ABSTRACT OF THESIS

THERMAL DEGRADATION AND AGING OF HIGH TEMPERATURE PIEZOELECTRIC CERAMICS
Piezoelectric materials have numerous applications like high temperature accelerometers, pressure, flow and NDT transducers, acoustic emission, ultrasonic cleaning, welding, high voltage generators, medical therapy etc. The commonly used piezoelectric material, PZT continues to dominate the commercial market for piezoelectric actuators applications. The primary limitations of PZT are the lower Curie temperature TC <3900C and rapid thermal degradation above 2000C. Continuing efforts are focused on the development of piezoelectric materials suitable for high temperature applications >2000C. These materials will be very useful for making sensors for space exploration, oil and geothermal well drilling tools, oil & gas pipeline health monitoring and automotive smart brakes. Recently material based on (1-x)Bi(Me)O3-xPbTiO3 developed with TC~4600C, and d33~500 pC/N compared to TC~3900C and d33~220 pC/N of pure PZT. Enhanced room temperature properties and higher transition temperature makes this material interesting for further investigation as a high temperature piezoelectric material. Reliability of technological piezoelectric devices is a major concern for their applications. Many piezoelectric materials undergo a process of aging, associated with a spontaneous decrease of electromechanical properties. In the current work thermal degradation and aging behavior of high temperature piezoelectric material BSPT was evaluated and compared with the commonly used PZT. KEYWORDS: Aging, Thermal degradation, BSPT, PZT, High temperature piezoelectric.

___________________________ (Sunil Gotmare) Date:

THERMAL DEGRADATION AND AGING OF HIGH TEMPERATURE PIEZOELECTRIC CERAMICS

By Sunil W. Gotmare

Director of Thesis

Director of Graduate Studies Date:

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Gotmare The Graduate School University of Kentucky 2008 .THESIS Sunil W.

Kentucky 2008 © Copyright Sunil W. Gotmare 2008 . Professor of Chemical and Material Science Engineering Lexington. Gotmare Lexington. Richard Eitel. Kentucky Director: Dr.THERMAL DEGRADATION AND AGING OF HIGH TEMPERATURE PIEZOELECTRIC CERAMICS ________________________________________ THESIS ________________________________________ A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Material Science and Engineering in the College of Engineering at the University of Kentucky By Sunil W.

Vandana Gotmare .This work is dedicated to my beloved parent Mr. Wasudeo Gotmare and Mrs.

I am thankful that in the midst of all their activity. John Balk. I express my appreciation and feel extraordinarily fortunate in having equally important support from family and friends. Sincere thanks goes to the faculty and staff of the Chemical and Materials Science Engineering department for the wonderful time in the department. they accepted to be members of my thesis committee. Finally. I wish to thank Dr. Richard Eitel. Many thanks to everyone that I have worked with. and technical guidance at every step and for providing me unflinching encouragement and support in various ways. my wife. Dr. I would like to express my deep and sincere gratitude to my thesis Advisor. advice. whose timely technical assistance benefited in assorted ways to the research. I thank him also for providing me an opportunity to grow as a engineer in the unique research environment and for his valuable supervision. and Dr.ACKNOWLEDGMENTS The following thesis. I wish to thank my research group and colleagues for contributing to a wonderful and memorable graduate school experience at the University of Kentucky. her loving support and understanding at every step. while an individual work. iii . for their advise and constructive comments on this thesis. Bruce Hinds. Shivani for her encouragement and persistent confidence in me. benefited from the insight and direction of several people.

.……….………1 Motivation ………………………………………….…...15 Piezoelectric constant (d) ……………………………..TABLE OF CONTENTS Acknowledgements…………………………………….…...12 Properties of piezoelectric materials …………………………….…ix List of Figures ………………………………………………….……………….…….14 Ferroelectric Curie temperature (TC) …………..…….……..…………………….17 Electromechanical coupling coefficient….…6 Intrinsic and extrinsic contributions …………………………………….………………….....…10 High temperature piezoelectric (1-x)BiScO3-xPbTiO3 ………….16 Dielectric constant (K) and loss (D) …………………………...…x Chapter One: Introduction ……………..……....…….….…………….……..……….……….....……………………..…17 Modification of properties by doping ………………………………….….………….…………………………….…….…….…….…….…………..……...……..…………………………...…….…5 Perovskite Structure ……………………………………………….…………..…....……………..…iii List of Tables ……………………………………………….9 Lead zirconate titanate (1-x)PbZrO3-xPbTiO3 ………………………..……..….18 iv ...…………3 Chapter Two: Background for piezoelectric materials and their aging behavior…………5 Introduction …………………………………..………1 Organization of thesis ……………………………….

22 Diffusion of defects through domain wall and consequent stabilization of domain wall ….………27 Electrode application ……………………………….……..…24 Powder preparation ……………………………………………….……………….31 Piezoelectric constant (d33) ……………….……………………………………………….….….………24 Introduction ……………………………………………..….…28 Structural and physical characterization…….....……..…...31 Planar coupling coefficient (kP) …………………………....…….……26 Sintering ……………………………………….………24 Preparation of piezoelectric ceramics …………………………………..….…….…………….…………….…19 Thermal degradation and aging of piezoelectric materials ………………...…28 Piezoelectric and dielectric characterization…….…………….…27 Poling …………………….31 v .20 Domain wall clamping by defects ………………......…30 Dielectric constant (K) and dielectric loss (D) ……..…………….………..…….…..…29 Polarization – electric field (P-E) hysteresis loop…………..………….……….…….……….Effect of processing on the properties of piezoelectric materials…………….…28 Characterization …………………………………………….…….…..….………22 Presence of space charges at the grain boundaries ………………..…….…….…………..………23 Chapter Three: Experimental procedures and methods ………….…………..………………..……..…..…32 Ferroelectric Curie temperature (TC) …….….….……24 Forming ……………………………….…….………………….……………….…………….

57 Introduction ……………………………………………………….…32 Thermal degradation and aging …………………………..………………58 Isothermal aging …….………………....…...………………55 Chapter Five: Thermal degradation and aging…………………………………...….57 Aging study ……………………………………………………….………….65 Thermal conditioning.…………44 Piezoelectric constant (d33) ………………………………....……………...…59 Thermal conditioning …………….………………………………………………....………34 Physical and structural analysis ………………………...………………………………...……49 Planar coupling coefficient (kP) …………………………………………49 Rayleigh analysis for dielectric and piezoelectric responses ….….…….....………..…………………………………..44 Dielectric constant (K) and dielectric loss (D) ……………….…………………….…43 Poled properties ………………………………………..…………..59 vi .51 Summary and conclusion ……………………………………….33 Chapter Four: Characterization ………………….………………58 Results and discussion …..….….………….………….……………...34 Unpoled properties …………………………………….……..….Rayleigh analysis for dielectric and piezoelectric response ….….....…………42 Ferroelectric Curie temperature (TC) ………………………..…….……..42 Dielectric constant (K) and dielectric loss (D) ….…….………….……42 Polarization – electric field (P-E) hysteresis loop …………………….……34 Introduction ……………………………………………...…………………………………..………...………………….…………….

..…72 Summary …………………………………………………….…62 Dielectric coefficient K and dielectric loss D ……………………….……………………………..67 Summary and conclusion ……………………………….....………76 Methodology for lifetime testing for piezoelectric ceramics ……………77 Appendices: Appendix A: Particle size and distribution for metal oxides / carbonate powders …………………………………………………………………….……………...Piezoelectric constant (d33) ………………………………….81 Appendix D: Sintering study for PZT and BSPT (bulk density..…80 Appendix C: XRD scans for PZT and BSPT powders before and after calcination ..…………...………………..….…76 Aging study for acceptor doped (1-x)BiScO3-xPbTiO3….………………72 Development of methodology for lifetime testing for piezoelectric ceramics ….……….…72 Thermal degradation and aging study for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3ceramics …………..…..…61 Planar coupling coefficient (kP) ………………………………….…62 Rayleigh analysis during aging study …………………………………………..………………………71 Chapter Six: Summary and future work ……………………….…76 Future work …………………………………………...……………….……..………………………………………………………………….for variable time vii ....……………….79 Appendix B: LOI results for metal oxides / carbonate powder………………..………………………......

…...…….82 Appendix E: Dielectric properties of poled sample at various frequencies ….…………….....…………..…...….…83 Appendix F: Details of dielectric properties (1kHz) with the aging time at 2500C ………………………………………………………………….………105 viii .101 Vita …………………………………………………………………...……………….…95 References ………………………………………………………………….……..92 Appendix H: Rayleigh analysis for piezoelectric and dielectric response during aging…….& temperature) …………..…..…84 Appendix G: Details of piezoelectric constant d33 after poling and with the aging time at ……………………………….………………………...…………………………..……….….

1. planar coupling coefficient kp. Measured electromechanical properties of poled (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 pellets ………………………….……………60 Table 5. Electromechanical properties of PZT and BSPT materials ………..65 ix ..3.…………..LIST OF TABLES Table 2.…….. and dielectric constant K for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 (at 2500C) ………………………………………………………….5...2.………….2.. Bulk density for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 after Sintering ………………………………………………………..4.…………40 Table 4. compared to poled properties ……………………………………………….54 Table 5.………15 Table 4.…………37 Table 4. Lattice parameters for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 calculated from XRD scans ……………………….………50 Table 4..…………….……………………44 Table 4.…... Electromechanical properties for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3xPbTiO3 pellets after thermal conditioning at 2500C for 1 min... Rayleigh parameters for PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3…….1. Coercive field EC.1. remnant polarization PR and high field d33 for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3- xPbTiO3. Aging rate for piezoelectric constant d33.…………………………… ….

LIST OF FIGURES

Figure 2.1, Charge- field hysteresis loop for ferroelectric materials ………………....…5 Figure 2.2, Schematic for a) Direct and b) Converse piezoelectric effect ………....…7 Figure 2.3, Perovskite ABO3 unit cell …………………………………………..………8 Figure 2.4, 180° and non-180° domain walls in a tetragonal unit cell .…….....………10 Figure 2.5, Temperature – composition phase diagram for PZT, a) after Jaffe, et al. 19711 and b) modified by B. Noheda,200022…...…..…11 Figure 2.6, Temperature–composition phase diagram for BSPT, Eitel et al. 2004 17…………………………………………….........….……13 Figure 2.7, a) Ferroelectric switching polarization loop, b) Bipolar strain loop, and c) Unipolar strain loop, for PZT and BSPT ceramics ………….…….……13 Figure 3.1, Set up for high temperature dielectric measurement ……………….......…30 Figure 3.2, Schematic of the circuit used for P-E loop measurement……….….......…30 Figure 4.1, Particle size distribution after milling for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 powder before and after calcinations………........…35 Figure 4.2, XRD scans after calcination for (1-x)PbZrO3-xPbTiO3 x= 0.48 and (1-x)BiScO3-xPbTiO3, x=0.64 and 0.66………………...…..………..……36 Figure 4.3, XRD scans of crushed pellets after sintering for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48, and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66 ……………………………………………………………………..….……38

x

Figure 4.4, Microphotographs of the polished and thermally etched pellets for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.48, and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66

……………………………………………………………..………………41 Figure 4.5a), High temperature dielectric constant K and dielectric loss D for unmodified (1-x)PbZrO3-xPbTiO3 x=0.48, and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66 ………………………………………………………………...……..….…45 Figure 4.5b), High temperature dielectric constant K and dielectric loss D for Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.48, and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66 ……...……….…………………………………..…….…46 Figure 4.6, Ferroelectric P-E hysterisis loop for unmodified and Fe modified (1-x)PbZrO3-xPbTiO3 x=0.48, and unmodified and (1-x)BiScO3-xPbTiO3 Mn-modified

x=0.64 and 0.66 (measured at 50kV/cm, 1 Hz)

…………………………………...…………………………..….…………47 Figure 4.7, Bipoar and unipolar strain loop for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (1-x)BiScO3-xPbTiO3 x=0.48, and unmodified and Mn-modified

x=0.64 and 0.66 (measured at 50kV/cm,1 Hz)

…….………………………………………………………………..………48 Figure 4.8, Rayleigh analysis, piezoelectric response as a function of applied electric field for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3xPbTiO3 ………………………………………………………...…………52

xi

Figure 4.9, Rayleigh analysis, dielectric responses as a function of applied electric field for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3 -

xPbTiO3 ………………………………...……………………...….………53 Figure 5.1, Aging study at 2500C, piezoelectic constant d33 as a function of aging time for unmodified and modified (1-x)PbZrO3- xPbTiO3 x=0.48, and (1-x)BiScO3 - xPbTiO3 x=0.64 and 0.66…………………………………..63 Figure 5.2, Aging study at 2500C, planar coupling coefficient kP as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48, and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66………………..…………………63 Figure 5.3, Aging study at 2500C, dielectric constant K as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48, and

(1-x)BiScO3- xPbTiO3 x=0.64 and 0.66…………………..…….…………66 Figure 5.4, Aging study at 2500C, dielectric loss D as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48, and

(1-x)BiScO3-xPbTiO3 x=0.64 and 0.66……………………...……………66 Figure 5.5, Aging study at 2500C, Rayleigh analysis for dielectric constant K as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48, and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66 ……..…………...…68 Figure 5.6, Aging study at 2500C, Rayleigh analysis of αε ( 10-3 m/V) for dielectric response as a function of aging time for unmodified and modified

(1-x)PbZrO3-xPbTiO3 x=0.48, and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.66 ………………………………………………………………..……………69

xii

.……….7. and (1-x)BiScO3-xPbTiO3 x=0.8. Rayleigh analysis of Piezoelectic constant d33 ( at 0 kV/cm) as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.. Aging study at 2500C. and (1-x)BiScO3-xPbTiO3 x=0.……………70 xiii ..64 and 0.Figure 5.64 and 0.48. Rayleigh analysis of αd ( 10-14 Cm/NV) for piezoelectric response as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0. Aging study at 2500C.……….48.66……………………………………………………….66 …………………………………….………70 Figure 5.

3. high voltage generators. First demonstration of the piezoelectric effect by Currie brothers (Pierre and Jacques) was done in 1880. pressure. ultrasonic cleaning. welding. Since then. Long term reliability is one of the most important requirements for the technologically important piezoelectric devices. and lifetime analysis at high temperature. Current understanding of the long-term reliability and degradation mechanisms of piezoelectric materials is largely based on empirical evidences.1 Motivation The conversion of mechanical energy in a piezoelectric material into electrical energy and reverse effect is the basis for sensors and actuators. with the development of ABO3 type perovskite structure. This project will be focused to study thermal degradation and aging of piezoelectric and dielectric properties. medical therapy etc. Discovery of piezoelectric effect goes back to 19th century. flow and NDT transducers. 1 .Chapter 1: Introduction 1. Significant work has been done on the development of new piezoelectric materials to meet the requirements of various applications.20 The most important piezoelectric material lead zirconate titanate (1-x)PbZrO3-xPbTiO3 (PZT) was developed in 1950’s. lots of work has been done on the development of various piezoelectric materials. The main breakthrough in the field came during early to mid 1940’s.52 However there has been less work done on long term degradation and life time analysis of these materials and no widely accepted technique exists for reliability and lifetime testing. acoustic emission. Piezoelectric materials have numerous applications like ultra high temperature accelerometers.

46 There are several applications where piezoelectric materials are required to operate above this temperature range.4 Large piezoelectric coefficient.3 PZT has TC ∼ 3860C and shows rapid thermal degradation above 2000C. Acceptor doping is known as “hard” doping and donor doping is called “soft” doping.41 Enhanced room temperature properties and higher transition temperature makes this material more interesting for further investigation as a high temperature piezoelectric material.and after 50 years it remains the most widely used piezoelectric ceramic. oil & gas pipeline health monitoring and automotive smart brakes.3. These materials will be useful for making sensors for space exploration. In acceptor doped piezoelectric ceramics. oil and geothermal well drilling tools. alignment of defect dipoles in the direction of polarization vector tend to stabilize the domain structure and increase coercive field EC to 2 . and d33 ∼ 460 pC/N compared to TC ∼ 386 0C and d33 ∼ 223 pC/N for pure PZT. Significant work is going on for development of new piezoelectric materials suitable for extreme temperature applications. It was anticipated that due to high TC these materials are likely to have better resistance against thermal degradation and aging. large coupling factor and high Curie temperature (TC) makes this material suitable for a wide range of piezoelectric applications. Doping can be either by addition of acceptor dopants to create anion vacancies or by addition of donor dopants to create cation vacancies. The point defects created by intrinsic and dopant reactions are believed to impact its domain structure and domain wall stability on microscopic level. Recently materials based on (1-x)BiScO3-xPbTiO3 (BSPT) were developed with TC ∼ 4500C. In PZT one method of tailoring the performance is doping.3.

Piezoelectric and dielectric characterization of virgin and poled pellets is covered in Chapter 4 including sintering study. and thermal degradation and aging study.15 For the current work “hard” doping will be studied in order to improve aging behavior of PZT and BSPT. Changes in the properties will be compared with the initial and conditioned properties of these materials to establish the aging rates. Unmodified and doped BSPT and PZT ceramics will be synthesized using conventional mixed oxide method and thermal degradation and aging study will be conducted at 2500C for 1000 hrs. This thesis consists of six chapters. 1. Goal of this work is to conduct the thermal degradation and aging study for the high temperature piezoelectric ceramic BSPT and comparing it with PZT. phase 3 . Piezoelectric and dielectric characterizations will be done at predetermined intervals throughout the aging period.2 Organization of Thesis This thesis is formatted to provide comprehensive review of the work performed for the thermal degradation and aging study of high temperature piezoelectric ceramic (1-x)BiScO3-xPbTiO3 to evaluate suitability of this material for high temperature remote sensing applications. details the experimental procedures and methods used for the processing of above ceramics by solid state route. structural and physical characterization of the processed ceramics. Chapter 3. It also covers brief introduction about the two important piezoelectric systems PZT and BSPT selected for thermal degradation and aging study and summary of their important properties. The Chapter 2 consists of literature review and classical background related to piezoelectric materials and their aging behaviors.make these materials hard for poling and depoling.

microstructure analysis and grain size measurement. summary of the initial piezoelectric and dielectric properties along with ferroelectric Curie temperature. dielectric loss D. P-E hysteresis loops. planar coupling coefficient kP. dielectric constant K .identification. and Rayleigh analysis for piezoelectric and dielectric responses as a function of aging time. bipolar and unipolar strain loops and Rayleigh analysis for piezoelectric and dielectric response. presents the details of thermal degradation and aging study. 4 . change in piezoelectric constant d33. Chapter 5. Chapter 6 summarizes the work done for thermal degradation and aging study for BSPT system and roadmap for future studies. high temperature dielectric measurements.

Figure 2. Charge.1. Poling process aligns domains in the direction of the applied field yielding a net remnant polarization (PR).1 Introduction: Ferroelectric materials posses a local spontaneous polarization which can be reoriented between two or more equivalent crystallographic directions under application of a DC electric field.Chapter 2: Background for piezoelectric materials and their aging behavior 2.field hysteresis loop for ferroelectric materials Ferroelectricity can be verified through polarization of the material by application of electric field. The most important characteristic of ferroelectric material is switching of 5 . Piezoelectric materials can be polarized by application of an electric field and also by application of mechanical stresses. Ferroelectric ceramics can be made piezoelectric (poled) below Curie temperature (TC) by application of electrical field (E) greater than Coercive field (EC).

When the field is applied in opposite direction. Piezoelectricity is related to lack of a center of symmetry.2 shows the schematic illustration for direct and converse piezoelectric effect.2. Figure 2. some domains will remain aligned in the positive direction.polarization. Figure 2. the dipoles reverse their orientation and then saturate in other direction. Under the application of homogeneous stress materials which lack a center 6 .5. 21 of them are noncentrosymmetric and 20 are piezoelectric. direct and converse. That is called as remnant polarization (PR). Field in negative direction when all domains are back to original position (zero polarization) is called coercive field (EC).2 Perovskite Structure Crystal structure is very important for the performance of piezoelectric ceramics. Experimentally ferroelectric hysteresis loop can be observed using Sawyer-Tower circuit. With the application of increasing field domains start orienting in the direction of field. The relation between polarization (P) and electric field (E) is represented by hysteresis loop. The mathematical equation for theses effects are discussed in section 2. Production of electric charge when stress is applied is known as direct piezoelectric effect whereas the production of stress and/or strain when an electric field is applied is known as converse piezoelectric effect. Even after decreasing the field strength to zero all domains will not go back to original position. 2. Crystal structures can be divided into 32 point groups. 11 The piezoelectric effect includes two types of responses.1 shows the typical charge – field hysteresis loop for ferroelectric materials. extreme ends of the hysteresis loop (tail) represent the saturation where most of the domains are aligned in the direction of the applied field.

The perovskite structure applies to series of compounds with three types of atoms with general formula ABO3 described by a simple cubic unit cell with oxygen atoms at the face centers.2. Since the discovery of piezoelectric effect. lots of work has been done on development of various ferroelectric materials. The main breakthrough in the field came in the mid 1900’s with the synthesis and characterization of materials with perovskite structure.3.20 Large numbers of technologically important piezoelectric materials crystallize in the perovskite structure.of symmetry observe a net movement of positive and negative ions with respect to each other developing an electrical polarization proportional to an applied stress. Mechanical Stress Voltage Field Strain PZT + V - PZT Input Output Input Output Figure 2. Schematic for a) Direct and b) Converse piezoelectric effect Discovery of the piezoelectric effect goes back to 19th century.32 There are 7 . larger cations at the cube corners (A sites) and smaller cations in body center(B sites). Two of the most interesting piezoelectric materials selected for aging study are lead zirconate titanate (1-X)PbZrO3-xPbTiO3 or PZT and Bismuth scandium – lead titanate (1-x)BiScO3-xPbTiO3 or BSPT belong to perovskite family. Typical perovskite ABO3 unit cell is shown in Figure 2.

