrum of Mn2O3 (dashed line). This clearly indicates the similarity
between the two spectra.

Figure 2. XRD patterns of Ba(Ti1-xMnx)O3 ceramics with x = 0.01 to 0.2.


0.05
0.045
0.04

o
o

Absorption [a.u]

0.035

2.0 A

3.5 A

0.03
0.025
0.02
0.015
0.01
0.005
0
6510

6520

6530

6540

6550

6560

6570

6580

6590

6600

Photon energy [eV]

Figure 3. The experimental Mn K-edge XANES spectrum of BaTi0.8Mn0.2O3 taken at SPL (solid
line) compared with the spectrum of Mn2O3 (dashed line): Inset is the possible site of Mn atom in
the BaTiO3 unit cell (MnTi).
Figure 4 shows the normalized Mn K-edge XANES spectra measured from Mn-doped BT samples
with the Mn concentrations of 5%, 10%, 15%, and 20% with standard MnO2 powder for
comparison. The fact that all spectra contain the same main features implies that the majority of Mn
atoms assume the same lattice locations in these samples, with the possible site of Mn atom B-site
(Ti) in the BaTiO3 unit cell (MnTi).
The obtained experimental XAS spectra were fitted with the theoretical spectra using a novel
method developed at SPL [7]. XANES is very sensitive to the local structure around the interested
atom. Recent research at SPL suggested that it is possible to extract the local structure around Mn
atoms using the similar kind of XANES spectrum [8]. The preliminary theoretical calculation
results indicate a good agreement with the experimental results, both of which show Mn
substituting for Ti in BaTiO3.

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Figure 4. The experimental Mn K-edge XANES spectra of Ba(Ti1-xMnx)O3 powders with x = 0.05
to 0.2.
Summary
In this work, an experimental X-ray Absorption Spectroscopy (XAS) measurement was employed
to determine the local structure of Mn in BaTiO3. Synchrotron X-ray absorption near-edge structure
(XANES) experiments were performed on Mn-doped BaTiO3 samples. The BaTi0.8Mn0.2O3 powder
samples were used for the XAS experiment. XAS spectra at the Mn K-edge were recorded in
transmission mode. The spectra were collected at ambient temperature with a Ge(111) double
crystal monochromator and recorded after performing an energy calibration. The features of the
measured Mn K-edge XANES were consistent with Mn on the Ti site and inconsistent with Mn on
other sites. The clear agreement was the strongest evidence of Mn substituting for Ti in BaTiO3.
Acknowledgment
This work was supported by the National Synchrotron Research Centre (NSRC), Thailand under
contact No. 2550/02 and PS04/2550.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]

A. J. Moulson and J. M. Herbert: Electroceramics: Materials, Properties, Applications (John


Wiley & Sons Ltd., Chichester, 2003).
K. Uchino: Ferroelectric Devices (Marcel Dekker, New York, 2000).
T. R. Shrout and J. P. Dougherty: Ceramic Transactions Vol. 8 (1990), p. 3.
K. W. Kirby and B. A. Wechsler: J. Am. Ceram. Soc. Vol. 74 (1991), p. 1841.
J. Akimoto, Y. Gotoh and Y. Oosawa: Acta Cryst. Vol. C50 (1994), p. 160.
D.C. Koningsberger and R. Prins: X-ray Absorption: Principles, Applications, Techniques of
EXAFS, SEXAFS and XAES (John Wiley & Sons, New York, 1988).
A. Boonchun, M. F. Smith, B. Cherdhirunkorn, and S. Limpijumnong: J. Appl. Phys. Vol.
101 (2007), p. 043521.
S. Limpijumnong, S. Rujirawat, A. Boonchun, M. F. Smith, and B. Cherdhirunkorn: Appl.
Phys. Lett. Vol. 90 (2007), p. 103113.

Advanced Materials Research Vols. 55-57 (2008) pp 277-280


(2008) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.55-57.277

Changes in Ferroelectric Properties of 0.7PMN0.3PT Ceramic with


Compressive Stress
M. Unruana, R. Wongmaneerungb, Y. Laosiritawornc,
S. Anantad and R. Yimnirune
Department of Physics, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand
a

