Thermodynamic optimization of the PbO-ZrO_1tn2-TiO_1tn2 (PZT) system and its application to the processing of composites of PZT ceramics and copper [Elektronische Ressource] / vorgelegt von Marija Čančarević
184 Pages
English

Thermodynamic optimization of the PbO-ZrO_1tn2-TiO_1tn2 (PZT) system and its application to the processing of composites of PZT ceramics and copper [Elektronische Ressource] / vorgelegt von Marija Čančarević

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Max-Planck-Institut für Metallforschung Stuttgart Thermodynamic optimization of the PbO-ZrO -TiO2 2 (PZT) system and its application to the processing o f composites of PZT ceramics and copper Marija anarevi Dissertation an der Universität Stuttgart Bericht Nr. 198 März 2007 Thermodynamic optimization of the PbO-ZrO -2TiO (PZT) system and its application to the 2processing of composites of PZT ceramics and copper Dissertation Von der Fakultät Chemie der Universität Stuttgart Zur Erlangung der Würde eines Doktors der Naturwissentschaften (Dr. rer. nat) Genehmigte Abhandlung Vorgelegt von Marija anarevi Aus Belgrad Hauptberichter: Prof. Dr. rer. nat. Fritz Aldinger Mitberichter: Prof. Dr. rer. nat. Dr. hc. Mult. Günter Petzow Prüfungsvorsitzender: Prof. Dr. Ir. E. J. Mittemeijer Tag der mündlichen Prüfung: 23.03.2007.

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Published 01 January 2007
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Max-Planck-Institut für Metallforschung
Stuttgart







Thermodynamic optimization of the PbO-ZrO -TiO2 2
(PZT) system and its application to the processing
o f composites of PZT ceramics and copper


Marija anarevi
Dissertation
an der
Universität Stuttgart

Bericht Nr. 198
März 2007





































Thermodynamic optimization of the PbO-ZrO -2
TiO (PZT) system and its application to the 2
processing of composites of PZT ceramics and
copper


Dissertation


Von der Fakultät Chemie der Universität Stuttgart
Zur Erlangung der Würde eines
Doktors der Naturwissentschaften (Dr. rer. nat)
Genehmigte Abhandlung


Vorgelegt von
Marija anarevi
Aus Belgrad



Hauptberichter: Prof. Dr. rer. nat. Fritz Aldinger
Mitberichter: Prof. Dr. rer. nat. Dr. hc. Mult. Günter Petzow
Prüfungsvorsitzender: Prof. Dr. Ir. E. J. Mittemeijer


Tag der mündlichen Prüfung: 23.03.2007.


Max-Planck Institut für Metallforschung und Institut für Nichtmetallische
Anorganische Materialien der Universität Stuttgart, Stuttgart
Pulvermetallurgische Laboratorium
2007














Dedicated to my parents














































Acknowledgments


It is a pleasure for me to express my thanks to Prof. Dr. Fritz Aldinger for providing
me the possibility to carry out my thesis work in his department.

I am very thankful to Dr. M. Zinkevich for the supervision of my work and his
thorough reading of my thesis.

I would like to thank Prof. Dr. G. Petzow for his support and accepting to be the
“Mitberichter” for my thesis. I am also grateful to Prof. E.J. Mittemeijer for his interest in
my work and accepting to examine my thesis.

Many thanks to Dr. O. Fabrichnaya who gave me many important hints that deepened
my understanding of thermodynamic modelling as well as to my colleges D. Djurovic
and N. Solak for stimulating discussions about my experimental work.

I would like to thank Mr. R. Mager for the careful preparation of my experimental
set-up and further experimental support.

Finally, I express my thanks to my family, especially my parents for their support,
and my husband who kept me holding on by continuous encouragement and to my son
who gave me warm smile in each difficult moment.

































i
Contents

ZUSAMMENFASSUNG UND AUSBLICK................................................................iii

ABSTRACT................................................................................................................... vii