In PZT. where XII and VI represent coordination numbers.is situated at face center position forming octahedra around the B site (BO6). for tetragonal <001>. given in equation (2.1). RB. Polarization direction for rhombohedral is <111>. and anion respectively. Pb2+ ions are situated at the corner of the unit cell (A sites).0 are cubic.13 Ideal perovskite structure is simple cubic lattice.6 This provide 8 equivalent 8 .tetragonal. In general it is observed that perovskite structures with t = 0.A″)XII(B′.many complex perovskites which can be describe with the formula (A′. B″)VIO3. t < 0. Type of the perovskite crystal structure can be predicted using Goldschmidt tolerance factor (t).95 – 1. Figure 2.0 . small cation. Zr4+ or Ti4+ at body center positions (B site).3. Pb2+ and Bi3+ share the A sites whereas Ti4+ and Sc3+ share the B sites.1)3 where RA. In both material O2. Perovskite ABO3 unit cell. and for monoclinic phase it contained in monoclinic plane between [001] and [111]. and t > 1.rhombohedral or monoclinic. In BSPT. and RO are the ionic radius of large cation. Depending on the ionic radii of cations and anions the perovskite unit cell may be distorted to rhombohedral or tetragonal symmetry.3 t = (RA + RO) / √2 (RB + RO) (2.95 .

9 Depending on the relative orientation between polarization directions in neighboring domains there 180° and non-180° domain walls. The movement of domain walls due to external field affects the polarization and influences the piezoelectric and dielectric properties of ferroelectric materials. In the case of a monoclinic ferroelectric phase the polarization may continuously rotate between up to 24 different states. 2. A schematic representation of 180° and non-180° domain walls is shown in Figure 2. This strain is typically ~ 0. Intrinsic contributions are due to relative shift between cation and anion. tetragonal or rhobohedral. Displacement of the cations with respect to oxygen octahedra causes distortion of the individual unit cell resulting strain in the piezoelectric material. Ferroelectric domain walls may move under weak or moderate fields.9 When a voltage is applied to the perovskite unit cells one or more of the cations move due to the local field.4. Both 180° and non-180° domain wall motion influences the changes in polarization. while only non-180° domain wall motion 9 .2% for high performing polycrystalline ceramics whereas single crystals may strain >1%. Extrinsic contributions are mainly due to presence of domain walls and defect dipoles and those are thermally activated.polarization states for rhombohedral and 6 for tetragonal.3 Intrinsic and extrinsic contributions In polycrystalline ceramics piezoelectric and dielectric properties are depend on both intrinsic and extrinsic mechanisms.e. Displacement of the central atoms can only occur in certain crystallographic directions depending on the type of structure i.

3 In rhom mbohedral ph hase the pola arization is a along th body diag he gonal of unit cells which gives eight equivalent state of pola h t arization whe ereas 10 . since then it is bee the dom 3.4. show the temp e ws perature–com mposition p phase rh diagrams for PZT syste 3. 15 Fig 2. nd mperature an ability to tailor proper nd rties make th material suitable for wide his an Curie tem ra ange of app plications. a) b) ) gure 2.influe ences the st train output The real ferroelectri ceramics always co t.3 The high e the cial electromechanical prope erties.7 At ro r em.4 piezoelectric ceramic in t commerc market. 180° a) and no on-180° b) do omain walls in a tetragonal unit cell.5.4 Lead Zirconate T Z Titanate (1 1-x)PbZrO3-xPbTiO3 O O The most important piezoele m ectric materi lead zirc ial conate titana (1-x)PbZ 3ate ZrO xP PbTiO3 or PZT s d n en minant was developed in 1950’s. and T rich regio has tetrag ps Ti on gonal st tructure (FT) with space group P4mm. ZT ng e ructure is e either In PZ dependin on the % of Zr+4 or Ti+4 the crystal str hombhedral or tetragonal. oom tempera ature Zr ric region ha rhomboh ch as hedral st tructure (FR) with two space group R3m and R3c. Commonly u used PZT 5A has Curie temperatur TC∼3650C and A e re piezoelectric coefficient d33∼ 375 pC/ 52 /N. defects. The imperfec ese ctions and de efects may c cause pinning and clamping of domain wall 15 c ls. Figure 2. ic ontain im mperfections electrical and elastic d s.

am and bm 11 . the cubic to tetragonal phase transformation takes place at 660 K for MPB composition. Traditional understanding is that compositions near the MPB have coexistence of rhombohedral and tetragonal phases to give 14 possible polarization directions to optimize crystallographic orientation and resulting high dielectric and piezoelectric properties. PZT has nearly vertical MPB. The line separating two regions called morphotropic phase boundary (MPB) which is about x ~ 0. Noheda.3 Figure 2.6 The monoclinic unit cell is rotated 450 about c axis with respect to tetragonal cell. 19713 and b) modified by B.in tetragonal phase polarization is parallel to the edges of the unit cell and has six equivalent state of polarization. Temperature – composition phase diagram for PZT a) after Jaffe et al.6 PZT has the cubic structure at high temperatures. 2002 reported the presence of the monoclinic structure (FM) with space group Pc at the MPB.48.5.20007 Recently Noheda et al. The tetragonal to monoclinic phase transformation was discovered at ∼ 300K.

6 shows the temperature composition phase diagram for BSPT system.46 There are several applications where piezoelectric materials are required to operate above this temperature range. and unipolar strain loop (c) for PZT and BSPT ceramics with the MPB compositions which compare the behavior of these two important piezoelectric systems.lie along the tetragonal face diagonals [110] and [110] directions and cm deviates slightly from [001] direction. Lots of work is going on in the development of new piezoelectric materials suitable for extreme temperature applications. compared to TC ∼ 3860C and d33 ∼ 223 pC/N for pure PZT. Materials based on (1-x)BiScO3-xPbTiO3 (BSPT) have a TC ∼ 4500C and d33 ∼ 460 pC/N. Figure 2.3.cubic phase is about 4500C and increases with mol% of PbTiO3. oil and geothermal well drilling tools.3. bipolar strain loop (b). These materials will be very useful for making sensors for space exploration. 12 .42 It is clear from the below phase diagram that near the MPB region phase transition temperature from the tetragonal and rhombohedral phase to the paraelectric .5 High temperature piezoelectric (1-x)BiScO3-xPbTiO3 PZT with the MPB composition has TC∼ 386 0C and shows rapid thermal degradation above 2000C.7 shows ferroelectric switching polarization loop (a). 2. Figure 2. oil & gas pipeline health monitoring and automotive smart brakes.41 Enhanced room temperature properties and higher transition temperature makes this material interesting for high temperature application above 2000C.

Figure 2.6. Temperature–composition phase diagram for BSPT (Eitel et al. 2004) 42
a)
40

b)
BSPT (x=0.64) PZT (x=0.48)
0.2

BSPT (x=0.64) PZT (x=0.48)

Polarization (µC/m )

2

20

0.1

0

Strain (%)
-60 -40 -20 0 20 40 60

0.0

-20

-0.1

-0.2
-40

Field (kV/cm)

-60

-40

-20

0

20

40

60

Field (kV/cm)

c)
0.25
BSPT (x=0.64) PZT (x=0.48)

0.20

Strain (%)

0.15

0.10

0.05

0.00 0 10 20 30 40 50

Field (kV/cm)

Figure 2.7. a) Ferroelectric switching polarization loop, b) Bipolar strain loop, and c) Unipolar strain loop for PZT and BSPT ceramics 13

2.6 Properties of piezoelectric materials
The performance of piezoelectric devices depends on various electromechanical properties. Some of the important properties of piezoelectric materials are ferroelectric Curie temperature (TC), piezoelectric constant (d), dielectric constant (K) and loss (D or tanδ) and electromechanical coupling coefficient (k). Typical properties for various PZT and BSPT materials are given in Table 2.1. Shrout et al. 2007 showed that general piezoelectric properties of a ferroelectric ceramic can be expressed with a simple mathematical equation (2.2), dij ~ 2 Qij K ε0 Pi (2.2)52

where dij is the piezoelectric constant, Pi the remnant polarization, K the dielectric constant, ε0 the permittivity of free space, and Qij the electrostrictive coefficient.52 Since Qij exhibit little temperature dependant below Curie temperature TC, the perovskite ferroelectric ceramics with high piezoelectric constant dij also exhibits high dielectric constant K.52 Within the lead base piezoelectric family, materials with low ferroelectric Curie temperature TC exhibit high piezoelectric and dielectric properties. The reduction of ferroelectric Curie temperature is also associated with high thermal dependence of properties, and high aging rates. As a thumb rule piezoelectric ceramics can be used safely to ~ ½ TC (0C) without much change in piezoelectric properties.52 Hence engineering of piezoelectric ceramics is always an optimization of piezoelectric and dielectric properties and also ferroelectric Curie temperature TC.

14

2.6.1 Ferroelectric Curie temperature (TC) Ferroelectric materials posses a local spontaneous polarization and shows hysteresis relation between polarization and applied electric field. This behavior is observed in certain temperature region which depends on the transition of ferroelectric phase to paraelectric phase. Temperature above which the material loses its spontaneous polarization and piezoelectric characteristics is known as ferroelectric Curie temperature (TC). Depending on composition PZT has rhombohedral, tetragonal or mixed perovskite structure below TC and shows net dipole moment due to displaced central cation (Zr4+ or Ti4+). Above TC the material is cubic and the central cation is no longer displaced from the centre of the unit cell, leaving no net dipole moment and no spontaneous polarization. Table 2.1. Electromechanical properties of PZT and BSPT materials.
Material Curie point (0C) TC Dielectric Constant ( 1Khz) K Dielectric loss ( 1Khz) D Piezoelectric constant (10-12 C/N) d33 Electromechanical coupling coefficient k33

Pb(Zr0.52Ti0.48)O3 3 Hard PZT – 5H Hard PZT- 8 52 Hard PZT- 452 Hard PZT PCM-40 Soft PZT- 5A52 Soft PZT PCM-51 33 Soft PZT PIC 151 BSPT 64
41,50 34 33 52

386 190 300 328 325 330 365 340 250 450 460 445 468

730 3400 1000 1300 1250 1200 1700 1850 2400 2010 1370 1540 1112

0.004 0.02 0.004 0.004 0.003 0.003 0.02 0.019 0.02 0.05 0.03 0.01 0.01

223 590 225 290 290 265 375 405 500 460 260 390 270

0.67 0.75 0.64 0.70 0.67 0.66 0.71 0.74 0.69 0.56 0.43 0.69 0.65

Hard PZT PIC 181 34

BSPT 66 41 BSPT 64 + Mn48 BSPT 66 + Mn48

15

3) (2.3) and (2. maximum applications of materials are restricted to ∼½TC. The basic mathematical equations (2. hence may be specified in tensor form as in equation (2.As the temperature is increased.5) Depending on the application. T the stress. E the electric field. and d the piezoelectric constant which is numerically constant for both effects. High d is desirable for actuator applications like ultrasonic cleaner transducers.2 Piezoelectric constant (d) As discussed in section 2.E (Direct piezoelectric effect) (Converse piezoelectric effect) (2. Degradation of piezoelectric properties due to loss of polarization is called thermally activated aging. direct and converse.3 Piezoelectric properties are also anisotropic and vary with direction of polarization axis and strain.1.41. S the mechanical strain.46 2. piezoelectric devices may use one of the above piezoelectric effects. where materials are intended to develop motion or vibrations. Ei (2.5) to indicate directionality.52 PZT has TC ∼ 3860C and shows rapid degradation above 2000C.6. Di = dijk . In order to minimize the aging effect.3 Recently developed BSPT system has TC ∼ 4500C and are much more stable at temperature higher than 2000C. the piezoelectric effects include two types of responses. near TC the dipoles have the tendency to revert back to random orientation. 16 .4) where D is the dielectric displacement.T S=d. D=d.4) describe the above two types of piezoelectric effects are.Tjk and Sjk = dijk .

7) When an alternating voltage is applied to dielectric materials induced dielectric moment has both real and imaginary components.8) 2.Another frequently used piezoelectric constant is gij which is related to d by equation (2.41 K = ε / ε0 (2.3 Dielectric constant (K) and loss (D) The relative dielectric constant K is the ratio of the complex permittivity ε of the material and the permittivity of free space ε0 (8.85X 10-12 F/m).4 Electromechanical coupling coefficient Input energy to piezoelectric devices can be either in mechanical stress or electrical charge. The electromechanical coupling factor (k) is square root of the fraction 17 . Piezoelectric ceramics generally have a higher dielectric constant K.8). where materials are intended to generate voltage in response to mechanical stress. which is due to resistive leakage or dielectric absorption. D (tan δ) = ε˝ / ε΄ = k˝ / k΄ (2. The loss factor D is the ratio of imaginary component to the real component and expressed as equation (2. typical values for PZT and BSPT systems are 800 and as high as 2000 respectively. 3.5) where ε the dielectric permittivity of material. and ε0 the dielectric permittivity of vacuum.5).3 g = d / ε = d / K ε0 (2. High g is desirable for sensors applications like pressure sensors.6. 2.6.

70. Point defects created by intrinsic and dopant reaction are believed to impact domain structure and domain wall stability in piezoelectric materials. Fe3+.45 to 0. k= Energy converted (mechanical or electrical) Energy applied (mechanical or electrical) (2.of mechanical energy converted to electrical energy or vice versa. Na+) creating anion vacancies or “soft” by addition of donor dopants (Nb5+.3 k is the material constant for piezoelectric crystals and it depends on degree of poling for ceramics. Stability of domain wall structure increases the coercive field EC to make this material “hard” and reduces the piezoelectric constant d33 and dielectric loss D. Doping can be either “hard” by addition of acceptor dopants (Mg2+. La3+) eliminating VO¨. In donor doped materials anion vacancies are reduced and these piezoelectric materials exhibits low Ec. In acceptor doped materials mobility of point defects is relatively high due to large numbers of anion vacancies. and D. 3. 18 . Sb5+.9) Typical value of electromechanical factor for PZT and BSPT is in the range from 0.15 This allows alignment of paired defect dipoles in the direction of polarization vector stabilizing the domain structure. Lead volatility in Pb-based perovskites produces Pb vacancies (VPb″) which are naturally compensated by oxygen vacancies (VO¨) lead to acceptor (p-type) characteristics.41 2.7 Modification of properties by doping The electromechanical properties of piezoelectric ceramics can be tailored through compositional modification to make them suitable for different applications.

Sol gel process is expensive. sintering temperature and time. In the past various studies been carried out by several researchers to investigate effect of grain size on the properties of 19 . Solid state synthesis is more common due to its lower cost. Microstructure of the piezoelectric ceramic mainly depends on composition. In general bulk density of the ceramic after sintering should be more than 95% of theoretical densities. 2. The two most widely used methods for piezoelectric ceramics are sol gel processing and solid state synthesis. 1992 reported effects of two types of dopants on properties of PZT.Berlincourt et al.8 Effect of processing on the properties of piezoelectric materials Processing of the ceramic has great impact on its properties and performance of piezoelectric ceramics. On the other hand additions of acceptor dopants create vacancies on oxygen sites and help to reduce the dielectric losses and improve mechanical and electrical quality factors. primary particle size. Also donor doped PZT shows reduction in aging due to relaxation of internal stresses with less strain accommodation by Pb2+ vacancies.13 Addition of donor substitution to PZT improved piezoelectric coupling factor and dielectric permittivity. Processing parameters like milling time of the powders before and after calcinations and sintering time and temperature plays vital role in producing high density materials. Density is very important to achieve good piezoelectric and dielectric properties in a piezoelectric ceramic. it produces very fine high purity powders which can sinter at much lower temperatures to achieve densities close to theoretical value. Processing of ceramics mainly consist of forming a green body by mixing of metal oxide powders and then producing dense structure by sintering.

piezoelectric ceramics.46 Aging should be considered separately to thermal degradation. Aging is a process for a system to reach to an equilibrium state from a non-equilibrium state. fine grain microstructure leads to significantly higher dielectric constant and remnant polarization and a much lower coercive field with slight improvement in piezoelectric constant.52. Recently Randall el al. increase or 20 . under zero external stress and constant temperature. aging depends on material type.9 Results show that ferroelectric transition temperature is almost independent of grain size. piezoelectric coefficient d33 and d31 and electromechanical coupling coefficient kP and k31.56 Like other characteristics of piezoelectric materials. In order to minimize the thermal degradation. this loss of polarization is called thermal degradation. remnant polarization PR decreases and coercive field EC increases with decrease in grain size. maximum application of piezoelectric materials is generally restricted to ∼½ Tc. 1998 studied the effect of grain size on the dielectric and piezoelectric properties of PZT. General understanding was that. 2.9 Thermal degradation and aging of piezoelectric materials Piezoelectric ceramics suffer from loss of polarization as dipoles have a tendency to revert back to random orientation at high temperature. dielectric constant K. The thermal degradation is associated with an external influence and usually implies a large detrimental change to a property of a material. Aging can be characterized as thermally activated process as aging rate increases with increase in the temperature. More precisely aging can be defined as the spontaneous change of a material property with time. processing and poling condition.1 Change in property due to aging may be on either side.

aged samples show lower dielectric constant. 21 . In the ferroelectrics and related materials aging can be reversed or set back to initial property by long thermal cycle above ferroelectric Curie temperature TC. Stabilization of domains due to orientation of defects results an increase in the force constant for the 900 domain wall displacement. tanδ. It was also observed that polarization-field hysteresis loop of aged specimen acquires a pinched or propeller shape. 1993 reported aging study of acceptor doped BaTiO3 and PZT ceramics and proposed the quantitative model based on reorientation of defects with the time which causes clamping of domain walls and results in decrease of material properties during aging.55 Orientation of defects caused by slow diffusion of oxygen vacancies was attributed to splitting of energy due to electric and elastic dipoles. and electromechanical coupling factor. The main characteristics of aging process can be summarized as below.56 Investigation of BaTiO3 capacitors shows that aging of dielectric constant or capacitance follows a linear logarithmic relation with the time. 1988. which reflect buildup of an internal field due to migration of defects and also preferential location of electron trapping sites. aging rate decreases with increase in tetragonal distortion of perovskite cell but is not observed in paraelectric phase. aging can be completely reversed by heating the dielectric above Curie temperature and holding in the paraelectric phase.decrease.56 Robel et al. when mechanical quality factor and resonance frequency become higher. many researchers worked on aging studies of dielectrics and compressive review of these studies was presented by Schulze et al. polarizationfield hysteresis loop becomes constricted into a pinched or propeller shape with time. In the past.

Initially all elastic and electric defects are randomly oriented. 2.2 Diffusion of defects through domain wall and consequent stabilization of domain wall The driving force for migration of defects is likely to be relaxation of stresses or compensation of electric charges in the wall region. domain wall mobility and intrinsic dielectric response.1 Domain wall clamping by defects This mechanism is related to volumetric defect. With the time all these defect start relocating to energetically favorable position which is related to direction of polarization. development of internal bias field and stabilization domain structure. The defects act as pinning centers to restrict the wall motion hence contribution of domain wall to the properties get reduced. 22 .9. Broadly those can be classified as relocation of the charges. reorientation of defect dipole. Reorientation of polarization and displacement of domain walls by external field become more difficult once these defects are aligned.The basic modification happening in the piezoelectric material over a period of time due to aging is alignment of defect or space charge.15 In the past many authors have investigated the aging behaviors and several plausible models have been developed to interpret aging in the normal ferroelectric materials.9.1 2.

These heterogeneous space charges may require long time to reach to equilibrium positions. Details of the processing. MPB and tetragonal compositions. After reaching equilibrium positions.2. Compared to the MPB composition the tetragonal materials have lower piezoelectric constant d33 and planar coupling coefficient kP but they showed excellent thermal stability which make them better choice for high temperature applications. which is far below their ferroelectric Curie temperature. One of the most important requirements for any material or devices in the service is long term reliability. characterization and aging study are presented in the following chapters. the local electric field created by space charges stabilize the domain wall configuration and whole grain become biased in certain directions. 23 .3 Presence of space charges at the grain boundaries Grain boundaries are always higher energy location compared to grains hence it is more energy favorable location for segregation of dopants or secondary phases. 1000 hr aging study was conducted for (1-x) BiScO3-xPbTiO3 and results were compared with (1-X)PbZrO3-xPbTiO3.9. Recently Chen et al.46 Study reveals that tetragonal compositions of (1-x)BiScO3xPbTiO3 showed good resistance to thermal depoling up to the temperature close to their ferroelectric Curie temperature TC~4450C. 2006 reported the thermal depoling study for high temperature piezoelectric ceramic (1-x)BiScO3-xPbTiO3 with rhombohedral. Rhombohedral and MPB compositions started to depole at ~ 3000C.

it produces very fine high purity powders which can sinter at much lower temperatures to achieve densities close to theoretical value.1 Introduction Processing of piezoelectric ceramics consists of reacting metal oxide powders to achieve the desire phase. Alfa 24 . Sol gel process is expensive. Solid state synthesize is more common due to its lower cost. 3.Chapter 3: Experimental procedures and methods 3. Measurement of piezoelectric and dielectric properties was done at predetermined intervals to analyze the thermal degradation of properties as a function of time. compaction of powder to form a green body and then sintering to produce dense structure. ZrO2 (99.2. Halstab).5%. The two most widely used methods to produce piezoelectric ceramic powders are sol gel processing and solid state synthesis. Poled pellets were kept in oven at 2500C for 1000 hrs. For the current work (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 were synthesize by solid state mixed oxides method.2 Preparation of piezoelectric ceramics 3.1 Powder preparation The conventional mixed oxide (solid state) route was used to synthesize (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 ceramics of the MPB and tetragonal composition with and without acceptor doping. Piezoelectric and dielectric properties were evaluated for the set of virgin poled pellets. Commercially available reagent grade metal oxides and carbonates including PbCO3 (white lead A.