muangjaiunruan@yahoo.com, bre_nok@yahoo.com, cyongyut_laosiritaworn@yahoo.com


d

suponananta@yahoo.com, erattikornyimnirun@yahoo.com

Keywords: Ferroelectric properties, PMN-PT, Compressive stress

Abstract. In this work, effects of compressive stress on the ferroelectric properties of 0.7PMN
0.3PT ceramics were investigated. The ceramics with the formula (0.7)Pb(Mg1/3Nb2/3)O3(0.3)PbTiO were prepared by a conventional mixed-oxide method. The ferroelectric properties
under compressive stress were observed at stress up to 80 MPa using a compressometer in
conjunction with a modified Sawyer-Tower circuit. The results showed that applied stress had a
significant influence on the ferroelectric properties of 0.7PMN0.3PT ceramics. Ferroelectric
characteristics, i.e. the area of the ferroelectric hysteresis (P-E) loop, the saturation polarization
(Psat), the remanent polarization (Pr) and loop squareness (Rsq), decreased with increasing
compressive stress, while the coercive field (Ec) remained relatively constant. Stress-induced
domain wall motion suppression and non-180oC ferroelectric domain switching processes are
responsible for the changes observed.
Introduction
Ferroelectric ceramics have been established as good candidates for actuator and transducer
applications. Widely used materials include barium titanate (BaTiO3 or BT) and lead-based
materials such as lead magnesium niobate (Pb(Mg1/3Nb2/3)O3 or PMN) and lead zirconate titanate
(Pb(Zr1_xTix)O3 or PZT) [1]. As a prototypic relaxor ferroelectric, PMN exhibits a high dielectric
constant and a broad range transition of dielectric constant with temperature as a function of
frequency [2]. The main feature of the dielectric properties of PMN is a broad and frequencydependent dielectric constant peak just below room temperature. This behavior is typical of relaxor
ferroelectrics. The dielectric properties of PMN can be enhanced by the addition of PbTiO3 (PT)
[3,4]. PMN-PT materials are useful in electrostrictive actuator applications because of their large
electric-field-induced strains [5]. This system also has a morphotropic phase boundary (MPB) about
0.7PMN0.3PT. The compositions near MPB of PMNPT system exhibit unusual high dielectric
permittivity, low dielectric loss and high strain. It is a very promising material for the applications
of multilayer ceramic capacitors as well as ceramic electrostrictive actuators and electro-mechanical
transducers [6]. In many of these applications, the ceramics are often subjected to mechanical
loading, either deliberately in the design of the device itself or the device is used under
environmental stresses. Despite this fact, material constants used in any design calculations are
often obtained from a stress-free measuring condition, which in turn may lead to incorrect or
inappropriate actuator and transducer designs [7]. It is therefore important to determine the
electrical properties of 0.7PMN0.3PT ceramics as a function of applied stress. Thus far, there have
been no systematic studies on the ferroelectric properties of 0.7PMN0.3PT ceramics. Therefore,
this work will be the first to investigate the dependence of hysteresis loop with stress for 0.7PMN
0.3PT ceramic. The major purpose of this work is to report the result of P-E hysteresis loops of
0.7PMN-0.3PT ceramic under various compressive stress and to discuss these new experimental
results. Moreover, the ferroelectric data, i.e. the saturation polarization (Ps), the remanent

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polarization (Pr), the coercive field (Ec) and the loop squareness (Rsq), of 0.7PMN0.3PT ceramic
under compressive stress will also be reported.
Experimental
Investigations were performed on 0.7PMN0.3PT ceramics produced by the conventional mixed
oxide method [8]. Disc samples with a diameter of 12.5 mm and a thickness of 0.8 mm were chosen
for the electrical measurements and the samples were electroded by silver painting.
The ferroelectric hysteresis (P-E) loop were characterized by using a computer controlled
modified Sawyer-Tower circuit. The electric field was applied to a sample by a high voltage ac
amplifier with the input sinusoidal signal with a frequency of 60 Hz from a signal generator
(Goodwill, model GAG-809). To study the effect of the compressive stress on the ferroelectric
properties, the uniaxial compressometer was constructed. The detailed descriptions of this system
are explained elsewhere [7]. During the measurements, the specimen was immersed in silicone oil
to prevent high-voltage arcing during electric loading. Measurements were performed as a function
of mechanical stress applied discretely between 0 and 80 MPa. The ferroelectric hysteresis (P-E)
loop was recorded at room temperature (25oC). The parameters obtained from the loops were the
saturation polarization (Ps), the remanent polarization (Pr), and the coercive field (Ec), which are
defined as the points where the loops reach the maximum polarization, cross the zero field and the
zero polarization, respectively.
Results and Discussion
The polarization versus electric field (P-E) hysteresis loops of the 0.7PMN0.3PT ceramics under
different compressive stress are shown in Fig. 1. It should first be noted that the area of these P-E
hysteresis loops slightly decreases with increasing stress. The P-E loop area represents the unitvolume polarization dissipation energy of a ferroelectric material subject to one full cycle of electric
field loading [9].

Figure 1. Polarization versus electric field


(P-E) hysteresis loops as a function of
compressive stress for 0.7PMN-0.3PT
ceramic.

Figure 2. Changes in dissipation energy


(hysteresis loop area) with compressive
stress for 0.7PMN-0.3PT ceramic.

The change in polarization dissipation energy is plotted in Fig. 2 as a function of compressive stress,
in which the dissipation energy is found to decrease linearly with the stress increment. The
polarization dissipation energy is also termed energy loss consumed for self-heating of the specimen
and related directly to the number of domains participating in the switching process during an
electric loading cycle [10].

Advanced Materials Research Vols. 55-57

279

From Fig. 2, it is clear that the number of domains contributing to polarization reversal gradually
decreases with increasing compressive stress. In the stress-free state (0 MPa), the dissipation energy
is 236 kJm-3, whereas at maximum stress (80 MPa), the dissipation