1. INTRODUCTION..................................................................................................... 1
1.1. Piezoelectricity and piezoelectric actuators..................................................... 1
1.1.1. Working principle ..................................................................................... 3
1.1.2. Synthesis and properties of the PZT ceramics.......................................... 4
1.2. Aim of the study ................................................................................................ 5
2. FUNDAMENTALS................................................................................................... 6
2.1. Experimental determination of phase diagrams and thermodynamic
quantities............................................................................................................. 6
2.2. Phase diagram calculations............................................................................... 7
2.2.1. The Calphad method................................................................................. 7
2.2.2. Analytical description of the Gibbs energy ............................................ 10
2.2.2.1. Pure elements and stoichiometric phases....................................... 10
2.2.2.2. Substitutional solutions.................................................................. 11
2.2.2.3. The compound energy formalism (CEF) ....................................... 14
2.2.3. The chemical potential diagrams ............................................................ 16
3. EXPERIMENTAL PROCEDURES AND THERMODYNAMIC
MODELLING ......................................................................................................... 18
3.1. Experimental procedures................................................................................ 18
3.1.1. Sample preparations................................................................................ 18
3.1.2. Characterization methods........................................................................ 19
3.2. Description of phases in the Cu-Pb-Zr-Ti-O system .................................... 20
3.2.1. The gas phase.......................................................................................... 20
3.2.2. The liquid phase...................................................................................... 21
3.2.3. The fcc, bcc and hcp phases.................................................................... 21
3.2.4. The PbO solid solutions ( PbO, PbO) ................................................. 22
3.2.5. The Zr Ti O solid solution ................................................................ 23 x 1-x 4
3.2.6. The ZrO solid solutions ......................................................................... 23 2
3.2.7. The PbZr Ti O solid solution............................................................ 23 x 1-x 3
3.2.8. The TiO solid solution........................................................................... 24 x
3.2.9. The TiO (rutile) phase.......................................................................... 25 2-z
3.2.10. The (Cu,Ti)O and CuTi O phases ........................................................ 28 z 2 z

4. BINARY SYSTEMS ............................................................................................... 30
4.1. The Ti-O system .............................................................................................. 31
4.2. The Pb-O system ............................................................................................. 35
4.3. The Cu-O system ............................................................................................. 38
4.4. The Zr-O system .............................................................................................. 39
4.5. The Cu-Pb system............................................................................................ 41
4.6. The Cu-Ti system............................................................................................. 42
4.7. The Cu-Zr system ............................................................................................ 44
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5. TERNARY SYSTEMS ........................................................................................... 46
5.1. The Cu-Pb-O system........................................................................................ 46
5.1.1. Experimental results................................................................................ 49
5.1.2. Thermodynamic optimization................................................................. 54
5.1.3. Discussion............................................................................................... 54
5.2. The Cu-Ti-O system ........................................................................................ 63
5.2.1. Thermodynamic optimization................................................................. 66
5.2.2. Discussion............................................................................................... 68
5.3. The Cu-Zr-O system........................................................................................ 81
5.3.1. Experimental results................................................................................ 81
5.3.2. Thermodynamic calculation and discussion ........................................... 83

6. QUASITERNARY PbO-ZrO -TiO SYSTEM .................................................... 92 2 2
6.1. Survey of literature data ................................................................................. 92
6.1.1. PbO-ZrO ............................................................................................... 92 2
6.1.2. PbO-TiO ............................................................................................... 95 2
6.1.3. ZrO -TiO .............................................................................................. 96 2 2
6.1.4. PbO-ZrO -TiO ....................................................................................... 97 2 2
6.2. Thermodynamic optimization ...................................................................... 102
6.3. Discussion ....................................................................................................... 102


7. EXTRAPOLATION INTO TO MULTICOMPONENT Cu-Pb-Zr-Ti-O
SYSTEM ................................................................................................................ 118
7.1. Evaluation of phase relations in the Cu O-CuO-PbO-ZrO 2 2
and Cu O-CuO-PbO-TiO systems ........................................................... 118 2 2
7.1.1. Extrapolating calculations..................................................................... 118
7.1.2. Experimental results and discussion ..................................................... 123
7.2. Evaluation of phase relations in the Cu-PbO-ZrO -TiO system ............. 128 2 2
7.2.1. Extrapolating calculations..................................................................... 128
7.2.2. Experimental results and discussion ..................................................... 131
7.2.2.1. PbO-free samples......................................................................... 131
7.2.2.2. PbO-bearing samples ................................................................... 138

8. CONCLUSIONS AND OUTLOOK.................................................................... 142

Appendix...................................................................................................................... 145

REFERENCES............................................................................................................ 155