Alfa Aesar). larger surface area is required to accelerate diffusion between various oxide particles to form uniform phase in the calcination. density.66. shape of powders. Alfa Aesar). The metal oxide powders were mixed in stochiometric ratio in the batches of ~80 g considering hydration and ignition losses to form the intended compositions (1-x)PbZrO3-xPbTiO3 x =0.48 and (1-x)BiScO3-xPbTiO3 x=0. This can be achieved by reducing particle size of the powder mixture in milling. In solid state synthesis.Aesar). MnO2 (99. Alfa Aesar).64 and 0.975%. and size distribution.95%. For the current work the MPB and tetragonal compositions for (1-x)BiScO3xPbTiO3 and the MPB composition for (1-x)PbZrO3-xPbTiO3 with and without addition of acceptor dopant were selected for thermal degradation and aging study.41. Loss on ignition (LOI) was carried out for starting metal oxide powders to improve accuracy of the batching by compensating for hydration and ignition losses. 3. and porosity. surface area. purity. Particle size analysis of metal oxide powders was done by light scattering technique.5%.59 An acceptor dopant reduces dielectric losses and should improve resistance to aging. particle size. and degree of agglomeration. Powder preparation is important for adequate control of microstructure and properties of the final product. and Fe2O3 (99.9%. while the tetragonal compositions are anticipated to have high curie temperatures and resistance against aging.9%. To make milling more effective. TiO2 (99. Sc2O3 (99. PIDC). Bi2O3 (99. For the MPB type of piezoelectric ceramics it is well known that compositions near the MPB have enhanced piezoelectric and dielectric properties. Important characteristics of the powders that have a great impact on final product properties are chemical composition. were used as starting materials. highly concentrated aqueous 25 . Ishihara). Mean particle size of starting powders was in the range of 1 to 10 µm.

3. Suspensions were vibratory milled for 24 hrs using ф 5mm spherical yttrium stabilized zirconia media (Nikkato. Binder was burnt out by slow heating of the pellets to 5000C (10C/min) for 2 hrs in the box furnace prior to sintering.2 Forming Forming is the consolidation of loose calcined powders to a homogeneously packed green body prior to densification. The milled slurry was dried for 12 hours at 1200C. Vanderbilt Company Inc. Each calcination was followed by 24 hrs vibratory milling and drying as above to improve homogeneity and to expose new surfaces to improve diffusion in thermal treatment.E. circular pellets of ~ Φ13mm x 1 mm thickness were uniaxially pressed at 8000 psi in a hydraulic press using rigid steel die. The calcination process was repeated to get uniform perovskite phase with very little impurity level. 26 . Calcination of milled and dried (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 powders was done for 6 hours at 8500C and 7500C respectively. Powder binder mixed were dried at 1200C and crushed using mortar and pestle and passed through 80 mesh sieve. For the current work.2. Japan). R.suspension of powders was prepared by addition of ammonium polyacrylate (Darvan 821TM. These dopants were added in the calcined powders before final milling.4% wt was added to ceramic powders to provide the necessary plasticity for forming and green strength to facilitate handling of pellets after compaction.) as a dispersant and controlling its PH. Mistler) ~ 3. Acrylic copolymer (R. Modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 were prepared using Fe2O3 and MnO2 as acceptor dopants respectively.T. The perovskite phase development after calcination was evaluated by X-ray diffraction (XRD).

Sintering of unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 pellets was done in box furnace at the temperature range from 10000C to 11000C for 1 hr. After optimizing the sintering parameters.2. sets of 15 pellets for each composition were prepared for thermal degradation analysis.64 with ~ 5% excess Pb and Bi were used as source powder for sintering of (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 pellets respectively. low porosity and uniform microstructure with average grain size ~10µm and to achieve good piezoelectric and dielectric properties in the sintered pellets.4 Electrode application Sintered pellets were ground parallel to ~0.1ZrO3.3 Sintering Densification of the powders in to a pore-free. Ground pellets were cleaned ultrasonically with methanol and dried at 1200C 27 .3. high quality final product is achieved through the sintering. Sintering parameters were optimized to achieve high density. 3. Pb1. The two most commonly used densification methods are hot pressing and conventional sintering process. For the current work conventional sintering process was utilized. Unmodified (1-x)PbZrO3-xPbTiO3 pellets were sintered at 12000C for 1 hr whereas Fe-modified (1-x)PbZrO3-xPbTiO3 pellets were sintered at 11000C for 1 hr.2. Sintering for pressed pellets was done in the tube furnaces for 1 hr at the temperature range from 12000C to 13000C for unmodified (1-x)PbZrO3xPbTiO3 and 10500C to 12500C for Fe-modified (1-x)PbZrO3-xPbTiO3.5mm using 280 and 600 grit abrasive paper disk. Final batches of unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 were sintered at 11000C for 1 hr. Volatilization losses were controlled by using source powder and sealed crucibles.1 and (1-x)BiScO3xPbTiO3 x= 0.

Siemens) with CuKα1 radiation (1. X ray diffraction (XRD) of calcined powders and crushed sintered pellets was done for phase determination using θ-2θ diffractometer (ModelD500. apparent density and porosity were calculated from the measured data. Sintered pellets were polished and thermally etched at 9000C for 15 minutes.3. and theoretical density of the ceramics were calculated by indexing peaks from XRD scan.5418 A0).2. The densities of sintered pellets were measured in water using Archimedes method. Dielectric and piezoelectric properties of poled pellets were measured after 24 hr of the poling.3 Characterization 3. Grain size of the sintered pellets for all compositions except Fe-modified (1-x)PbZrO3xPbTiO3 was determined from the microphotographs taken by optical microscope 28 . 3. c/a ratio. Bulk density.5 Poling Electroded pellets were poled in an oil bath at 1000C under 40kV/cm DC field for 15 min. Pellets with bulk density more than 95% theoretical value were used for characterization of piezoelectric and dielectric properties. Conductive Ag electrode paste (DuPont 6160) was applied and dried at 1600C for 15min and then fired at 8500C after cleaning the edges. Lattice parameters. 3.1 Structural and physical characterization The properties of piezoelectric ceramics are mainly dependant on the phases present in the structure.for 12 hrs to remove moisture from the pellets prior to electrode application.

and spontaneous polarization PS are determined through P-E hysteresis loops.2.3.2 Piezoelectric and dielectric characterization 3. 29 . Hitachi). remnant polarization PR. Grain size for Fe-modified (1-x)PbZrO3-xPbTiO3 was determined from the microphotographs taken by scanning electron microscope SEM (Model-S3200-N.2 Polarization – electric field (P-E) hysteresis loop The most important characteristic of ferroelectric materials is the switching of polarization.1 Ferroelectric Curie temperature (TC) As the temperature is increased.(Model.3. 3. The set up used for high temperature dielectric measurement is shown in Figure 3. The temperature above which the material loses its spontaneous polarization and piezoelectric characteristics is known as Curie temperature. near TC the dipoles have the tendency to revert back to random orientation.Nikon).LV100POL. High temperature dielectric measurement was done up to 6000C for unpoled pellets in a vertical tube furnace (Model-F21130.2. Dielectric constant increases with increasing temperature. Ferroelectric properties such as coercive field EC.28 3. Average grain size was calculated using lineal intercept technique.1. Agilent) and data acquisition. Nikon) with digital camera (Model-DXM 1200C.3. reaches to the peak value and then decreases. Barnstead) using computerized control LCR meter (Model–E4980A. This peak corresponds to ferroelectric Curie temperature.

3 Sample Waveform generator V Voltage divider H Integrating capacitor Figure 3.2. Schematic of the circuit used for P-E loop measurement.610B. Schematic for the Sawyer-Tower circuit used for P-E loop measurement is shown in Figure 3. Set up for high temperature dielectric measurement Ferroelectric hysteresis loops. were measured at an electric field of 50kV/cm and frequency 1 Hz using a Sawyer-Tower circuit with a linear variable differential transducer (LVDT). bipolar and unipolar strain loops.1. 3 30 .2. TReK).LCR meter Vertical tube furnace Sample Holder Sample Figure 3. high voltage power supply (Model. and computerized control and data acquisition.

5 Planar coupling coefficient (kP) Planar coupling coefficient kP was measured using Impedance / Gain. t the thickness.85X 10-12 F/m). CP the ε is the permittivity of the material.1) the permittivity of free space. capacitance. and expressed by simple mathematical equation (3.2) tanδ = ε″/ ε′ (3.2.).2) 3. Dielectric permittivity is a complex value. This method gives direct reading for d33.4 Piezoelectric constant (d33) Piezoelectric constant d33 was measured using Berlincourt type d33 meter (ModelYE2730A.3 Room temperature capacitance CP and dielectric loss D were measured using multi frequency LCR meter (Model4274A. K = ε / ε0 and where ε = CP x ( t /A) ε0 (3. under the application of alternating voltage it has both real (in phase) and imaginary (out of phase) components ε = ε '+iε " .phase analyzer (Model. Room temperature dielectric measurements were done for the electroded pellets before and after poling.4194A. Hewlett Packard). 3. and A the area of pellets. Dielectric constant K was calculated from the measured capacitance using equation (3.3. APC International Ltd.3 Dielectric constant (K) and dielectric loss (D) The relative dielectric constant K is the ratio of the permittivity ε of the material and the permittivity of free space ε0 (8.2.3. Dielectric loss (D or tanδ) is the ratio of imaginary and real components. The parallel resonance frequency fp and the 31 .3. Hewlett Packard).3.1).2.

3. Rayleigh law indicates a liner dependence on the piezoelectric constant and dielectric constant with increasing field.σE) J1[ η1 ( 1 + Δf / fs ) ] .3 kP 2 1.16-18 Rayleigh measurement for dielectric and piezoelectric response were made using a Sawyer-Tower circuit with a linear variable differential transducer (LVDT). Two polled pellets 32 . η1 the lowest positive root of cross contraction ratio.kP 2 = (1.η1 ( 1 + Δf / fs ) J0 [η1 ( 1 + Δf / fs) ] (1+ σE) J1[ η1 ( 1 + Δf / fs ) ] (3. and field. (1- σE) J1( η1) .series resonance frequency fs were obtained from the measurements and kP was calculated from using the equation (3.3).2. Intrinsic contributions are mainly due to strain in crystal lattice.6 Rayleigh analysis for dielectric and piezoelectric response Rayleigh law was used originally to describe the dependence of magnetization and magnetic permeability in ferromagnetic materials. Rayleigh law is suitable in low field region where density and domain wall structure remain unchanged.12.12.3)3 where J0 is the Bessel function of first kind and zero order . in general those are reversible and with no loss. Piezoelectric response in ferroelectric material contains both intrinsic and extrinsic contribution. and σE the Poisson’s 3.16-18 Same approach is being used in piezoelectric materials to quantify irreversible and irreversible piezoelectric response. Extrinsic contribution are generally non linear and lossy and varies as a function of time. Extrinsic contribution is mainly due to motion of non-1800 domain walls. frequency. J1 the Bessel function of first kind and first order. and computerized control and data acquisition. high voltage power supply.

The sets of poled pellets were loaded at 2500C in the oven for 1 min for thermal conditioning treatment. which can be describe with the general equation (3. dielectric loss D. t0 is the starting time for the measurements. 400h. Samples were reloaded after characterization for 1000 h. Pellets with the maximum 10% variation from mean value of the above properties were used for the thermal degradation and aging study. kP.were evaluated for dielectric and piezoelectric responses at low field for unmodified and modified compositions of (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 . 10 h. Standard statistical methods were used to evaluate errors. and A is the aging rate (constant) which can be either positive or negative. Poled pellets were characterized for dielectric constant K. variability and standard deviations for the above measurements. 100 h. It shows the linear relation with t on logarithmic scale. 200h. 33 . piezoelectric constant d33.4) p(t) = p(t0) + A log(t) (3. aging of the piezoelectric and dielectric properties (d33. 700h and 1000h. For piezoelectric materials. 3. and electromechanical coupling coefficient kP and Rayleigh measurement for piezoelectric and dielectric response. Changes in the above properties were evaluated at predetermined interval of 1 h. The results were evaluated to find out aging rate for piezoelectric and dielectric properties.4) where p is the material property.4 Thermal degradation and aging Sets of 15 pellets for each composition were prepared for thermal degradation and aging study. and K) can be describe as a function of time (t).

66 ceramics were prepared using solid state route as discussed in Chapter 3. shows the plots of particle size distribution and Appendix-B summaries LOI results for starting powders used for synthesis of (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3.1 Introduction For the thermal degradation and aging study one of the important step is the characterization of the processed materials to evaluate their properties in comparison with the studies done in past. dielectric constant K.48 and unmodified and Mn-modified (1-x)BiScO3xPbTiO3 x=0. Unmodified and Femodified (1-x)PbZrO3-xPbTiO3 x=0.64 and 0. piezoelectric constant d33. Particle size less than 1µm were aimed 34 . P-E hysteresis. planar coupling coefficient kP.Chapter 4: Characterization 4. Additionally measured properties provide the basis for further study to evaluate the degradation and calculate the aging rates. microstructure and grain size for sintered ceramics in addition to piezoelectric and dielectric characterization for ferroelectric Curie temperature TC. bipolar and unipolar strain loops. Appendix-A. 4. Measurement procedures and methods used for these characterizations are discussed in previous chapter. This chapter details the characterization for phase identification.2 Physical and structural analysis Analysis of starting metal oxide and carbonate powders was done for mean particle size. dielectric loss D and Rayleigh analysis for piezoelectric and dielectric response. Particle size of the starting powders found in the range of 1 to 10 µm. particle size distribution and LOI.

The development of perovskite phase after calcination was evaluated by θ-2θ XRD using 1. a) (1-x)PbZrO3-xPbTiO3 x=0.66 shows small peak between {100} and {110} peaks which corresponds little impurity phase which was reacted completely in the sintering process.64 and 0. 35 .46µm) 10 Milled after 1st calcination (0. shows the XRD scans for powders after calcination.for satisfactory processing of these ceramics. mean particle size after post calcination milling was found less than 0.5418A0 CuKα1 radiation. and second calcination for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3xPbTiO3.37µm) Quantity (%) Quantity (%) Milled after 2nd calcination (0. Particle size distribution after milling for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 powder before and after calcinations. XRD scans for (1-x)PbZrO3-xPbTiO3 x=0.33µm) b) (1-x)BiScO3-xPbTiO3 x=0.5 µm.2. after first. shows the distribution of particle size after 24 hrs milling for mixture of raw powders.48 Milled after 2nd calcination (0.71µm) Milled after 1st calcination (0.64 10 Raw Material .35µm) 5 Raw Material . Figure 4. Particle size analysis was done after each 24 hr milling.1. Figure 4.48 shows well defined single phase perovskite peaks.1.Milled (0.23µm) 5 0 0 1 2 3 4 0 0 1 2 3 Diameter (µm) Diameter (µm) Figure 4.Milled (1. XRD scans for (1-x)BiScO3-xPbTiO3 x=0.

66 36 .64 Intensity A.64 and 0.66 Intensity A.48 and (1-x)BiScO3-xPbTiO3. 20 30 40 50 60 70 Intensity A.2.48 b) (1-x)BiScO3-xPbTiO3 x=0. x=0. 20 Angle 2θ 30 40 50 60 70 Angle 2θ c) (1-x)BiScO3-xPbTiO3 x=0. U.a) (1-x)PbZrO3-xPbTiO3 x=0. U. XRD scans after calcination for (1-x)PbZrO3-xPbTiO3 x= 0. 20 30 40 50 60 70 Angle 2θ Figure 4. U.

Table 4.48) is almost similar to unmodified composition whereas for Mn-modified (1-x)BiScO3-xPbTiO3 (x=0. The lattice parameters were calculated from the peak position in the XRD scans.1.023 1.023 and 1.028 1.1382 4.64 (1-x)BiScO3-xPbTiO3 x=0.48 Unmodified Fe-modified Unmodified Mn-modified Unmodified Mn-modified a (A0) c(A0) c/a (1-x)BiScO3-xPbTiO3 x=0.3.9872 3.9788 3.XRD scans for crushed sintered pellets were done to analyze the crystal structure as shown in Figure 4.64 and 0.64) showed splitting of {100} and {110} peaks which indicate presence tetragonal phase along with rhombohedral phase.64 and 0.0800 4.66 4.028 respectively whereas for (1-x)PbZrO3-xPbTiO3 x=0. and c/a ratio.022 1.1.48) and (1-x) BiScO3xPbTiO3 (x=0.9747 4.028 37 .0290 3.026 1.0676 4.0333 4.026 1.66 were 1. Lattice parameters for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 calculated from XRD scans.48 it was 1. Calculated c/a ratio for the BiScO3-xPbTiO3 x=0.66) intensity of all peaks was suppressed compared to unmodified compositions.66) showed more splitting of these peaks which suggest more tetragonality.0852 4. Material (1-x)PbZrO3-xPbTiO3 x=0.0850 1. XRD scans for the MPB compositions of (1-x)PbZrO3-xPbTiO3 (x=0. XRD scans for (1-x)BiScO3-xPbTiO3 (x=0. The MPB region corresponds to a mixed phase region. XRD scan for Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. summarizes lattice parameters.026.9735 3. Table 4.1338 4.

(counts) (111) (002) (200) (201) (211) (100) (110) (1-x)BiScO3-xPbTiO3 x=0.66 + Mn Intensity A. U.(counts) (211) (111) (002) (200) (100) (220) (100) (111) (200) (002) (201) (201) (211) (110) (1-x)PbZrO3-xPbTiO3 x=0. U.48 (002) (200) (211) (111) (100) (110) (1-x)BiScO3-xPbTiO3 x=0. microstructure and grain size using methods and procedures as described in previous chapter.64 and 0. Results of sintering studies for 38 . and (1-x)BiScO3-xPbTiO3 x=0.3. XRD scans of crushed pellets after sintering for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.(110) a) (1-x)PbZrO3-xPbTiO3 x=0.64 (111) (100) (201) (220) (002) (200) (201) (211) 20 30 40 50 60 70 20 30 40 50 60 (220) (220) 70 Angle 2θ Angle 2θ c) (110) (100) (1-x)BiScO3-xPbTiO3 x=0.48.48 + Fe b) (110) (1-x)BiScO3-xPbTiO3 x=0.64 + Mn Intensity A. The detail sintering study was carried out to achieve maximum possible density and minimum volatilization loss of lead (Pb) in (1-x)PbZrO3-xPbTiO3 and Bismuth (Bi) and Pb in (1-x)BiScO3-xPbTiO3 system.66. U.66 (111) (002) (200) (201) (211) 20 30 40 50 60 (220) (220) 70 Angle 2θ Figure 4.(counts) Intensity A. Physical characterization of sintered pellets were carried out to evaluate density.

Figure 4. 10 µm and 12 µm for unmodified and Mnmodified (1-x)BiScO3-xPbTiO3 x=0.48 was achieved at 12000C and addition of acceptor dopant Fe2O3 to it assisted to lower the sintering temperature to 11000C. 39 . Measured bulk density of sintered pellets decreases with increase in sintering temperature. Sintering for unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 was done at temperature 11000C.66. Average grain size determined were 11 µm and 3 µm for unmodified and Femodified (1-x)PbZrO3-xPbTiO3 x=0. Average grain size for Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.64. Microphotographs were taken using either optical microscope or SEM. Microstructures do not show any abnormal grain growth.2.48. whereas in case of (1-x)BiScO3-xPbTiO3 doping with MnO2 did not act as sintering aid. Best densification of unmodified (1-x)PbZrO3-xPbTiO3 x=0. depending on the grain size. Microstructure for all the compositions shows equiaxed grains with scattered porosity and some grain pull out due to polishing of pellets. Reduction in bulk density at high temperature is associated with higher weight loss due to volatilization. Average grain size was targeted ~10 µm for each composition to neutralize the grain size effect on aging study.4 shows the microphotographs for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3.(1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 are summarized in Table 4.48 was smaller than the targeted value but high sintering temperature were resulting low resistivity for the sintered pellets. 8 µm and 11 µm for unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.

9 95.42 7.02 0.29 -0.66 1000 1050 1100 (1-x)BiScO3-xPbTiO3 x=0.7 .15 0.36 (1-x)PbZrO3-xPbTiO3 x=0.48 7.50 7.24 0.8 95.21 0.14 0.14 0.52 7.39 7.7 95. Composition Sintering Temperature 0C Bulk density (gm/cm3) % Theoretical density % Weight loss (1-x)PbZrO3-xPbTiO3 x=0.31 0.66 + Mn 1000 1050 1100 40 .4 96.6 95.4 95.42 0.54 7.42 7.2 96.54 7.8 96.9 97.8 95.48 + Fe (1-x)BiScO3-xPbTiO3 x=0.69 7.81 7.71 7.06 0.46 96.2 96.01 0.09 0.4 96.12 0.53 7.53 7.67 7.64 1000 1050 1100 (1-x)BiScO3-xPbTiO3 x=0.31 0.8 95.65 7.8 96.64 + Mn 1000 1050 1100 (1-x)BiScO3-xPbTiO3 x=0.48 1200 1225 1250 1050 1100 1200 1250 7.47 7.83 7.0 95.0.13 0.1 95.2.69 7.37 0. Bulk density for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 after sintering.22 -0.27 0.5 96.Table 4.3 95.

48 (1-x)BiScO3-xPbTiO3 x=0.64 (1-x)BiScO3-xPbTiO3 x=0.64 and 0.(1-x)PbZrO3-xPbTiO3 x=0. .48.66 (1-x)PbZrO3-xPbTiO3 x=0.66 .48 + Fe (1-x)BiScO3-xPbTiO3 x=0. Microphotograph of the polished and thermally etched pellets for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.4. and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.64 + Mn (1-x)BiScO3-xPbTiO3 x=0.66 + Mn 41 Figure 4.

64 and 0. 1250 and 0.48.008 for Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.3.64.04 for Mn-modified (1-x)BiScO3-xPbTiO3 x=0.48 was 3860C and 3880C respectively. 950 and 0.1 Dielectric constant (K) and dielectric loss (D) Dielectric constant K and dielectric loss D were measured on virgin pellets prior to poling. Relative permittivity K and dielectric losses D were measured as a function of temperature as shown in Figure 4.64.5(a & b).3. Ferroelectric Curie temperature TC measured at the frequency 10 KHz are summarized in Table 4.48 showed reduction in K after poling whereas (1-x)BiScO3-xPbTiO3 x=0.015 for (1-x)PbZrO3-xPbTiO3 x=0. 1070 and 0. TC for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.66.3 Unpoled properties 4. (1-x)BiScO3-xPbTiO3 x=0.64 and 0.03 for Mn-modified (1-x)BiScO3-xPbTiO3 x=0. (1-x)PbZrO3-xPbTiO3 x=0.4.66 showed TC of 4360C and 4460C. 4. whereas modification with Mn for these compositions increased their TC to 4380C and 4480C respectively.2 Ferroelectric Curie temperature (TC) The high temperature dielectric measurements were done on unpoled pellets at various frequencies from 1 KHz to 1 MHz.06 for (1-x)BiScO3-xPbTiO3 x=0.4.66. 1100 and 0.05 for (1-x)BiScO3-xPbTiO3 x=0. 42 .48. 1040 and 0.66 showed improvement which distinguish behavior of these two systems. The measured K and D were ~ 1050 and 0.

7(d.3. Substantial reduction in measured strain was observed for acceptor doped materials compared to unmodified compositions.64 shows high field d33 = 489 pC/N and 488 pC/N respectively.66 looks like soft piezoelectric material but those were hard for poling and this shape is likely to be due to low frequency used for the measurement. P-E hysteresis loop for Femodified (1-x)PbZrO3-xPbTiO3 x=0. and 0.4. P-E hysteresis loops for Mn modified (1-x)BiScO3-xPbTiO3 x=0.6. b.64. High field d33 were obtained from the unipolar strain loops as summarized in Table 4. e. and c) have the symmetrical butterfly shape.3. The MPB compositions (1-x)PbZrO3xPbTiO3 x=0. 43 . Bipolar strain loops as shown in Figure 4. and 0.3.64. EC for unmodified (1-x)PbZrO3-xPbTiO3 x=0. Unipolar strain loops were measured on poled pellets as shown in Figure 4. and f).3 Polarization – electric field (P-E) hysteresis loop Ferroelectric P-E hysteresis loops were measured at an electric field of 50kV/cm and frequency 1 Hz as shown in Figure 4.7(a.66. Coercive field EC and remnant polarization PR were extracted from P-E loops as summarized in Table 4. 31kV/cm and 33 kV/cm respectively.48 and (1-x)BiScO3-xPbTiO3 x=0.48 and (1-x)BiScO3-xPbTiO3 x=0.66 was 20kV/cm. PR was 29 µC/cm2 for (1-x)BiScO3-xPbTiO3 x=0.48 shows pinching effect which indicate the instantaneous aging at ambient temperature for this material.64 and 33 µC/cm2 for (1-x)BiScO3-xPbTiO3 x=0.

66.66.64 (1-x)BiScO3-xPbTiO3 x=0.1 Dielectric constant (K) and dielectric loss (D) Dielectric constant K and dielectric loss D were measured for the sets of 15 poled pellets for each composition.006 for BiScO3-xPbTiO3 x=0.006. showed average K= 1678 and 1276 and average D = 0.016 respectively.011 for (1-x)PbZrO3xPbTiO3 x=0. Results for K and D measured at 1 kHz are summarized in Table 4. 1 kHz. Coercive field EC. Refer APPENDIX-E for the details of dielectric measurement done at frequency 100Hz.3. 10 kHz and 100 kHz for individual samples.4 Poled properties 4. Material (1-x)PbZrO3-xPbTiO3 x=0.Table 4.4.64 and 0. (1-x)BiScO3-xPbTiO3 x=0.48 Unmodified Fe-modified Unmodified Mn-modified Unmodified Mn-modified Coercive field EC (kV/cm) Remnant polarization PR (µC/cm2) High field d33 (10-12 C/N) (1-x)BiScO3-xPbTiO3 x=0.66 21 31 18 33 20 18 29 15 33 11 489 208 488 360 362 245 4.025 and 0. Mnmodification reduced the dielectric losses to 0.4. Addition of acceptor dopants to (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 both shows substantial reduction in dielectric losses D.48 and Fe-modification improved K to 885 and reduced D to 0. The average K and D were 766 and 0. 44 . remnant polarization PR and high field d33 for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3.

High temperature dielectric constant K and dielectric loss D for unmodified (1-x)PbZrO3-xPbTiO3 x=0.01 0.64 and 0.1 0.01 1E-3 100 (1-x)PbZrO3-xPbTiO3 x=0.66.1 0.48 1 KHz 10 KHz 100 KHz 1 MHz 100 (1-x)BiScO3-xPbTiO3 x=0.66 1 KHz 10 KHz 100 KHz 1 MHz Tc= 446 C (10 KHz) 0 40000 40000 40000 Relative Permitivity (K) Relative Permitivity (K) Relative Permitivity (K) 30000 30000 30000 20000 20000 20000 10000 10000 10000 0 100 200 300 400 0 0 0 500 600 100 200 300 400 0 500 600 100 200 300 400 0 500 600 Temperature ( C) Temperature ( C) Temperature ( C) Dielectric loss (D) Dielectric loss (D) 1 1 Dielectric loss (D) 45 100 10 0.48 and (1-x)BiScO3-xPbTiO3 x=0. .01 200 300 400 0 500 600 1E-3 100 200 300 400 0 1E-3 500 600 Temperature ( C) 100 200 300 400 0 500 600 Temperature ( C) Temperature ( C) Figure 4.50000 (1-x)PbZrO3-xPbTiO3 x=0.1 0.66 1 KHz 10 KHz 100 KHz 1 MHz 10 10 1 0.64 1 KHz 10 KHz 100 KHz 1 MHz Tc= 436 C (10 KHz) 0 50000 (1-x)BiScO3-xPbTiO3 x=0.5 a).48 1 KHz 10 KHz 100 KHz 1 MHz Tc= 386 C (10 KHz) 0 50000 (1-x)BiScO3-xPbTiO3 x=0.64 1 KHz 10 KHz 100 KHz 1 MHz 100 (1-x)BiScO3-xPbTiO3 x=0.

48.1 0.01 0.48 + Fe 100 (1-x)BiScO3-xPbTiO3 x=0.1 0. .66.66 + Mn 1 KHz 10 KHz 100 KHz 1 MHz 10 1 KHz 10 KHz 100 KHz 1 MHz 10 1 KHz 10 KHz 100 KHz 1MHz 10 1 1 0.48 + Fe 50000 1 KHz 10 KHz 100 KHz 1 MHz (1-x)BiScO3-xPbTiO3 x=0.1 0.01 0.66 + Mn 1 KHz 10 KHz 100 KHz 1 MHz 40000 Relative Permitivity (K) 40000 40000 30000 Tc= 388 C (10 KHz) 0 Relative Permitivity (K) Relative Permitivity (K) 30000 Tc= 438 C (10 KHz) 0 30000 Tc= 448 C (10 KHz) 0 20000 20000 20000 10000 10000 10000 0 100 200 300 400 0 500 600 0 100 200 300 400 0 0 Temperature ( C) 500 600 100 200 300 400 0 500 600 Temperature ( C) Temperature ( C) Dielectric loss (D) 1 Dielectric loss (D) Dielectric loss (D) 46 100 (1-x)PbZrO3-xPbTiO3 x=0.64 and 0.01 1E-3 100 200 300 400 0 500 600 1E-3 100 200 300 400 0 1E-3 Temperature ( C) 500 600 100 200 300 400 0 500 600 Temperature ( C) Temperature ( C) Figure 4. High temperature dielectric constant K and dielectric loss D for Fe-modified (1-x)PbZrO3-xPbTiO3 x=0. and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.64 + Mn 1 KHz 10 KHz 100 KHz 1MHz 50000 (1-x)BiScO3-xPbTiO3 x=0.50000 (1-x)PbZrO3-xPbTiO3 x=0.5 b).64 + Mn 100 (1-x)BiScO3-xPbTiO3 x=0.

48 40 (1-x)BiScO3-xPbTiO3 x=0.64 + Mn 40 (1-x)BiScO3-xPbTiO3 x=0. and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.48.1 Hz) .48 +Fe 40 40 (1-x)BiScO3-xPbTiO3 x=0.6 Ferroelectric P-E hysterisis loop for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 x=0.64 40 40 (1-x)BiScO3-xPbTiO3 x=0.66 ( measured at 50kV/cm.66 Polarization (µC/m ) Polarization (µC/m ) 20 Polarization (µC/m ) 2 2 2 20 20 0 0 0 -20 -20 -20 -40 -60 -40 -20 0 20 40 60 -40 -40 Field (kV/cm) -60 -40 -20 0 20 40 60 -60 -40 -20 0 20 40 60 Field (kV/cm) Field (kV/cm) Polarization (µC/m ) Polarization (µC/m ) 20 20 Polarization (µC/m ) 2 2 2 47 (1-x)PbZrO3-xPbTiO3 x=0.66 + Mn 20 0 0 0 -20 -20 -20 -40 -60 -40 -20 0 20 40 60 -40 -60 -40 -20 0 20 40 60 -40 -60 -40 -20 0 20 40 60 Field (kV/cm) Field (kV/cm) Field (kV/cm) Figure 4.64 and 0.(1-x)PbZrO3-xPbTiO3 x=0.

15 Strain (%) Strain (%) 48 0.48 / +Fe) 0.7 Bipoar and unipolar strain loop for unmodified and Fe modified (1-x)PbZrO3-xPbTiO3 x=0.1 -0. and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 x=0.2 -60 -40 -20 0 20 40 60 Field (kV/cm) Field (kV/cm) Field (kV/cm) Strain (%) 0.2 -60 -40 -20 0 20 40 60 -0.00 0 10 20 30 40 50 Field (kV/cm) Field (kV/cm) Field (kV/cm) Figure 4.25 e) (1-x)BiScO3-xPbTiO3 x=0.66 ( measured at 50kV/cm.64 / +Mn 0.1 0.66 / +Mn 0.10 0.0 + Mn 0.64 and 0.48 / +Fe 0.20 0.05 0.10 0.64 / +Mn 0.a) (1-x)PbZrO3-xPbTiO3 x=0.15 + Mn 0.1 -0.1 Strain (%) Strain (%) Strain (%) + Fe 0.1 Hz) .10 + Fe 0.66 / +Mn 0.2 b) (1-x)BiScO3-xPbTiO3 x=0.0 -0.2 c) (1-x)BiScO3-xPbTiO3 x=0.2 -60 -40 -20 0 20 40 60 -0.15 0.25 f) (1-x)BiScO3-xPbTiO3 x=0.25 d) (1-x)PbZrO3-xPbTiO3 x=0.0 + Mn 0.05 0.48.00 0 10 20 30 40 50 0.2 0.00 0 10 20 30 40 50 0.1 -0.05 + Mn 0.1 0.20 0.20 0.

66 were 215 pC/N.64 and 0.4.2 Piezoelectric constant (d33) Piezoelectric constant d33 was measured using Berlincourt type d33 meter for the sets of 15 poled pellets for each composition.phase analyzer for two pellets for each compositions. Refer APPENDIX-G for the details of piezoelectric constant d33 for individual pellets.42 respectively.51 and 0.4. (1-x)PbZrO3-xPbTiO3 x=0.66 showed the average kP = 0. 382 pC/N and 256 pC/N respectively. 4.modification helped to improved kP for (1-x)PbZrO3xPbTiO3 x=0.3 Planar coupling coefficient (kP) Planar coupling coefficient kP was measured using Impedance/ Gain. (1-x)BiScO3-xPbTiO3 x=0.4. Complete summary of measured planar coupling coefficient kP is given in Table 4. Addition of acceptor dopants made these materials hard for poling and reduced the piezoelectric constant d33.48 showed the average kP = 0. Complete summary of measured piezoelectric constant d33 is given in Table 4.48. The measured low field piezoelectric constants d33 are ~ 45% to 85% compared to high field d33 obtained from unipolar loops for these materials. Fe.26 and (1-x)BiScO3-xPbTiO3 x=0.4.48. Average d33 for (1-x)PbZrO3-xPbTiO3 x=0. 49 .4.64 and 0.

014 0.8) 215 177 193 .016 0.006) (+/.20) (+/.025 0.010 0.841 823 .012) (+/.0.4.010 .64 1678 382 234 256 1103 (1-x)BiScO3-xPbTiO3 x=0. Material Curie temperature (0C) Tc Dielectric constant ( 1Khz) K Average* Range (Min-Max) Dielectric loss ( 1Khz) D Average* Range (Min-Max) Piezoelectric constant ( pC/N) Average* Planar coupling coefficient Average# d33 Range (Min-Max) kp (1-x)PbZrO3-xPbTiO3 x=0.0.0.0.1826 1082 .008 .35 0.1015 0.48 Unmodified Fe-modified Unmodified Mn-modified Unmodified Mn. Measured electromechanical properties for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 pellets.020 .Table 4.007) (+/.15) (+/.005) (+/.118 (+/.006 0.427 207 .37 0.207 354 .0.283 103 .005 0.27) (+/.009 0.42 0.19) (+/.018) 0.256 235 .236 162 .006 (+/.41) (+/.66 1276 985 50 109 * Average of 15 pellets.011 0.0.1365 963 . # Average of 2 pellets .015 .28) 766 696 .modified 386 388 436 438 446 448 (+/.008 0.0.0.51 0.970 1547 .018 0.0.0.004 .008) (+/.0.99) (+/.71) (+/.26 0.18 885 (1-x)BiScO3-xPbTiO3 x=0.48) (+/.005 .16) (+/.0.28) (+/.1127 1151 .028 0.

(1-x)BiScO3xPbTiO3 x=0. K and d33 showed linear relation with the applied field.48 and (1-x)BiScO3-xPbTiO3 x=0.4.8 and Figure 4.9 respectively. Rayleigh analysis for acceptor doped compositions showed more deviation from the low field measurements.66 respectively.48. The d33init (Y-intercept) obtained from Rayleigh analysis were 357 pC/N.5 along with low field d33 and K. Plots for Rayleigh analysis for piezoelectric and dielectric responses as a function of applied electric field are shown in Figure 4. The tetragonal composition (1-x)BiScO3-xPbTiO3 x=0.66 respectively.1% compared to low field K measured for the same samples. Similarly Kinit obtained from Rayleigh analysis were 750. High values of αd (10-14 Cm/NV) for the MPB compositions (1-x)PbZrO3-xPbTiO3 x=0. and 1324 for (1-x)PbZrO3-xPbTiO3 x=0. which are within +/.64 indicate significant role of the extrinsic contribution due to motion of non-1800 domain walls.64 and x=0.64 and 0. and 272 pC/N for (1-x)BiScO3-xPbTiO3 x=0.5 Rayleigh analysis for dielectric and piezoelectric response Rayleigh measurement for dielectric and piezoelectric responses were done on two polled pellets for each composition. 51 . The summary of the results for the Rayleigh analysis for piezoelectric and dielectric responses is given in Table 4.10% compared to low field d33 measured for the same samples. 1639. which are within +/.66 showed lower αd (10-14 Cm/NV) and αε (10-3 m/V). which is most likely due to addition of dopant to these materials with out charge and site compensations.

48 600 500 400 d 33 (pC/N) 300 200 (1-x)PbZrO 3-xPbTiO3 x=0.600 500 400 d33 (pC/N) 300 200 100 0 4 (1-x)PbZrO3 -xPbTiO3 x=0.37x + 161. 52 .02x + 272.96 11 13 Field ( kV/cm ) 600 500 400 (1-x)BiScO3 -xPbTiO3 x=0.66 R2 = 0.64 +Mn d33 (pC/N) 300 200 100 0 7 9 11 13 15 17 Field ( kV/cm ) y = 11. piezoelectric response as a function of applied electric field for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3.66 R2 = 0.11x + 97.66 600 500 400 d33 (pC/N) 300 200 (1-x)BiScO3 -xPbTiO3 x=0.59 R2 = 1.99 6 8 Field ( kV/cm ) 10 12 100 0 5 7 9 y = 4.48 + Fe y = 16.46 R2 = 0.64 600 500 400 d33 (pC/N) 300 200 (1-x)BiScO3-xPbTiO3 x=0.00 13 15 17 Field ( kV/cm ) 600 500 400 d 33 (pC/N) (1-x)BiScO3 -xPbTiO3 x=0.99 14 16 18 Field ( kV/cm ) Figure 4.28x + 138.32x + 174.66 +Mn 300 200 100 0 7 9 11 13 15 17 Field ( kV/cm ) y = 6.66 R2 = 0.8 Rayleigh analysis.98 100 0 8 10 12 y = 4.70x + 356.16 R2 = 0.99 100 0 7 9 11 y = 14.

30 R2 = 1.17 R2 = 1.00 11 13 Field ( kV/cm ) 3500 3000 2500 2000 K (1-x)BiScO3-xPbTiO3 x=0.64 3500 3000 2500 2000 K 1500 1000 (1-x)BiScO3 -xPbTiO3 x=0.48 3500 3000 2500 2000 K 1500 1000 (1-x)PbZrO3 -xPbTiO3 x=0.00 500 0 5 7 9 y = 27.18x + 955.00 500 0 7 9 11 y = 128.02x + 1612.66 3500 3000 2500 2000 K 1500 1000 (1-x)BiScO3 -xPbTiO3 x=0.26 R2 = 1.61x + 735. 53 .83 R2 = 1.9 Rayleigh analysis.47x + 754.51x + 632. dielectric responses as a function of applied electric field for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3.48 + Fe 1500 1000 500 0 4 6 8 Field ( kV/cm ) 10 12 y = 81.00 9 11 13 15 17 500 0 8 10 12 y = 46.75 R2 = 1.3500 3000 2500 2000 K (1-x)PbZrO3-xPbTiO3 x=0.66 + Mn y = 33.00 14 16 18 Field ( kV/cm ) Field ( kV/cm ) Figure 4.00 13 15 17 Field ( kV/cm ) 3500 3000 2500 2000 K 1500 1000 500 0 7 (1-x)BiScO3 -xPbTiO3 x=0.74x + 1292.64 +Mn 1500 1000 500 0 7 9 11 13 15 17 Field ( kV/cm ) y = 79.84 R2 = 1.

44 0.17 1. Rayleigh parameters of piezoelectric and dielectric responses for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 .79 1. Material (1-x)PbZrO3-xPbTiO3 x=0.64 x=0.48 Unmodified Fe-modified Unmodified Mn-modified Unmodified Mn.66 (1-x)BiScO3-xPbTiO3 54 .41 754 736 1613 632 1293 955 0.modified Piezoelectric response d33 init (pC/N) ( 10-14 Cm/NV) Dielectric response K init ( 10-3m/V) Measured properties d33 (pC/N) K αd αε 174 139 357 162 272 98 1.60 0.81 0.43 1.Table 4.29 0.5.63 0.28 0.46 223 188 390 237 282 117 750 886 1639 1111 1324 1002 (1-x)BiScO3-xPbTiO3 x=0.38 0.

P-E hysteresis and strain. Dielectric constant K.48 The average d33 . whereas Mnmodification to these compositions increased their TC to 4380C and 4480C respectively.48 were 3860C.64 and 0. Ferroelectric Curie temperature TC.66 showed TC= 4360C and 4460C. Unpoled pellets were characterized to evaluate ferroelectric Curie temperature TC. dielectric loss D and piezoelectric constant d33 were measured on optimally poled pellets. 2002.64 showed average d33 = 382 pC/N.66 were 256 pC/N.200C less compared to valued reported by Eitel et al.3 (1-x)BiScO3-xPbTiO3 x=0.6 Summary and conclusion The purpose of this study was to do the characterization of virgin pellets and obtain a set of electromechanical properties which would provide basis for further thermal degradation and aging study. dielectric constant K.41 The dielectric and piezoelectric properties for Mn-modified (1-x)BiScO3xPbTiO3 are much less than reported by peer studies which is most likely due to addition 55 . The TC measured for (1-x)BiScO3-xPbTiO3 compositions were ~150C . K and kP for (1-x)BiScO3-xPbTiO3 x=0.field loops. 2002 and 2005. Two pellets from each set were characterized for planar coupling coefficient kP and Rayleigh analysis. 215 pC/N respectively which are similar to the properties reported by Jaffe et al. and piezoelectric constant d33 measured for (1-x)PbZrO3-xPbTiO3 x=0. actual measurement for various sample in the set of 15 pellets showed d33 as high as 427 pC/N which is very close to the value reported by Eitel et al.41.42 which are similar to value reported for prior studies.41 The MPB composition (1-x)BiScO3-xPbTiO3 x=0. Set of 15 pellets from each compositions within +/10% of the mean properties were selected for thermal degradation and aging study. and 0.1971. 1365.4. 766.

For compositions near the MPB (1-x)BiScO3-xPbTiO3 system shows ΔTC ~ 40C/ mol% PbTiO3. It can be concluded from this study that the set of piezoelectric and dielectric properties obtained from above characterization are comparable with the novel studies done in the past and would provide good basis for thermal degradation and aging study. minor variation in compositions.42 Low TC obtained for the processed materials are possibly due to different raw materials.of dopant without charge and site compensation. and sintering conditions. 56 .

56 This study mainly focused to evaluate the isothermal aging effect on piezoelectric and dielectric properties of the high temperature piezoelectric ceramic (1-x)BiScO3-xPbTiO3 and compared to the commercially dominant piezoelectric ceramic (1-x)PbZrO3xPbTiO3. Characterization of the virgin poled pellets was done to evaluate initial piezoelectric and dielectric properties as discussed in Chapter 4.39. dielectric constant.1 Introduction Long term reliability of technological piezoelectric devices is a major concern for their applications. under zero external stress and constant temperature. Aging should be considered separately to thermal degradation which usually implies a large detrimental change to a property of a material. Unmodified and modified (1-x)PbZrO3-xPbTiO3 (x=0.48) and (1-x)BiScO3-xPbTiO3 (x=0.56 The most important parameters which cause degradation of piezoelectric properties are high temperature. such as piezoelectric coefficient. and electromechanical coupling factor etc. These pellets were kept at the controlled temperature of 2500C for 57 . Aging is the spontaneous change of a material property with time.19 Piezoelectric ceramics suffer from loss of polarization as dipoles have a tendency to revert back to random orientation at high temperature.64 and 0. this loss of polarization is called thermal degradation.66) ceramics were prepared using conventional mixed oxides solid state method as discussed in Chapter 3. stress and strong electrical filed. associated with the change in their electromechanical properties.Chapter 5: Thermal degradation and aging 5. Many piezoelectric materials undergo processes of degradation and aging.

dielectric loss D. dielectric constant K. dielectric constant K. 5. This was done to analyze the instantaneous thermal depoling effect.1 Thermal conditioning Characterization of poled virgin pellets was done after 24 hours for piezoelectric constant d33. Temperatures more than 2500C were resulted in excessive increase of dielectric loss D and accelerated degradation of (1-x)PbZrO3-xPbTiO3.66) were reloaded in the oven maintained at the constant temperature of 2500C (+/. The characterization of the pellets was done and properties after 1min heating was considered as conditioned properties for further aging study.2. Based on preliminary high temperature aging study carried out on limited samples for these material 2500C was selected as an optimum temperature for the thermal degradation and aging study. 5. planar coupling coefficient kP.2 Aging study 5.50C) for total time of 1000h after instantaneous thermal degradation analysis as above.64 and 0. and Rayleigh measurement for dielectric and piezoelectric responses. and dielectric loss D was analyzed at predetermined intervals to evaluated aging rates.1000 hours. Change in the piezoelectric constant d33. planar coupling coefficient kP. For the current aging study sets of pellets were heated to the temperature 2500C and removed from the oven after 1 min and allowed to cool down to ambient temperature.48) and (1-x)BiScO3-xPbTiO3 (x=0. Characterization 58 .2 Isothermal aging Sets of 15 pellets from each compositions of unmodified and modified (1-x)PbZrO3-xPbTiO3 (x=0.2.

and dielectric loss D. 10h.66) pellets were heated to the temperature 2500C for 1min and cooled down to ambient temperature. and planar coupling coefficient kP.56 Aging rates were calculated (%/decade) from the slope of the graphs.64 and 0. Piezoelectric and dielectric properties before and after thermal conditioning for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 are summarized in Table 5. planar coupling coefficient kP. As expected piezoelectric constant d33. 700h. dielectric constant K. 200h. Piezoelectric and dielectric characterization was done to evaluated instantaneous thermal degradation for piezoelectric constant d33.1 Thermal conditioning Unmodified and modified (1-x)PbZrO3-xPbTiO3 (x=0.3 Results and discussion 5.48) and (1-x) BiScO3-xPbTiO3 (x=0. Results were analyzed to establish the aging rates for piezoelectric constant d33. and 1000h.1. Aging of the piezoelectric and dielectric properties show linear change with time on logarithmic scale. 5. Rayleigh analysis was done on two pellets from each composition to evaluate the change in piezoelectric and dielectric responses with the aging time. 100h. 400h.64 and 0. and planar coupling coefficient kP showed reduction in comparison with virgin properties.66) showed reduction in dielectric constant K whereas 59 .3.of these pellets was done for piezoelectric and dielectric properties at predetermined intervals of 1h. Unmodified (1-x) BiScO3xPbTiO3 (x=0. Variation in aging rate for the individual samples were taken into consideration and reported as uncertainty along with the average values.

48 0.26 0.009 0.011 0.66 Unmodified Fe modified Unmodified Mn modified Unmodified Mn modified 386 388 436 438 446 448 215 177 382 234 256 109 200 145 356 228 245 84 0.025 0.35 0.005 0. Material Curie temperature (0C) Tc Piezoelectric constant * (10-12 C/N) Planar coupling coefficient # Dielectric constant * ( 1Khz) K Poled Conditioned Dielectric loss * ( 1Khz) D Poled Conditioned d33 kp Poled Conditioned Poled Conditioned (1-x)PbZrO3-xPbTiO3 x=0. Electromechanical properties for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 pellets after thermal conditioning at 2500C for 1 min.1. . compared to poled properties.019 0.37 0.004 0.42 0.64 (1-x)BiScO3-xPbTiO3 x=0.18 0.006 0.013 0. * Average of 15 pellets.40 0.22 0.32 0.35 0.48 (1-x)BiScO3-xPbTiO3 x=0.Table 5.034 0. # Average of 2 pellets.51 0.010 766 885 1678 1103 1276 985 786 941 1655 1187 1264 1021 60 Poled properties – after 24 hrs.018 0.15 0.016 0.

006 to 0.modification to (1-x)PbZrO3xPbTiO3 (x=0.48) showed the improvement in K after 1 min heating at 2500C.64 and 0.66) as well as unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. Tetragonal (1-x)BiScO3xPbTiO3 (x=0.1.48) whereas all other material showed little increase in dielectric loss D after the thermal treatment. Dielectric loss D was reduced from 0. Unmodified (1-x)PbZrO3-xPbTiO3 (x=0. At the high temperature the dipole have tendency to revert back to random orientation resulted in decrease of piezoelectric constant d33 with the increase in temperature similarly with time dipoles get more time to revert back to random orientation.004 for Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. The degradation of piezoelectric constant d33 as a function of aging time is shown in the Figure 5.66) at the predetermined intervals as stated above.2 Piezoelectric constant (d33) Piezoelectric constant d33 was measured using Berlincourt type d33 meter for the set of 15 pellets for unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. Analysis of the measured data was done to calculate aging rate for the piezoelectric constant d33. As expected all material showed reduction in piezoelectric constant d33 with the increase in aging time.9%/decade.48) showed high aging rate of 4.3.Mn-modified (1-x)BiScO3-xPbTiO3 (x=0.48).2. Fe.66) showed very low aging rate of 0.8% /decade and MPB composition 61 . and Fe-modified (1-x)PbZrO3-xPbTiO3 and (1-x) BiScO3-xPbTiO3 are summarized in Table 5. Aging rate for piezoelectric constant d33 for unmodified. and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 (x=0.8%/decade.48) reduced the piezoelectric constant d33 to 145 (10-12 C/N) from 200 (10-12 C/N) but assisted to reduce aging rate to 0. 5.64 and 0.

kP showed decreasing trends with increase in aging time for all above materials.4 shows the plots for measured dielectric constant K and dielectric loss D as a function 62 .2. 5.3.3 Planar coupling coefficient (kP) Planar coupling coefficient kP was measured using gain-impedance analyses for two pellets for each compositions of unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. Mnmodification to (1-x)BiScO3-xPbTiO3 did not help to lower the aging rates.48) showed high aging rate of 3.modification to (1-x)PbZrO3-xPbTiO3 (x=0. 0.6% /decade.(1-x)BiScO3-xPbTiO3 x=0. Unmodified (1-x)PbZrO3-xPbTiO3 (x=0. (1-x)BiScO3-xPbTiO3 x=0.1%/decade.9%/decade for planar coupling coefficient kP.22 to 0.64.3.2.66) at the predetermined intervals as stated above. Fe.48) improved planar coupling coefficient kP from 0. 5. followed by x=0. The degradation of planar coupling coefficient kP as a function of aging time is shown in the Figure 5. Hewlett Packard) at predetermined time interval as stated above. Mn-modification to (1x)BiScO3-xPbTiO3 (x=0.66 shows very low aging rate of 0.66) did not help to improve the aging behavior.48). Aging rates for planar coupling coefficient kP calculated based on the slope of the plots are summarized in Table 5.3 and 5. Figure 5. unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 (x=0.64 and 0.9%/decade.32 and also reduced the aging rate to 0.6%/decade from 3.8%/decade.4 Dielectric constant K and dielectric loss D Dielectric characterization of unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 pellets was done at using multi frequency LCR meter (Model4274A.64 and 0.64 showed moderate aging rate of 2.

48.2 Aging study at 2500C.1 1 10 100 1000 10000 Time (hr) Time (hr) Time (hr) Figure 5.01 0.14 (1-x)PbZrO3-xPbTiO3 (x = 0.48) + Fe 0. planar coupling coefficient kP as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.1 1 10 100 1000 10000 Time (hr) 0.64 and 0.0018 log(x) + 211.04 y = -8.66) + Mn 0.(1-x)PbZrO3-xPbTiO3 ( x = 0.39 y = -0.31 y = -0.0039 log(x) + 0.60 0.69 300 250 200 150 100 50 0 y = -2. (1-x)PbZrO3-xPbTiO3 ( x = 0.1 1 10 100 1000 10000 d33 (pC/N) 250 250 200 150 100 50 0 (1-x)BiScO3-xPbTiO3 (x = 0.64) (1-x)BiScO3-xPbTiO3 (x = 0.00 0.64) + Mn d33 (pC/N) y = -9.01 0.0127 log(x) + 0.xPbTiO3 x=0.0025 log(x) + 0.1 1 10 100 1000 10000 0.66) (1-x)BiScO3-xPbTiO3 (x = 0. piezoelectic constant d33 as a function of aging time for unmodified and modified (1-x)PbZrO3.64) 0.21 kP kP 63 (1-x)BiScO3-xPbTiO3 (x = 0.47 0.70 (1-x)PbZrO3-xPbTiO3 (x = 0.66.66) d33 (pC/N) 200 150 100 50 0 0.0053 log(x) + 0.20 0.14 y = -7.2917 log(x) + 75.61 y = -1.48) (1-x)PbZrO3-xPbTiO3 (x = 0.1 1 10 100 1000 10000 0.64) 400 350 300 400 350 (1-x)BiScO3-xPbTiO3 (x = 0.66) (1-x)BiScO3-xPbTiO3 (x = 0.32 0.20 y = -0.0020 log(x) + 0.01 0.48) 0.66) y = -0.60 (1-x)BiScO3-xPbTiO3 (x = 0.0284 log(x) + 242.01 0.64) (1-X)BiScO3-xPbTiO3 (x = 0.40 y = -0.48) (1-x)PbZrO3-xPbTiO3 (x = 0.66.64 and 0.48.20 y = -0.40 0.40 0.60 kP 0.6128 log(x) + 189.3039 log(x) + 139.1 Aging study at 2500C.48) 400 350 300 (1-x)BiScO3-xPbTiO3 (x = 0.3923 log(x) + 346.01 Time (hr) Time (hr) Figure 5.00 0.48) + Fe y = -3. and (1-x)BiScO3-xPbTiO3 x=0.1 1 10 100 1000 10000 0.0085 log(x) + 0.18 (1-x)BiScO3-xPbTiO3 (x = 0. and (1-x)BiScO3-xPbTiO3 x = 0.01 (1-x)BiScO3-xPbTiO3 (x = 0.66) + Mn 0. .00 (1-x)BiScO3-xPbTiO3 (x = 0.64) +Mn 0.

48) shows high aging rate of 2. Fe-modification to (1-x)PbZrO3 -xPbTiO3 (x=0.08% /decade. Mn-modification to (1-x)BiScO3-xPbTiO3 (x=0. Unmodified (1-x)PbZrO3-xPbTiO3 (x=0.of aging time.2%/decade for dielectric constant K.02 whereas unmodified and Mn-modified (1-x)BiScO3xPbTiO3 (x=0.64) showed dielectric loss D less than 0.2%/decade. Dielectric loss D did not show any abnormal increase during 1000 hr aging period for any of the above compositions. Unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0.66) did not help to improve the aging behavior. calculated aging rate was -0.66) showed dielectric loss D less than 0.48) and unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 (x=0. 64 .04.64 shows moderate aging rate of 0. whereas (1-x)BiScO3-xPbTiO3 x=0. Aging rate for Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0.2. Aging rates for dielectric constant K calculated based on the slope of the plots are summarized in Table 5. (1-x)BiScO3-xPbTiO3 x=0.6% /decade.64 and 0.48) changed the behavior of material and K showed improvement with aging.66 showed very high resistance against dielectric aging.48) was -0.

66 Unmodified Fe modified Unmodified Unmodified 386 388 436 446 215 177 382 256 200 145 356 245 4.48 0.22 0.6 0. Aging rate for piezoelectric constant d33.8 0.08 * Average of 15 pellets. planar coupling coefficient kp.64 (1-x)BiScO3-xPbTiO3 x=0.42 0. Material Curie temperature (0C) Tc Piezoelectric constant * (10-12 C/N) d33 Aging rate Poled Conditioned (% / decade) Planar coupling coefficient # kp Poled Conditioned Dielectric constant * ( 1Khz) K Aging rate Conditioned (% / decade) Aging rate (% / decade) Poled (1-x)PbZrO3-xPbTiO3 x=0.51 0.37 0.2.9 0. poled properties (after 24 hrs) 65 .2 0.2 -0. and dielectric constant K for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 (at 2500C).1 0.40 3.48 (1-x)BiScO3-xPbTiO3 x=0.9 2.Table 5.32 0.6 766 885 1678 1276 786 941 1655 1264 2.8 0.26 0.6 -0. # Average of 2 pellets.8 0.

(1-x)PbZrO3-xPbTiO3 ( x = 0.1 1 10 100 1000 10000 (1-x)BiScO3-xPbTiO3 (x = 0.04 0. Aging study at 2500C.48) 1800 1600 1400 1200 1000 1800 1600 1400 (1-x)BiScO3-xPbTiO3 (x = 0.64) (1-x)BiScO3-xPbTiO3 (x = 0.66) (1-x)BiScO3-xPbTiO3 (x = 0.05 (1-x)PbZrO3-xPbTiO3 (x = 0.5103 log(x) + 1025. and (1-x)BiScO3-xPbTiO3 x=0.64 and 0.48) + Fe 800 K y = +22.1088 log(x) + 926.1 1 10 100 1000 10000 0.66) y = -10. Aging study at 2500C.02 0.66.70 1400 1200 y = +1.66. and (1-x)BiScO3-xPbTiO3 x=0.64) + Mn 0.03 0.01 0.00 0.66) + Mn Time (hr) Time (hr) Time (hr) Figure 5.01 0.455 log(x) + 755.0689 log(x) + 1260.10 y = -17.66) (1-x)BiScO3-xPbTiO3 (x = 0.00 0.212 log(x) + 1220.40 y = +2.03 0.05 (1-x)BiScO3-xPbTiO3 (x = 0.48) (1-x)PbZrO3-xPbTiO3 (x = 0.02 0.1 1 10 100 1000 10000 (1-x)BiScO3-xPbTiO3 (x = 0. (1-x)PbZrO3-xPbTiO3 ( x = 0.48) 0. . dielectric constant K as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.48) + Fe 0.01 0.01 0.05 (1-x)BiScO3-xPbTiO3 (x = 0.1 1 10 100 1000 10000 Time (hr) Time (hr) Time (hr) Figure 5.64) + Mn (1-x)BiScO3-xPbTiO3 (x = 0.4.64) 0.3.64) (1-x)BiScO3-xPbTiO3 (x = 0.04 0.01 0.48.48) (1-x)PbZrO3-xPbTiO3 (x = 0.01 1200 1000 K K 800 600 400 200 0 0.735 log(x) + 1620. dielectric loss D as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.01 0.04 D D D 66 (1-x)BiScO3-xPbTiO3 (x = 0.01 0.66) 200 0 0.02 0.1 1 10 100 1000 10000 (1-x)PbZrO3-xPbTiO3 (x = 0.01 0.03 0.66) + Mn 0.10 1000 800 600 400 y = +5.64) 1800 1600 (1-x)BiScO3-xPbTiO3 (x = 0.00 0.48.01 0.51 600 400 200 0 0.1 1 10 100 1000 10000 0.64 and 0.

64). (1-x)BiScO3-xPbTiO3 (x=0.66 and 0.7 and 5.4 Rayleigh analysis during aging study Rayleigh analysis was done to evaluate change in non-linear dielectric and piezoelectric responses as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3. which suggest significant contribution of depoling in the aging of these materials.66) shows little degradation for d33init with the increase in aging time.64).48). There is no apparent change in relation of intrinsic and extrinsic contributions to piezoelectric coefficient. Plots for dielectric constant K init and αε (10-3 m/V) as a function of aging time for unmodified and modified (1-x)PbZrO3xPbTiO3 and (1-x)BiScO3-xPbTiO3 are shown in Figure 5. irreversible.6 respectively. 67 . K init for unmodified and modified (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 shows almost constant response for the aging period of 1000 hrs. Piezoelectric response for d33init (pC/N) and αd (10-14 Cm/NV) as a function of aging time are shown in Figure 5.5 and 5.64 and 0. unmodified and Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0.48) shows almost steady response for d33init throughout the aging period of 1000h.5. The overall piezoelectric response can be expressed as d d extrinsic. The above plots show that in general d33 and α have the similar trends during aging. Mn-modified (1-x)BiScO3-xPbTiO3 (x=0.48). reversible initial = d intrinsic + and α is proportional to d extrinsic.8 respectively. Slope for the piezoelectric response αd (10-14 Cm/NV) shows decreasing trends with increase in time for (1-x)PbZrO3-xPbTiO3 (x=0. Slope for the dielectric response αε( 10-3 m/V) decreases linearly with increase in aging time except for Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0. unmodified and Mn-modified (1-x)BiScO3-xPbTiO3 (x=0.

64) + Mn 10 100 1000 10000 0.5 Aging study at 2500C.48) + Fe 1800 1600 1400 1200 1000 (1-x)BiScO3-xPbTiO3 (x = 0.518 log(x) + 962.1 1 10 100 1000 10000 Time (hr) Figure 5.01 y = -10.01 0.1 1 10 100 1000 10000 0.9 (1-x)BiScO3-xPbTiO3 (x = 0.4.66) (1-x)BiScO3-xPbTiO3 (x = 0.48) 1800 1600 1400 1200 1000 1800 1600 1400 1200 1000 (1-x)PbZrO3-xPbTiO3(x = 0.64) y = -13.01 0.(1-x)PbZrO3-xPbTiO3(x = 0.1 1 y = .59 800 600 400 K 800 600 400 y = +1.48) + Fe 200 0 0. and (1-x)BiScO3-xPbTiO3 x=0.48.9 800 600 400 200 0 0.763 log(x) + 848.1 1 10 100 1000 10000 Time (hr) Time (hr) Time (hr) (1-x)BiScO3-xPbTiO3 (x = 0.4 K K 800 600 400 200 0 0.152 log(x) + 1620.26 (1-x)PbZrO3-xPbTiO3 (x = 0.66) 1800 1600 1400 1200 1000 K 68 y = +2.5837 log(x) + 835.01 (1-x)BiScO3-xPbTiO3 (x = 0.66) + Mn 0.88 y = +10. Rayleigh analysis for K as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0. .66.64) (1-x)BiScO3-xPbTiO3 (x = 0.797 log(x) + 1284.48) 200 0 (1-x)PbZrO3-xPbTiO3 (x = 0.64 and 0.82 log(x) + 827.

4383 -3 -3 0.66) + Mn (1-x)BiScO3-xPbTiO3 (x=0.60 y = -3E-05x + 0.40 y = -3E-05x + 0.20 0.80 0.64) + Mn 1.7102 0.40 y = 2E-05x + 0.60 0.20 1.20 0.64) (1-x)BiScO3-xPbTiO3 (x=0.20 (1-x)PbZrO3-xPbTiO3 (x=0.40 (1-x)BiScO 3-xPbTiO3 (x = 0.6929 0.64) 1.00 1.40 (1-x)PbZrO3-xPbTiO3 (x=0.66. Rayleigh analysis of slope αε ( 10-3 m/V) for dielectric response as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.00 1.48.3217 0.00 α ( 10 m/V) α ( 10 m/V) α ( 10-3m/V) y = -0.0839 0.60 y = -7E-05x + 0.48) 1.80 0. 69 .00 0 200 400 600 800 1000 1200 0.20 (1-x)BiScO3-xPbTiO3 (x=0.20 0.40 0.66) (1-x)BiScO3-xPbTiO3 (x=0.0001x + 1.48) + Fe 1.00 0 200 400 600 800 1000 1200 0.6 Aging study at 2500C.66) 1.(1-x)PbZrO3-xPbTiO3 1.80 y = -4E-05x + 0.1411 0. and (1-x)BiScO3-xPbTiO3 x=0.40 (1-x)BiScO3-xPbTiO3 (x = 0.00 0 200 400 600 800 1000 1200 Time (hr) Time (hr) Time (hr) Figure 5.64 and 0.

66) + Mn 1.1 1 10 100 1000 10000 0.48) 400 350 300 400 350 300 250 200 (1-x)BiScO3-xPbTiO3 (x = 0.50 α ( 10 -14Cm/NV) 70 (1-x)BiScO3-xPbTiO3 (x = 0.48) (1-x)PbZrO3-xPbTiO3 (x = 0.48) + Fe y = -4. and (1-x)BiScO3-xPbTiO3 x=0.01 (1-x)PbZrO3-xPbTiO3 (x = 0.00 y = -0.256 1.50 (1-x)PbZrO3-xPbTiO3 (x=0.48) (1-x)PbZrO3-xPbTiO3 (x=0.66) (1-x)BiScO3-xPbTiO3 (x=0.01 0.48) + Fe y = +0.66) (1-x)BiScO3-xPbTiO3 (x = 0.0013 log(x) + 0.00 y = -0.38 (1-x)BiScO3-xPbTiO3 (x = 0. (1-x)PbZrO3-xPbTiO3 (x = 0.3 y = -0.66.66) + Mn 0.5176 1.64 and 0.00 1.00 (1-x)BiScO3-xPbTiO3 (x=0.6532 0.66) (1-x)BiScO3-xPbTiO3 (x=0.7 Aging study at 2500C.0639 log(x) + 76.4735 log(x) + 250.1534 0.64) + Mn 1.00 2.00 0.66) y = -0.0524 log(x) + 1.00 0.66.00 y = +0.64) + Mn y = -3.8 Aging study at 2500C.67 d 33 (pC/N) d 33 (pC/N) 200 150 100 50 0 0.50 -0.64 and 0.00 0.1 1 10 100 1000 10000 0.00 (1-x)BiScO3 -xPbTiO3 (x = 0.1 1 10 100 1000 10000 Time (hr) Time (hr) Time (hr) Figure 5.2167 y = -0. Rayleigh analysis of slope αd ( 10-14 Cm/NV) for piezoelectric response as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.01 -1.0536 log(x) + 195. Rayleigh analysis for d33 as a function of aging time for unmodified and modified (1-x)PbZrO3-xPbTiO3 x=0.1 1 10 100 1000 10000 0.4102 0.50 0.50 1.0540 log(x) + 1.01 y = -0.1 1 10 100 1000 10000 0.5006 log(x) + 118.(1-x)PbZrO3-xPbTiO3 (x = 0.75 d33 (pC/N) 250 y = +1. .64) α ( 10 Cm/NV) α ( 10 Cm/NV) -14 -14 0.50 (1-x)BiScO3-xPbTiO3 (x=0.64) (1-x)BiScO3-xPbTiO3 (x = 0.0504 log(x) + 1.48.48.12 y = +0.517 log(x) + 156.0123 log(x) + 0.01 0.9962 log(x) + 317.50 y = -0.0019 log(x) + 0.01 (1-x)BiScO3-xPbTiO3 (x = 0. and (1-x)BiScO3-xPbTiO3 x=0.1 1 10 100 1000 10000 Time (hr) Time (hr) Time (hr) Figure 5.0504 log(x) + 1.64) 2.5176 (1-x)BiScO3-xPbTiO3 (x = 0.48) 2.64 150 100 50 0 0.64) 400 350 300 250 200 150 100 50 0 0.

5 Summary and conclusion Purpose of this study was to evaluate thermal degradation and aging behavior for (1-x)BiScO3-xPbTiO3 ceramics and compare it with (1-x)PbZrO3-xPbTiO3.1%/decade for piezoelectric constant d33. 3.2%/decade respectively by Fe modification.8%/decade for piezoelectric constant d33. which were reduced to 0.6%/decade for dielectric constant K.5.9%/decade. It showed aging rate of 0.08%/decade for dielectric constant K.6%/decade. 71 . and 0. and -0.8%/decade for piezoelectric constant d33.48 showed high aging rates of 4.2%/decade for dielectric constant K.8%/decade for planar coupling coefficient kP. Tetragonal (1-x) BiScO3-xPbTiO3 x=0. (1-x)PbZrO3-xPbTiO3 x=0. Rayleigh analysis for piezoelectric response indicates significant contribution of depoling mechanism in the aging of these materials.64 showed moderate aging rates of 2. 0. 0. and 2. The MPB composition of (1-x) BiScO3xPbTiO3 x=0.6%/decade for planar coupling coefficient kP.66 found to have the highest resistance against thermal aging. and -0.9%/decade for planar coupling coefficient kP. 0.

Recently Chen et al.Chapter 6: Summary and future work 6. 2006 reported that tetragonal compositions of (1-x)BiScO3-xPbTiO3 showed resistance to thermal depoling up to the temperature close to their ferroelectric Curie temperature TC~4450C. demonstrate improved aging of (1-x)BiScO3-xPbTiO3 compared with (1-x)PbZrO3-xPbTiO3. For the current work commonly used (1-x)PbZrO3-xPbTiO3 and recently developed high temperature piezoelectric ceramic (1-x)BiScO3-xPbTiO3 were prepared using solid state route.1. and establish a methodology for lifetime testing of piezoelectric materials. Recently materials based on (1-x)BiScO3-xPbTiO3 were developed with TC ∼4500C.46 This project was focused to study the thermal degradation and aging study for (1-x)BiScO3-xPbTiO3.1 Summary 6.41 Enhanced room temperature properties and higher transition temperature makes this material promising for high temperature applications above 2000C. The MPB and tetragonal compositions with and without 72 . and d33 ∼500 pC/N. For technologically important piezoelectric devices one of the most important requirements is long term reliability. Until now there has been less work done on long term degradation and life time analysis of these materials and no widely accepted technique exists for reliability and lifetime testing.1 Thermal degradation and aging study for (1-x)PbZrO3-xPbTiO3 and (1-x)BiScO3-xPbTiO3 ceramics Lots of work has been done on the development of new piezoelectric materials to meet the requirements of various applications in extreme operating conditions.

200h. 100 h. High aging rates for (1-x)PbZrO3-xPbTiO3 (x=0.48) is most likely due to the high temperature (~ 2/3 TC) used of the aging study. As a rule of thumb.39. and planar coupling coefficient kP due to the thermal depoling effect. The results were analyzed to find out aging of piezoelectric and dielectric properties. in order to minimize the aging effect maximum application of piezoelectric materials is generally restricted to ∼½ TC. The MPB composition of (1-x)PbZrO3-xPbTiO3 (x=0. Sets of 15 pellets for each compositions were characterized after 24 hours from poling for piezoelectric constant d33.modification of acceptor dopants were used for the thermal degradation and aging study.2%/decade for dielectric constant K. 10 h. hence high temperature 2500C was selected for the study. 400h.48) changed the behavior of this material and it showed very high degradation for d33 (~20%) and kP(~15%) in 73 . The conditioning treatment was done at 2500C for 1 min to evaluate instantaneous thermal degradation. dielectric loss D. and 2. and Rayleigh analysis for dielectric and piezoelectric responses. All compositions showed 5 to 20% reduction in piezoelectric constant d33.52 Purpose of this study was to evaluate the promise of (1-x)BiScO3-xPbTiO3 system as a high temperature piezoelectric material.56 After the conditioning treatment. Aging rates were calculated for piezoelectric constant d33 and planar coupling coefficient kP.48) has Curie temperature TC=3860C and showed very high aging rate of 4. planar coupling coefficient kP. which is consistent with previous researches. dielectric constant K. Changes in the above properties were evaluated at predetermined intervals of 1 h.9%/decade for planar coupling coefficient kP.8%/decade for piezoelectric constant d33. Fe-modification to (1-x)PbZrO3-xPbTiO3 (x=0. 700h and 1000h. pellets were reheated to the temperature of 2500C for 1000 hrs. 3.

64) has Curie temperature TC=4360C and showed less than 10% reduction for d33 and kP after conditioning treatment at 2500C.48) showed high degradation of d33 and kP in the conditioning treatment which is most likely due to relatively high mobility of defect dipoles during initial period.1) for this material. 2006 studied thermal stability for (1-x)BiScO3-xPbTiO3 and observed that the tetragonal phase shows excellent thermal stability up to ~4400C whereas the MPB and rhombohedral compositions began to depole when the temperature were >3000C.48) was also evident from pinched ferroelectric P-E hysteresis loop (Figure 4. The instantaneous aging effect in Fe-modified (1-x)PbZrO3-xPbTiO3 (x=0.40 Recently Chen et al.6%/decade for kP.conditioning treatment at 2500C.907) compared to PbZrO3 (t=0. After initial degradation in the conditioning treatment this material showed low aging rates 0. Acceptor doping to (1-x)PbZrO3-xPbTiO3 (x=0.96) which results higher TC for (1-x)BiScO3-xPbTiO3 compared to (1-x)PbZrO3-xPbTiO3.48) create anion vacancies. Alignment of defect dipoles in the direction of polarization vector within the domain stabilizes the domain structure which possibly helped to reduce aging rate after initial degradation.2 %/decade for K.9%/decade for d33. The mobility of defect dipoles is relatively high in acceptor doped materials due to easy movement of vacancies in oxygen octahedra network.15 Fe-modified (1-x)PbZrO3xPbTiO3 (x=0. BiScO3 has lower tolerance factor (t=0. and -0. and 0. This indicates higher depoling resistance of (1-x)BiScO3-xPbTiO3 system 74 . 46 The MPB composition (1-x)BiScO3-xPbTiO3 (x=0.

08%/decade for piezoelectric constant d33.compare to (1-x)PbZrO3-xPbTiO3. The MPB composition (1-x)BiScO3-xPbTiO3 (x=0. Thermal degradation and aging study conducted can be concluded that (1-x)BiScO3-xPbTiO3 has more stability compared to (1-x)PbZrO3-xPbTiO3 at high temperature >2000C . The same behavior is evident for (1-x)BiScO3-xPbTiO3 system.66) has high distorted perovskite unit cells (c/a =1.66) in particular has 75 .66) has Curie temperature TC=4460C and showed least degradation due to thermal depoling. Calculated aging rates for (1-x)BiScO3xPbTiO3 (x=0. and dielectric constant K respectively.8%/decade. 0.8%/decade for kP.023) and showed high resistance against aging. less than 5% for d33 and kP after conditioning at 2500C. and -0.64) were 2. and 0. The Rayleigh analysis for piezoelectric response showed that there is no apparent change in the relation of intrinsic and extrinsic contributions to piezoelectric coefficient. Calculated aging rate for (1-x)BiScO3-xPbTiO3 (x=0. The tetragonal (1-x)BiScO3-xPbTiO3 (x=0. planar coupling coefficient kP. which suggest significant contribution of depoling mechanism in the aging of these materials.1%/decade for d33. It was concluded through the dielectric aging study of BaTiO3 in 1950’s that aging rate reduces as the tetragonal distortion of the perovskite unit cell is increases6.028) compared to the MPB composition (c/a=1.64) has the coexistence of rhombohedral and tetragonal phases to give 14 possible polarization directions to optimize crystallographic orientation and resulting high dielectric and piezoelectric properties. The tetragonal composition (1-x)BiScO3-xPbTiO3 (x=0.66) were 0. Tetragonal phase also showed very high resistance against the aging of electromechanical properties. and 0. The tetragonal (1-x)BiScO3xPbTiO3 (x=0.6%/decade.6%/decade for K.

64) and reported 76 . During thermal degradation and aging study it was observed that heating of pellets to the temperature 2500C for 1 min caused 5 to 20% reduction in piezoelectric constant d33 and planar coupling coefficient kP.2 Future work 6.1 Aging study for acceptor doped (1-x)BiScO3-xPbTiO3 Fe-modification to (1-x)PbZrO3-xPbTiO3 (x=0.6%/decade and -0. and kP after initial conditioning treatment. and dielectric constant K. For the current study. In the past aging studies were done generally up to 104 min. Winotai et al. Mn-modification to (1-x)BiScO3xPbTiO3 did not help to improve the aging behavior of the system. 2005 studied the effect of Fe2O3 doping on (1-x)BiScO3-xPbTiO3 (x=0. 39.56 6.66) stronger for the high temperature piezoelectric sensor applications.08%/decade for piezoelectric constant d33 and planar coupling coefficient kP.8%/decade.very low aging rates of 0. The aging study showed that most of the reduction in electromechanical properties occurred up to 500hrs. temperature of 2500C was selected based on preliminary study.2 Development of methodology for lifetime testing for piezoelectric ceramics The second goal of this study was to establish a methodology for lifetime testing of piezoelectric materials.2. This makes claim of (1-x)BiScO3-xPbTiO3 (x=0.1. Outcome of this study indicate that instantaneous thermal degradation and aging should be evaluated separately. 0.48) helped to reduce the aging rates for d33. 6. and dielectric constant K respectively. this should be considered to decide the length of aging study.

particularly in low field region where density and domain wall structure remain unchanged. in general those are reversible with no loss. The piezoelectric response in ferroelectric materials contains both intrinsic and extrinsic contribution.36 Thermal degradation and aging study of (1-x)BiScO3-xPbTiO3 with Fe3+. 77 . 6. generally those are non linear and lossy and varies as a function of time. For the current work Rayleigh analysis was done to evaluate aging effect on overall dielectric and piezoelectric response and observed that there is no apparent change in the relation of intrinsic and extrinsic contributions to piezoelectric coefficient.12. For the current study Mn-doping to (1-x)BiScO3-xPbTiO3 was done without charge compensation and site balance and did not helped to improve aging behavior. In future thermal degradation and aging study can be tried for the compositions with charge compensation and site balance. and other acceptor dopant like Nb5+ can be conducted to develop and evaluate better material with higher thermal stability and higher resistance against the piezoelectric and dielectric aging.16-18 Intrinsic contributions are mainly due to the strain in crystal lattice.2. frequency. Extrinsic contributions are mainly due to the motion of non 1800 domain walls.2 Methodology for lifetime testing for piezoelectric ceramics Rayleigh law is being used in piezoelectric materials to quantify the irreversible and irreversible piezoelectric response. Rayleigh law indicates a liner dependence of the piezoelectric constant and dielectric constant with the increasing field.improvement in overall piezoelectric properties with addition of 1 mol% Fe2O3. and field.

extrinsic reversible and nonreversible components separately during aging study by using Rayleigh analysis.Future work can be focused to study the change in intrinsic. 78 .

6259(µm) RAW MATERIAL ZrO2 10 B 9 8 Median Size Mean Size Std.1 1 Diameter(µm) 0 10 100 0.6589(µm) q(%) 12 Median Size Mean Size Std.4786(µm) q(%) 10 q (%) q(%) 6 5 4 8 6 3 4 2 0 0. q(%) 1.1 1 10 100 Diameter(µm) 79 .1 1 10 100 Diameter(µm) Diameter(µm) RAW MATERIAL PbCO3 16 14 12 7 Median Size Mean Size Std. 7.52971(µm) 4.19895(µm) 0. 2. 1.Dev.1 1 Diameter(µm) 2 1 0 10 100 0. 7.05491(µm) 1.68221(µm) 2.Dev.43194(µm) 7.55794(µm) 3.Appendix – A Particle size and distribution for metal oxides / carbonate powders.18839(µm) 0.Dev. RAW MATERIAL Bi2O3 18 16 14 RAW MATERIAL Sc2O3 14 Median Size Mean Size Std.01 0.1 1 10 100 q (%) 10 8 6 8 6 4 4 2 0 2 0 0. 4.34191(µm) 7.67452(µm) 1.18016(µm) 2.Dev.87174(µm) 2.4561(µm) q(%) q(%) 12 10 12 q (%) 0.Dev.3243(µm) Median Size Mean Size Std.6177(µm) 10 10 8 6 q (%) 8 q(%) 6 4 4 2 2 0 0.03366(µm) 1.Dev.1 1 Diameter(μm) 10 100 RAW MATERIAL TiO2 14 RAW MATERIAL MnO2 12 Median Size Mean Size Std.

2 Hrs 6000C – 2 Hrs 6500C – 2 Hrs 0 1.2 Hrs 6500C .0263 1.0262 1.0027 1.0262 80 .1657 1.1657 1.0025 1. Material LOI parameter Multiplying factors LOI-II LOI-I Average PbCO3 ZrO2 TiO2 Bi2O3 SC2O3 6500C .0033 1.0024 1.2 Hrs 650 C .0034 1.0027 1.0025 1.0027 1.0034 1.1656 1.Appendix – B LOI results for metal oxides / carbonate powders.

48) 5000 003 .64) 004-BSPT66-RAW 5000 0 20 30 40 50 60 70 80 004-BSPT66 -1st.66) 81 .CALCINATION.6 Hrs 1000 100 20 30 40 50 60 70 BSPT ( X = 0.750* C .2nd Calc 750*C.CALC 750*C 6HRS 011-PZT5248-2ND CALC 850*C -6HRS 1000 100 20 30 40 50 60 70 PZT ( X = 0.BSPT64-RAW 0 20 30 40 50 60 70 80 003-BSPT64-1st CAL 750*C .6hrs 1000 100 20 30 40 50 60 70 80 BSPT ( X = 0.Appendix – C XRD scans for PZT and BSPT powders before and after calcinations PZT raw Material 1000 100 20 10000 1000 100 10 20 10000 30 40 50 60 70 30 40 50 60 70 011-PZT5248.2nd CALC 750*C .6 Hrs 1000 100 20 30 40 50 60 70 80 003-BSPT64.6Hrs 1000 100 20 30 40 50 60 70 80 004-BSPT66.

0 0 2 4 6 8 10 12 14 950 1000 1050 1100 1150 1200 T emperature 0 C T ime Hrs BSPT 66.7 7.8 7.0 900 950 1000 1050 1100 1150 T emperat ure 0 C 1200 BSPT 64 + 0.0 900 950 1000 1050 1100 1150 1200 T emperat ure 0 C 7.2 7.9 6.3 7. Time 1 Hr 7. Time 2 Hr 7.2% Fe2O3.4 6.6 Bulk Density gm/cm3 7.6 7.4 7.5 7. Time 2 Hr 7. Time 1 Hr 8.4 7.0 6.5 Hrs 82 .2 7.5 7. Time 1. Time 1.8 7.6 7.1 7.4 7.5 7.2 7. Temperature 10250C 7.8 7.8 7.5 7.0 900 950 1000 1050 1100 1150 1200 T emperature C 0 7.6 900 Bulk Density gm/cm3 BSPT 64.6 7.1 7.4 100 105 110 115 120 125 130 135 0 0 0 0 0 0 0 0 T emperat ure 0 C 7.7 7.6 7.2% MnO2.1 7.4 7.8 6.7 7.1 7.2 7.2 7.1 7.7 7.7 6.6 7.1 7.6 6.2 7.5 7.4 7.5 Hrs PZT5248 + 0.0 1150 1200 1250 1300 1350 T emperature 0 C PZT 5248.3 7.0 0 2 4 6 8 10 12 14 T ime Hrs BSPT 64.3 7.4 7.6 3 B ulk Density gm/cm 7.3 7.4 7.0 7.5 7.0 6.9 Bulk Density gm/cm3 7.7 3 Bulk Density gm/cm BSPT 66. Temperature 10250C 7.2 6.6 7.8 7.8 6.Appendix – D Sintering study for PZT and BSPT (bulk density.2 7.for variable time & temperature) Bulk Density gm/cm3 Bulk Density gm /cm3 7.3 7.5 BSPT 66 + 0.8 Bulk Density gm/cm3 7.3 7.2% MnO2.

004 0.004 0.004 0.004 0.013 0.012 0.013 0.012 0.012 0.004 0.004 0.005 Continued… 83 .004 100 KHz K D 873 876 843 865 906 913 931 873 864 830 946 903 891 898 988 0.011 0.013 0.012 0.003 0.012 0.004 0.010 0.004 0.009 0.011 0.011 0.010 0.005 0.004 0.007 0.004 0.012 0.004 0.E Dielectric properties of poled pellets at various frequencies Material : PZT ( x= 0.003 0.Appendix .004 0.005 0.011 0.011 0.012 0.010 K 754 712 772 828 744 703 686 713 725 743 750 779 822 826 D 0.003 0.004 0.011 0.004 0.005 0.004 0.013 741 700 758 815 731 692 677 702 713 733 739 767 808 813 743 705 757 816 742 696 686 706 715 735 736 768 809 813 Material : PZT (x=0.007 0.013 0.003 0.004 0.004 0.013 0.010 0.004 0.011 0.011 0.004 0.004 0.010 0.013 0.005 K 863 865 832 855 889 899 917 861 851 817 924 886 874 885 964 D 0.004 0.011 0.013 0.004 0.010 0.004 0.011 0.48) + Fe Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 100Hz K 871 871 837 860 893 906 924 866 856 823 931 891 880 892 970 1 KHz D 0.011 K 100 KHz D 0.004 0.004 0.007 0.004 0.004 0.004 0.010 0.004 0.004 0.004 0.007 0.004 0.004 10 KHz K D 858 860 828 851 885 894 912 857 846 812 919 881 870 880 958 0.014 0.012 0.004 0.004 0.011 0.48) Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 100Hz K 768 724 785 841 756 714 696 722 737 754 762 791 834 838 1 KHz D 0.004 0.004 0.004 0.010 0.013 0.012 0.004 0.005 0.012 0.005 0.007 0.009 0.010 K 10 KHz D 0.008 0.012 0.013 0.011 0.010 0.014 0.010 0.012 0.003 0.012 0.013 0.010 0.013 0.007 0.005 0.011 0.011 0.

4239 1056.1846 1106.043 0.048 0.3723 1074.7201 1 KHz D 0.8007 1427.025 0.012 0.8708 1046.4373 1102.034 0.033 0.7659 1626.6091 1430.043 0.5052 1709.8004 1061.2207 1062.076 0.1754 1653.5056 1104.5201 1445.6388 1444.033 0.6097 1041.021 0.008 0.011 0.042 0.0833 1457.043 0.1392 1420.613 1391.009 0.3026 1098.288 1076.042 0.008 K 1080 1084 1108 1088 1105 1087 1089 1078 1071 1081 1111 1068 1099 1091 1071 D 0.022 0.5978 1059.021 0.008 0.011 0.9645 1087.3216 1065.076 0.6603 1826.012 0.022 0.029 0.034 0.080 0.043 0.1233 1441.026 0.7572 1084.1986 1644.3246 1060.043 0.7849 1604.9948 1700.043 0.3015 1588.022 0.5303 1645.4996 1553.032 0.2738 1746.157 1097.4401 1065.1081 1547.025 0.4513 0.044 0.011 10 KHz K D 1057.033 0.227 1082.076 0.011 0.033 0.394 1622.008 0.021 0.2535 1535.042 0.0969 1559.065 0.085 0.044 100 KHz K D 1644.025 0.042 0.009 0.7294 1031.021 0.045 0.6766 1558.021 0.1235 1409.026 0.046 0.026 0.1496 0.602 1590.011 0.035 0.3239 1494.046 0.5588 1482.033 0.031 0.024 0.0822 1581.6743 1115.010 0.021 0.009 0.022 K 1755 1748 1643 1732 1500 1484 1692 1523 1657 1648 1579 1526 1539 1529 1639 D 0.1187 1403.6793 0.2564 1432.028 0.158 1127.2321 1564.046 0.021 0.026 0.063 0.077 0.043 0.7964 1094.046 0.3189 1045.0375 1559.011 0.080 Material : BSPT64 + Mn Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 100Hz K 1095.8347 1085.033 0.1762 1709.046 0.7887 1053.4895 1085.024 0.020 100 KHz K D 1050.0618 1052.8559 1803.031 0.028 0.3846 1081.5398 1124.020 0.4495 1049.076 0.802 1544.5701 1055.046 0.0723 1102.042 Continued… 84 .6768 1082.012 0.021 0.594 1120.5055 1646.2239 1031.026 0.042 0.029 10 KHz K D 1671.021 0.075 0.1659 1032.013 0.033 0.077 0.008 0.024 0.021 0.2308 1593.042 0.012 0.1354 1 KHz D 0.6654 1067.9048 1065.011 0.026 0.012 0.8709 1593.012 0.046 0.Material : BSPT64 Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 100Hz K 1822.0036 1446.013 0.022 0.079 0.075 0.7545 1078.009 0.027 0.009 0.046 0.009 0.008 0.1243 1057.044 0.5248 1627.044 0.008 0.021 0.462 1049.009 0.4055 1718.077 0.

017 0.010 0.019 0.006 0.010 0.017 0.006 0.017 0.005 0.006 0.016 0.006 K 976 985 998 1002 956 1001 962 972 966 978 957 960 975 978 1007 956 K 963 975 985 992 946 991 951 961 956 965 947 950 965 968 996 946 D 0.005 0.015 0.017 K 1212 1142 1124 1272 1258 1333 1250 1273 1166 1201 1255 1230 1323 1331 1324 1232 K 1181 1113 1096 1238 1225 1298 1217 1238 1136 1170 1221 1196 1282 1292 1285 1199 D 0.018 0.016 0.025 0.038 0.024 0.015 0.032 0.009 0.015 0.008 0.012 0.035 0.006 0.016 0.006 0.005 0.015 0.019 0.029 0.021 0.017 0.005 10 KHz D 0.006 0.016 85 .031 0.009 0.020 0.016 0.023 0.031 0.018 0.020 0.007 0.006 0.016 0.016 0.011 0.009 0.017 0.017 0.027 0.020 0.006 0.015 0.022 0.020 0.007 0.009 100 KHz K D 951 965 975 986 938 982 941 953 951 952 943 945 956 960 988 941 0.007 0.006 0.010 0.005 0.009 0.009 0.017 0.031 0.022 0.032 1188 1117 1100 1246 1232 1306 1225 1243 1137 1172 1228 1200 1292 1303 1297 1206 Material : BSPT66 + Mn Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 100Hz K 985 994 1007 1011 963 1009 970 981 974 988 964 967 984 986 1015 963 1 KHz D 0.029 0.017 0.017 0.006 0.010 0.015 0.018 0.018 0.017 0.019 0.031 0.018 0.006 0.022 0.017 0.009 0.009 0.018 0.009 0.006 0.017 0.012 0.027 0.005 0.006 0.005 0.029 0.031 0.022 0.018 0.005 0.016 0.006 0.021 0.015 10 KHz D 0.017 0.017 0.022 0.016 0.021 0.021 0.017 0.006 0.006 0.037 0.020 0.033 0.006 0.021 K 100 KHz D 0.018 0.021 0.006 0.Material : BSPT66 Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 100Hz K 1242 1169 1151 1302 1288 1365 1280 1306 1195 1231 1286 1261 1358 1365 1357 1262 1 KHz D 0.019 0.005 0.017 0.

011 0.01 0.011 0.012 0.Appendix .01 0.012 0.010 0.012 0.014 0.00 K 778 739 800 876 757 733 701 757 767 778 775 818 862 866 786 1.012 0.011 0.011 0.011 0.011 0.012 0.016 0.009 0.013 0.012 0.013 0.009 0.0118 1.012 0.016 0.011 0.010 0.95 K 200Hr D 0.011 0.48) Poled D 0.013 0.012 0.00 :PZT (x=0.010 0.011 0.011 0.012 0.010 0.011 0.012 0.015 0.015 0.010 0.011 0.93 0.013 0.10 700Hr K D 686 659 731 826 676 622 657 666 683 736 712 779 839 841 722 0.92 679 630 712 799 684 601 632 637 662 717 715 755 811 815 704 0.016 0.012 0.011 0.014 0.01 0.010 0.011 0.013 0.03 1Min D 0.011 0.017 0.015 0.014 0.014 0.017 0.06 K 721 678 752 840 694 668 623 688 703 752 731 797 827 843 736.011 0.010 0.013 0.011 0.012 0.011 1.012 0.00 K 400Hr D 0.011 0.013 0.011 0.011 1.011 0.006 0.00 1Hr D 0.013 0.013 0.013 0.92 674 645 717 809 667 611 641 654 671 724 700 764 823 826 709 0.012 0.012 1.0109 0.012 0.01 0.013 0.013 0.011 0.011 0.013 0.017 0.013 0.010 0.011 0.012 0.01 0.42 1000Hr K D 678 648 717 811 664 609 645 653 670 726 700 766 825 827 710 0.012 0.014 0.014 0.011 0.011 0.011 0.012 0.013 0.012 0.013 0.015 0.93 86 6 7 8 9 10 11 12 13 14 Avg Ratio Continued… .010 0.012 0.014 0.016 1.011 0.012 0.011 0.012 0.013 0.94 0.010 0.012 0.010 0.19 K 759 719 781 858 743 712 686 731 746 761 733 794 839 843 764.08 674 635 704 792 682 597 624 641 664 715 714 754 811 815 702 0.012 0.8 0.017 0.8 1.010 0.962 10Hr D 0.012 0.013 0.012 0.013 0.010 0.013 0.98 K 100Hr D 0.011 0.010 0.011 0.012 0.014 0.012 0.013 1.018 0.012 0.012 0.016 0.010 0.012 0.011 0.F Details of dielectric properties (1 KHz) with the aging time at 2500C Material Sample No 1 2 3 4 5 K 768 724 785 841 756 714 696 722 737 754 762 791 834 838 766 1.012 1.013 0.

002 0.003 0.003 0.003 0.003 0.003 0.002 0.004 0.003 0.48) +Fe Poled D 0.003 0.005 0.003 0.003 0.05 899 916 898 919 955 946 958 933 919 847 975 935 932 934 998 931 1.003 0.99 10Hr D 0.003 0.003 0.004 0.06 87 Continued… .003 0.003 0.003 0.002 0.004 0.003 0.004 0.004 0.003 0.52 K 851 861 841 863 898 891 897 873 864 803 927 888 880 878 934 877 0.003 0.002 0.003 0.004 0.Material Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Avg Ratio K :PZT (x=0.002 0.002 0.34 K 100Hr D 0.003 0.003 0.004 0.05 904 920 903 924 957 947 960 937 926 849 977 936 936 939 1010 935 1.003 0.003 0.004 0.003 0.06 871 871 837 860 893 906 924 866 856 823 931 891 880 892 970 885 1.003 0.69 1000Hr K D 918 932 913 935 967 957 970 949 939 862 992 948 948 950 1014 946 1.003 0.003 0.07 0.003 0.003 0.002 0.004 0.003 0.003 0.003 0.003 0.002 0.003 0.63 K 903 911 890 915 947 943 951 928 918 852 982 937 929 930 994 929 1.003 0.007 0.003 0.00 1Min D 0.003 0.003 0.004 0.003 0.003 0.004 0.005 0.003 0.003 0.006 1.004 0.004 0.007 0.003 0.004 0.003 0.004 0.003 0.003 0.002 0.003 0.004 0.003 0.52 K 400Hr D 0.007 0.004 0.004 0.003 0.003 0.003 0.003 0.004 0.005 0.004 0.003 0.004 0.003 0.53 K 200Hr D 0.004 0.003 0.002 0.003 0.003 0.003 0.003 0.003 0.002 0.003 0.003 0.003 0.005 0.005 0.003 0.00 K 913 926 905 928 959 952 962 945 929 861 990 944 939 939 1020 941 1.002 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.004 0.007 0.003 0.003 0.007 0.004 0.004 0.002 0.003 0.003 0.53 901 916 898 919 954 947 958 932 921 849 977 937 933 935 997 932 1.005 0.004 0.003 0.54 700Hr K D 912 929 912 932 964 954 968 946 933 856 984 943 943 947 1018 943 1.003 0.003 0.05 1Hr D 0.003 0.003 0.007 0.008 0.002 0.005 0.002 0.004 0.07 0.004 0.003 0.005 0.003 0.002 0.003 0.

4 0.037 0.037 0.028 0.036 0.033 0.0323 1.028 0.037 0.025 0.036 0.26 K 100Hr D 0.035 0.037 0.032 1.038 0.035 0.022 0.037 0.037 0.021 0.032 0.037 0.037 0.025 0.94 1648 1660 1544 1601 1507 1483 1606 1528 1579 1647 1585 1527 1546 1527 1632 1571 0.29 K 400Hr D 0.021 0.025 0.96 1Hr D 0.037 0.037 0.036 0.030 0.94 88 Continued… .028 0.037 0.024 0.036 0.026 0.033 0.037 0.038 0.022 0.029 0.030 0.037 0.021 0.038 0.037 0.023 0.038 0.028 0.020 0.036 0.028 0.025 0.038 0.97 0.024 0.031 1.027 0.032 0.027 0.29 K 200Hr D 0.25 1684 1712 1577 1634 1537 1511 1629 1554 1607 1680 1617 1559 1576 1560 1665 1607 0.026 0.022 0.037 0.99 1823 1826 1710 1803 1564 1547 1746 1589 1709 1719 1646 1591 1605 1594 1701 1678 1.030 0.030 0.027 0.024 0.034 1.031 0.032 1.036 0.022 0.036 0.034 0.026 0.037 0.027 0.037 0.029 0.037 0.95 0.029 0.022 0.Material Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Avg Ratio K :BSPT64 Poled D 0.029 0.029 0.13 1000Hr K D 1668 1670 1561 1617 1526 1504 1625 1550 1597 1670 1607 1547 1565 1546 1645 1589.036 0.036 0.037 0.030 0.035 0.00 1Min D 0.031 0.021 0.036 0.038 0.032 0.032 0.033 0.029 0.032 0.032 0.037 0.031 1.025 0.037 0.020 0.034 0.022 0.038 0.026 0.038 0.031 0.026 0.032 0.036 0.026 0.026 0.030 0.026 0.027 0.00 K 1742 1791 1656 1726 1567 1538 1674 1590 1648 1732 1657 1598 1613 1598 1693 1655 0.38 K 1692 1747 1608 1670 1544 1513 1636 1567 1612 1678 1616 1556 1576 1545 1685 1616 0.019 0.026 0.037 0.034 0.021 0.026 0.94 10Hr D 0.036 0.028 1.021 0.02 0.037 0.30 700Hr K D 1703 1713 1598 1655 1580 1557 1651 1604 1625 1731 1665 1603 1620 1601 1692 1636 0.031 0.037 0.032 0.30 K 1646 1709 1561 1622 1498 1488 1607 1546 1584 1646 1584 1529 1546 1519 1661 1583 0.038 0.027 0.037 0.036 0.037 0.036 0.037 0.032 1.027 0.025 1.96 1655 1678 1555 1613 1518 1490 1609 1537 1589 1657 1594 1536 1556 1538 1646 1580 0.025 0.024 0.037 0.028 0.033 0.

03 0.028 0.025 0.11 1000Hr K D 1260 1268 1345 1291 1304 1287 1268 1258 1244 1278 1295 1227 1283 1266 1233 1276.15 1265 1277 1343 1297 1315 1290 1278 1270 1256 1287 1300 1237 1292 1277 1246 1282 1.030 3.026 0.76 0.027 0.027 0.014 0.03 0.029 0.009 0.008 0.014 0.009 0.008 0.20 0.015 0.015 0.027 0.03 0.030 0.07 10Hr D 0.26 K 1230 1275 1228 1162 1314 1299 1290 1271 1252 1238 1213 1165 1291 1275 1232 1249 1.50 700Hr K D 1298 1307 1385 1367 1346 1326 1321 1302 1287 1319 1334 1268 1304 1311 1276 1319 1.023 0.03 0.45 K 400Hr D 0.03 0.030 0.00 1Min D 0.024 0.009 0.027 0.008 0.03 0.029 0.019 2.03 0.029 0.029 3.008 0.Material Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Avg Ratio K :BSPT64+Mn Poled D 0.027 0.027 0.022 0.026 0.029 1.024 0.021 0.028 0.029 0.024 0.023 0.031 0.015 0.028 0.030 0.15 1248 1256 1330 1279 1295 1276 1267 1249 1236 1267 1283 1217 1272 1259 1227 1267 1.03 0.021 0.03 0.029 0.024 0.03 0.029 0.029 0.009 0.026 0.009 0.03 0.029 0.16 1261 1262 1329 1284 1298 1250 1273 1256 1244 1272 1289 1226 1278 1263 1231 1270 1.03 0.13 1Hr D 0.030 0.03 0.021 0.03 0.027 0.9 0.030 0.031 0.016 0.029 0.027 0.023 0.020 0.020 0.027 0.030 0.029 0.031 0.03 0.03 0.030 3.023 0.15 89 Continued… .00 K 1187 1189 1210 1152 1231 1202 1202 1180 1169 1197 1193 1124 1207 1198 1172 1187 1.023 2.021 0.022 0.029 0.023 0.028 0.41 K 200Hr D 0.029 0.022 0.029 0.03 0.029 0.031 0.030 0.029 0.028 0.027 0.008 0.03 0.009 0.009 0.029 0.021 0.028 0.023 0.03 0.021 0.008 0.08 1095 1099 1124 1103 1120 1103 1105 1095 1085 1097 1127 1082 1115 1107 1084 1103 1.03 0.03 0.010 0.016 0.024 0.029 0.024 0.03 0.027 0.71 K 100Hr D 0.029 0.029 0.027 0.027 0.029 0.027 0.92 K 1160 1169 1236 1188 1199 1182 1176 1163 1152 1176 1196 1135 1181 1169 1146 1175 1.03 0.031 0.023 0.025 2.009 1.025 0.030 0.017 0.027 3.023 0.008 0.030 0.03 0.023 0.030 0.024 0.023 0.

019 0.016 0.018 1.017 0.016 0.016 0.016 0.016 0.018 0.021 0.020 0.02 0.018 0.016 0.Material Sample No 1 2 3 4 5 6 7 8 9 K :BSPT66 Poled D 0.018 0.016 0.018 0.018 0.76 0.016 0.016 0.017 0.019 0.016 0.017 0.016 0.018 0.017 0.017 0.016 0.018 0.00 90 10 11 12 13 14 15 16 Avg Ratio Continued… .018 0.017 0.021 0.0174 1.018 0.016 0.017 0.018 0.018 1.017 0.017 0.020 0.019 0.016 0.017 0.021 0.016 0.13 100Hr K D 1298 1147 1259 1274 1305 1278 1267 1160 1196 1212 1228 1265 1335 1354 1361 1270 1263 0.017 0.017 0.02 0.015 0.018 0.018 1.017 0.015 0.016 0.017 0.021 0.02 0.17 K 1294 1154 1259 1270 1294 1283 1263 1162 1196 1215 1230 1262 1320 1338 1354 1269 1260 0.018 0.017 0.016 0.017 0.015 0.019 0.02 0.019 0.018 0.019 0.020 0.0166 1.017 0.018 0.016 0.018 0.017 0.017 0.020 0.99 0.019 0.017 0.016 0.016 0.018 0.018 0.017 0.018 0.017 0.017 0.015 0.017 0.017 1.016 0.019 0.019 0.016 0.00 K 1299 1155 1256 1273 1295 1284 1265 1168 1205 1223 1234 1266 1322 1338 1355 1280 1264 0.17 K 1292 1141 1251 1267 1295 1271 1260 1153 1188 1205 1222 1257 1323 1333 1348 1265 1254 0.70 1150 1143 1330 1245 1303 1205 1359 1271 1083 1262 1185 1300 1374 1330 1328 1280 1253 0.017 0.015 0.017 0.018 1.018 0.98 1147 1139 1323 1239 1298 1199 1353 1266 1081 1258 1181 1295 1369 1326 1324 1275 1248 0.020 0.016 0.016 0.017 0.11 K 700Hr D 0.015 0.017 0.00 1Min D 0.016 0.99 1151 1169 1262 1280 1288 1302 1365 1195 1231 1242 1261 1286 1357 1358 1365 1306 1276 1.021 0.018 0.018 0.06 1000Hr K D 1160 1152 1335 1252 1313 1212 1367 1278 1093 1272 1194 1310 1386 1342 1342 1289 1274.017 0.016 0.02 0.016 0.98 1174 1166 1353 1269 1330 1228 1385 1297 1106 1289 1212 1328 1410 1364 1362 1307 1279 1.016 0.018 0.13 K 200Hr D 0.017 0.019 0.016 1.018 0.98 10Hr D 0.015 0.017 0.018 0.017 0.017 0.017 0.018 0.11 K 400Hr D 0.020 0.017 0.016 0.02 0.016 0.016 0.017 0.017 0.021 0.017 0.018 0.99 1Hr D 0.017 0.8 0.016 0.018 0.019 0.018 0.018 0.016 0.016 0.017 0.016 0.019 0.017 0.021 0.017 0.018 0.

013 0.009 0.014 0.010 0.015 0.010 0.011 0.014 0.011 0.016 0.015 0.00 K 1032 1041 1051 1018 1005 1042 1016 1014 1004 1007 1001 984 1028 1035 1064 996 1021 1.014 0.015 0.005 0.015 0.011 0.48 K 1022 1019 1020 998 970 1031 987 969 958 1015 964 958 998 1008 1030 955 994 1.015 0.015 0.006 0.014 0.011 0.017 0.013 0.011 0.016 0.06 1057 1057 1059 1039 1010 1071 1023 1014 1003 1049 1005 1000 1035 1044 1069 997 1033 1.015 0.015 0.014 0.014 0.011 0.009 0.016 0.015 0.04 985 994 1007 1011 963 1009 970 981 974 988 964 967 984 986 1015 963 985 1.015 0.008 0.011 0.005 0.014 0.011 0.015 0.014 0.006 0.014 0.75 K 200Hr D 0.019 0.005 0.015 0.009 0.014 0.014 0.76 K 700Hr D 0.014 0.015 0.008 0.014 0.015 0.013 0.016 0.014 0.014 0.012 0.015 2.010 1.014 0.014 0.016 0.58 1065 1067 1067 1051 1020 1081 1034 1025 1015 1055 1013 1010 1046 1054 1080 1007 1043 1.014 0.013 0.07 91 .014 0.014 0.015 0.018 0.006 0.017 0.014 0.014 0.014 0.006 0.015 2.014 0.014 0.015 0.014 0.005 0.05 1078 1078 1080 1058 1029 1091 1042 1033 1023 1074 1023 1018 1055 1064 1088 1014 1053 1.015 0.015 0.90 100Hr K D 1072 1075 1078 1059 1027 1088 1042 1031 1021 1062 1019 1016 1052 1061 1086 1012 1050 1.014 0.006 0.014 0.015 0.013 0.014 0.018 0.0144 2.005 1.010 1.006 0.008 0.015 0.005 0.011 0.011 0.016 0.018 0.014 0.014 0.014 0.008 0.015 0.65 1000Hr K D 1061 1061 1063 1044 1013 1075 1026 1019 1006 1056 1008 1005 1040 1048 1073 1000 1038.005 0.014 0.Material Sample No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Avg Ratio K : BSPT66+Mn Poled D 0.01 10Hr D 0.014 0.011 0.014 0.011 0.014 0.018 0.00 1Min D 0.014 0.014 0.015 0.015 0.018 0.009 0.78 K 400Hr D 0.07 0.018 0.014 0.014 0.05 1Hr D 0.010 0.005 0.005 0.91 K 1069 1069 1073 1006 1022 1042 1038 1027 1016 1001 1013 980 1053 1059 1084 1009 1035 1.014 0.008 0.014 0.014 0.018 0.015 2.006 0.014 0.015 0.62 0.005 0.010 0.4 0.014 0.011 0.015 0.014 0.010 0.014 0.011 0.014 0.012 0.008 0.015 0.014 2.008 0.008 0.008 0.

78 700Hr 134 129 122 125 135 137 137 128 132 139 157 144 137 137 160 137 0.77 1000Hr 134 127 123 126 135 135 138 125 133 136 158 145 137 138 159 137 0.76 155 159 154 161 187 182 176 171 162 157 147 153 155 150 162 0.82 0.78 400Hr 134 131 124 125 137 141 136 127 134 139 158 144 141 136 158 138 0.48) + Fe 1 1 S.77 Continued… 92 .No Poled Min Hr 1 179 144 143 2 172 135 131 3 162 132 126 4 172 129 126 5 180 145 141 6 175 146 140 7 172 144 138 8 164 135 128 9 171 139 135 10 176 147 145 11 198 168 165 12 188 158 153 13 180 142 138 14 166 137 132 15 207 170 163 Avg 177 145 140 Ratio 1.74 Material : PZT (x.87 176 183 158 168 196 190 186 177 172 166 158 159 159 157 172 0.Appendix .48) S.No Poled 1 Min 1 Hr 10Hr 100Hr 200Hr 400Hr 700Hr 1000Hr 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Avg Ratio 208 226 218 216 236 221 220 228 220 193 223 193 199 210 215 1.0.74 100Hr 133 134 125 124 136 140 137 127 131 138 158 144 138 135 156 137 0.91 186 192 177 184 209 205 195 201 197 177 166 175 174 170 186 0.0.75 154 159 154 155 180 172 169 168 162 158 149 154 158 147 160 0.00 195 202 191 190 232 212 213 222 210 183 192 187 185 183 200 0.80 156 159 152 161 191 185 181 173 164 158 154 155 156 152 164 0.93 189 198 188 187 232 209 211 216 207 183 168 182 178 179 195 0.79 10Hr 128 122 115 118 131 135 132 119 126 131 152 144 133 123 148 130 0.74 154 158 153 156 178 169 167 166 162 158 149 155 156 146 159 0.G Details of piezoelectric constant d33 with the aging time at 2500C Material : PZT (x.77 200Hr 133 134 126 125 136 140 138 128 134 137 158 147 141 135 157 138 0.00 0.

82 196 187 229 212 199 198 192 186 157 199 180 175 185 177 158 189 0.81 193 185 226 214 201 195 189 185 156 199 181 172 182 178 157 188 0.Material : BSPT64 S.00 232 224 250 244 244 245 232 226 206 242 218 210 226 219 199 228 0.No 358 427 369 376 388 389 349 390 354 382 387 380 387 390 405 382 1.No Poled 1 Min 1 Hr 10Hr 100Hr 200Hr 400Hr 700Hr 1000Hr 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Avg Ratio S.93 1 Min 311 389 336 331 363 356 398 342 313 358 363 359 355 357 367 353 0.89 10Hr 284 364 305 298 351 345 284 332 297 342 349 346 347 351 354 330 0.85 1000Hr Material : BSPT64+Mn 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Avg Ratio 235 228 256 256 245 249 235 236 210 246 237 218 231 225 207 234 1.87 201 193 235 222 212 207 199 194 169 205 186 182 189 185 170 197 0.89 205 198 239 231 219 211 206 201 175 213 189 188 201 194 170 203 0.86 100Hr 277 360 298 296 348 341 282 334 294 337 346 338 349 346 352 327 0.85 700Hr 281 341 291 290 347 340 281 339 290 347 353 338 350 346 350 326 0.80 Continued… 93 .85 400Hr 281 351 292 292 347 341 280 338 289 341 352 337 348 346 348 326 0.97 213 207 246 231 221 214 211 203 186 214 198 194 204 198 176 208 0.92 1 Hr 300 379 330 323 356 353 296 340 307 351 355 354 354 355 363 341 0.84 200 190 227 217 209 207 197 192 164 206 178 178 186 182 165 193 0.85 200Hr 281 353 292 293 346 342 281 337 292 341 351 337 347 347 352 326 0.83 198 189 226 215 205 204 195 189 161 209 178 175 185 177 162 191 0.00 Poled 321 398 345 343 371 364 308 355 327 365 370 361 362 371 373 356 0.

62 74 64 64 64 59 63 59 68 69 83 74 75 66 63 62 68 67 0.92 Material : BSPT66 + Mn S.94 228 217 248 240 245 246 242 226 215 217 249 225 278 274 274 244 242 0.61 94 .00 93 86 84 88 79 83 77 78 86 86 89 87 82 82 80 82 84 0.No  Poled  1 Min  1 Hr  10Hr  100Hr  200Hr  400Hr  700Hr  1000Hr  1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Avg Ratio 242 237 258 254 263 265 252 243 236 235 264 243 283 283 282 256 256 1.62 74 63 64 65 61 62 60 69 69 82 74 75 65 64 63 69 67 0.92 217 211 240 233 244 241 238 219 211 215 245 220 278 270 271 238 237 0.77 79 71 70 69 65 71 65 71 76 74 79 77 70 69 69 72 72 0.62 73 64 64 64 59 62 58 69 66 80 72 74 64 62 62 66 66 0.00 233 228 253 243 248 248 243 228 219 226 257 229 279 274 276 241 245 0.92 215 208 241 229 245 243 235 217 210 215 244 217 272 271 272 235 236 0.No Poled 1 Min 1 Hr 10Hr 100Hr 200Hr 400Hr 700Hr 1000Hr 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Avg Ratio 107 106 106 111 104 106 103 105 112 117 118 117 105 104 103 114 109 1.64 74 66 65 65 63 64 60 67 72 77 76 76 69 66 65 71 69 0.93 217 209 241 231 243 244 234 215 209 216 244 219 273 270 271 237 236 0.94 219 210 245 235 242 242 237 224 212 215 245 224 273 270 270 239 238 0.63 74 64 64 66 63 63 59 69 71 74 74 74 67 64 64 71 68 0.93 215 207 242 233 243 238 237 217 211 216 245 221 277 269 269 237 236 0.66 75 68 66 65 63 65 62 67 72 77 78 77 69 68 66 72 69 0.96 229 218 248 240 246 247 239 227 215 219 249 227 278 274 274 237 242 0.Material : BSPT66 S.

1min 2500 2000 1500 Field ( kV/cm) PZT.23 8 10 12 0 4 6 8 10 12 Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) .17 0 4 6 8 10 12 y = 77.1000hr y = 71.72 0 4 6 8 10 12 y = 68.50 0 4 6 8 10 12 y = 14.09x + 823.11x + 839.poled 2500 2000 1500 Field ( kV/cm) PZT.19 4 6 8 10 12 10 4 6 8 10 12 4 6 8 10 12 Field ( kV/cm) Field ( kV/cm) PZT.1min 600 600 Appendix .65x + 187.43x + 206.90 4 6 8 10 12 8 10 12 Field ( kV/cm) PZT .200hr 600 600 PZT.80x + 182.69x + 188.03 0 4 6 8 10 12 0 4 6 y = 72.12 K K 95 200 y = 13.96x + 826.28x + 848.81 0 0 12 y = 13.10hr 600 PZT.24 0 4 6 8 10 12 d33 400 400 400 400 K K K K 1000 500 1000 500 1000 500 1000 500 K K K 1000 500 1000 500 1000 500 y = 67.400hr PZT.46 0 4 6 8 Field ( kV/cm) y = 17.100hr y = 81.32x + 174.1000hr 600 d33 d33 200 200 d33 200 y = 14.78 8 10 12 Field ( kV/cm) PZT.1hr 2500 2000 1500 Field ( kV/cm) 2500 2000 1500 PZT.100hr d33 (cP/N) d33 d33 200 200 200 d33 d33 400 400 400 400 400 200 200 y = 16.10hr 2500 2000 1500 1000 500 PZT.400hr 2500 2000 1500 PZT.58 0 0 4 6 8 10 12 4 6 y = 68.35x + 805.00x + 203.Material: PZT (x=0.21x + 817.48) PZT -Poled 600 Rayleigh analysis for piezoelectric and dielectric response during aging PZT.200hr Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) 2500 2000 1500 2500 2000 1500 PZT.52x + 795.47x + 754.33 0 4 6 8 10 12 0 4 6 y = 13.H PZT.1hr 600 PZT.73x + 808.22 0 8 10 12 y = 64.20 0 4 6 8 10 12 4 6 y = 70.38x + 205.50x + 206.23 0 y = 13.92x + 200.18 0 y = 14.700hr 600 Field ( kV/cm) Field ( kV/cm) PZT.700hr 2500 2000 1500 1000 500 PZT.

200 hr PZT+Fe .56x + 833.07x + 119.88 0 5 7 9 11 13 5 7 y = 16.61x + 735.Material: PZT (x=0.21 0 0 5 7 9 11 13 5 7 y = 2.58 0 5 7 9 11 13 0 5 7 y = 14.57 0 5 7 9 11 13 5 7 d33 100 y = 2.27x + 110.10 hr 1500 PZT+Fe .400 hr PZT+Fe.65 0 9 11 13 5 7 y = 15.84 0 9 11 13 5 7 y = 10.Poled 300 PZT+Fe.400hr 300 Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) 300 PZT+Fe.1hr 300 PZT+Fe.58 9 11 13 11 13 5 7 9 11 13 Field ( kV/cm) PZT+Fe.1 Min PZT+Fe .69 0 5 7 9 11 13 5 7 y = 14.66 0 5 7 9 Field ( kV/cm) y = 2.10hr 300 PZT+Fe .45 0 9 11 13 y = 1.1000 hr 1500 Field ( kV/cm) PZT+Fe .56x + 835.42 0 5 7 9 11 13 5 7 y = -1.33x + 852.96x + 849.84 0 5 7 9 11 13 y = 15.86x + 118.28x + 138.1 hr PZT+Fe .70x + 841.700 hr 1000 1000 1000 1000 500 y = 15.33x + 852.86 9 11 13 Field ( kV/cm) 1500 Field ( kV/cm) 1500 Field ( kV/cm) 1500 Field ( kV/cm) PZT+Fe.1000hr 300 200 200 200 200 d33 d33 d33 100 100 100 y = 2.10x + 119.40x + 117.37 9 11 13 K K K K 500 500 500 500 K K K K 500 500 500 K 96 1500 1000 0 Field ( kV/cm) PZT +Fe .700hr 300 PZT+Fe.51x + 119.100hr 200 d33 (cP/N) 200 200 200 200 d33 d33 d33 C 100 100 100 100 d33 100 y = 4.73x + 121.1min 300 PZT+Fe .15 0 9 11 13 5 7 y = 2.poled Field ( kV/cm) 1500 Field ( kV/cm) 1500 Field ( kV/cm) 1500 PZT+Fe .04x + 855.19x + 119.44 0 0 y = 1.200hr PZT+Fe.96 0 y = 16.100 hr 1000 1000 1000 1000 500 y = 27.48) + Fe 300 PZT+Fe .32 9 11 13 9 11 13 Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) .31x + 784.

100hr BSPT64 .1min 800 BSPT64 .700hr 3500 3000 2500 2000 1500 1000 Field ( kV/cm) Field ( kV/cm) 3500 3000 2500 2000 BSPT64 .100hr 600 d33 (pC/N) 600 600 600 600 d33 d33 400 d33 400 400 400 d33 400 200 200 200 200 200 y = 11.Poled 800 800 BSPT64 .22 11 13 15 17 500 0 7 9 y = 68.79x + 313.11 11 13 15 17 Field ( kV/cm) Field ( kV/cm) BSPT64 .20x + 1600.83x + 309.26x + 314.61x + 1610.28x + 317.15 13 15 17 Field ( kV/cm) BSPT64 .29x + 1635.64) BSPT 64 .99 11 13 15 17 Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) .46x + 316.400hr 3500 3000 2500 2000 Field ( kV/cm) BSPT64 .76 13 15 17 K K K K 1500 1000 500 0 7 9 11 13 15 17 1500 1000 1500 1000 1500 1000 K K K K 1500 1000 500 0 7 9 11 13 15 17 1500 1000 1500 1000 y = 67.70 11 13 15 17 500 0 7 9 y = 68.86x + 1574.80 0 0 7 9 11 13 15 17 7 9 11 y = 10.71 0 13 15 17 7 9 11 y = 10.200hr BSPT64 .76x + 1631.Material: BSPT (x=0.36 0 13 15 17 y = 10.1min 3500 3000 2500 2000 Field ( kV/cm) Field ( kV/cm) BSPT64 .66 0 7 9 11 13 15 17 Field ( kV/cm) y = 13.36 11 13 15 17 500 0 7 9 y = 65.37x + 1581.75 500 0 7 9 y = 72.70x + 356.40 0 7 9 11 13 15 17 7 9 11 d33 400 200 y = 10.24x + 318.02x + 1612.700hr 800 BSPT64 .92x + 318.61 0 7 9 11 13 15 17 0 7 9 11 y = 12.10hr 800 BSPT64 .17x + 1569.200hr BSPT64 .1hr 800 BSPT64 .1000hr 800 600 600 600 600 d33 d33 d33 400 400 400 200 200 200 y = 11.Poled 3500 3000 2500 2000 3500 3000 2500 2000 3500 3000 2500 2000 1500 1000 y = 79.10hr BSPT64 .28x + 316.1hr 3500 3000 2500 2000 BSPT64 .97x + 1605.86 500 0 7 9 y = 63.40 11 13 15 17 500 0 7 9 y = 69.400hr 800 Field ( kV/cm) Field ( kV/cm) Field ( kV/cm) 800 BSPT64 .74 0 13 15 17 7 9 11 y = 11.52 11 13 15 17 500 0 7 9 K 97 Field ( kV/cm) Field ( kV/cm) BSPT64 .1000hr 3500 3000 2500 2000 y = 62.

Material: BSPT (x=0.64) + Mn
600 BSPT 64+Mn - Poled

600

BSPT64+Mn - 1min

600

BSPT64+Mn - 1hr

600

BSPT64+Mn- 10hr

600

BSPT64+Mn - 100hr

d33 (pC/N)

400

400

400

400

400

d33

d33

d33

200

200

200

200

d33
200

y = 14.37x + 161.59
0 7 9 11 13 15 17
Field ( kV/cm)

y = 13.57x + 161.81
0 7 9 11 13 15 17 0 7 9 11

y = 12.98x + 161.55
0 13 15 17 7 9 11

y = 11.12x + 147.96
0 13 15 17 7 9

y = 11.70x + 150.68
11 13 15 17

Field ( kV/cm) BSPT64+Mn - 400hr
600

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

600

BSPT64+Mn - 200hr

BSPT64+Mn - 700hr
600

BSPT64+Mn - 1000hr

600

400

400

400

400

d33

d33

d33

200

200

200

y = 11.62x + 146.99
0 0 7 9 11 13 15 17 7 9 11

y = 11.47x + 146.29
0
13 15 17

y = 10.81x + 145.86
0

d33
200

y = 10.79x + 136.90
7 9 11 13 15 17

K

K

K

1000 500 0 7 9 11 13 15 17

K

1000

1000

1000

K

K

K

K

1500 1000 500 0 7 9 11 13 15 17

1500 1000

1000

y = 104.04x + 879.23

500 0 7 9

y = 98.73x + 863.40
11 13 15 17

500 0 7 9 11

K

98

7

9

11

13

15

17

Field ( kV/cm)
3000 2500 2000 1500 BSPT64+Mn - Poled

Field ( kV/cm) BSPT64+Mn - 1min
3000 2500 2000 1500

Field ( kV/cm)
BSPT64+Mn - 1hr
3000 2500 2000 1500

Field ( kV/cm)
BSPT64+Mn - 10hr
3000 2500 2000 1500 1000

BSPT64+Mn - 100hr

3000 2500 2000 1500

y = 128.51x + 632.26

500 0 7 9

y = 115.26x + 849.68
11 13 15 17

500 0 7 9

y = 115.06x + 839.38
11 13 15 17

500 0 7 9

y = 99.75x + 824.47
11 13 15 17

500 0 7 9

y = 106.98x + 873.57
11 13 15 17

Field ( kV/cm)

Field ( kV/cm) BSPT64+Mn - 400hr
3000 2500 2000 1500

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm )

3000 2500 2000

BSPT64+Mn - 200hr

BSPT64+Mn - 700hr
3000 2500 2000 1500 1000

BSPT64+Mn - 1000hr

3000 2500 2000

y = 98.36x + 880.69
13 15 17

500 0 7 9 11

y = 99.90x + 906.03
13 15 17

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Material: BSPT (x=0.66)
BSPT 66 - Poled 600

600

BSPT66 - 1min

600

BSPT66 - 1hr

600

BSPT66 - 10hr

600

BSPT66 - 100hr

d33 (pC/N)

400

400

400

400

400

d33

d33

d33

200

200

200

200

d33
200

y = 6.02x + 272.16
0 7 9 11 13 15 17
Field ( kV/cm)

y = 6.61x + 249.21
0 7 9 11 13 15 17 0 7 9 11

y = 6.72x + 250.33
0 13 15 17 7 9 11

y = 5.93x + 254.06
0 13 15 17 7 9 11

y = 6.54x + 253.33
13 15 17

Field ( kV/cm) BSPT66 - 400hr
600

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

600

BSPT66 - 200hr

BSPT66 - 700hr
600

BSPT66 - 1000hr

600

400

400

400

400

d33

d33

d33

200

200

200

y = 6.81x + 251.63
0 0 7 9 11 13 15 17 7 9 11

y = 6.85x + 246.70
0
13 15 17

y = 6.27x + 255.81
0 7 9 11 13 15 17 7 9 11

d33
200

y = 6.37x + 250.12
13 15 17

K

K

K

K

1000 500 0 7 9 11 13 15 17

1000 500 0 7 9 11 13 15 17

1000 500

1000 500

K

K

K

K

1000 500

1000 500

1000 500

K

99

Field ( kV/cm)
2500 2000 1500 BSPT66 - Poled
2500 2000 1500

Field ( kV/cm) BSPT66 - 1min
2500 2000 1500

Field ( kV/cm)
BSPT66 - 1hr
2500 2000 1500

Field ( kV/cm)
BSPT66 - 10hr
2500 2000 1500 1000 500

BSPT66 - 100hr

y = 33.74x + 1292.83

y = 34.21x + 1279.86

y = 33.20x + 1277.00
0 7 9 11 13 15 17 0 7 9

y = 30.77x + 1299.81
0 11 13 15 17 7 9

y = 31.61x + 1296.85
11 13 15 17

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

2500 2000 1500

BSPT66 - 200hr

2500 2000 1500

BSPT66 - 400hr

2500 2000 1500

BSPT66 - 700hr
2500 2000 1500 1000 500 0 7 9 11 13 15 17 7 9

BSPT66 - 1000hr

y = 31.16x + 1291.09
0 7 9 11 13 15 17 0 7 9

y = 29.83x + 1275.17
0
11 13 15 17

y = 29.51x + 1292.33

y = 30.81x + 1300.58
11 13 15 17

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Material: BSPT (x=0.66) + Mn
200 BSPT66+Mn- Poled

200

BSPT66+Mn - 1min

200

BSPT66+Mn- 1hr

200

BSPT66+Mn- 10hr

200

BSPT66+Mn- 100hr

150
d33 (pC/N)

150

150

150

150

d33

d33

d33

100

100

100

100

d33 y = 3.32x + 71.65

100

50

50

50

50

50

y = 4.11x + 97.66
0 8 10 12 14 16 18
Field ( kV/cm)

y = 4.50x + 80.76
0 8 10 12 14 16 18 0 8 10 12

y = 3.89x + 76.72
0 14 16 18 8 10 12

y = 4.15x + 70.79
0 18 8 10 12 14 16 18

14

16

Field ( kV/cm) BSPT66+Mn - 400hr
200

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

200

BSPT66+Mn - 200hr

BSPT66+Mn- 700hr
200

BSPT66+Mn- 1000hr

200

150

150

150

150

d33

d33

d33

100

100

100

50

50

50

d33 y = 4.57x + 66.09

100

50

y = 4.43x + 72.76
0 8 10 12 14 16 18 0 8 10 12

y = 4.09x + 70.82
0
14 16 18

y = 3.05x + 62.78
0 8 10 12 14 16 18

K

K

K

1000 500

K

1000 500

1000 500

1000 500

K

K

K

K

1000 500

1000 500

1000 500

K

100

8

10

12

14

16

18

Field ( kV/cm)
2500 2000 1500 BSPT66+Mn - Poled
2500 2000 1500

Field ( kV/cm) BSPT66+Mn- 1min

Field ( kV/cm)
BSPT66+Mn - 1hr

Field ( kV/cm)
BSPT66+Mn -10hr BSPT66+Mn - 100hr

2500 2000 1500

2500 2000 1500

2500 2000 1500 1000 500

y = 46.18x + 955.30
0 8 10 12 14 16 18
0 8 10

y = 46.75x + 991.48
0 12 14 16 18 8 10

y = 44.79x + 977.05
0 12 14 16 18 8 10

y = 41.73x + 915.69
0 12 14 16 18 8 10 12

y = 43.28x + 968.31
14 16 18

Field ( kV/cm)
BSPT66+Mn - 200hr

Field ( kV/cm) BSPT66+Mn - 400hr
2500 2000 1500

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

BSPT66+Mn - 700hr
2500 2000 1500 1000 500

BSPT66+Mn - 1000hr

2500 2000 1500

2500 2000 1500

y = 42.62x + 961.91
0 8 10 12 14 16 18 0 8 10 12

y = 40.44x + 938.74
0
14 16 18

y = 40.42x + 940.07
0 8 10 12 14 16 18 8 10 12

y = 41.38x + 944.30
14 16 18

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

Field ( kV/cm)

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Executive (S. Pune.M. India Educational institutions: 1. India 2. Certified Welding Inspector – American Welding Society 2. Ahmedabad.C. Surveyor (Quality) – M/s Bureau Veritas. College of Engineering. India 3. Ahmedabad. India Professional honors: 1. India Bachelors of Engineering – Metallurgy (1996) Professional positions: 1. Pune. IRCA certified Lead Auditor in ISO 9001: 2000 QMS 105 . Senior Engineer (Quality) – M/s Choksi Tubes.Vita Name Date of birth Place of birth : Sunil Wasudeo Gotmare : 02 July 1975 : Nagpur.) – M/s Dresser Rand.

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