Skip to main content
SpringerLink
Log in

Phase transitions in PbTixHf1-xO3 determined by thermal analysis and impedance spectroscopy

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

The objective of this study is to determine the influence of partial substitutions of Ti4+ by isovalent Hf4+ in the perovskite-type crystalline structure of PbTiO3. Different samples over the whole composition range (0 ≤ x≤1) in the PbTi1-xHfxO3 family have been prepared. Phase transitions have been determined by thermal analysis (differential scanning calorimeter: DSC) and complex impedance spectroscopy (IS) over a wide temperature range. As a consequence of the cation replacement the changes that take place in the different phase transition temperature are reported. By both techniques, thermal analysis and electrical characterization, it is shown that for all compositions prepared there is only one phase transition in a temperature range between 230 and 460 °C. With these results and the previously known crystalline structure of pure PbTiO3 and PbHfO3 perovskites, the phase diagram of the PbTi1-xHfxO3 family is presented including a morphotropic phase transition at x ~ 0.5.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Colon G, Aviles MA, Navio JA, Sanchez-Soto PJ. Thermal behaviour of a TiO2–ZrO2 microcomposite prepared by chemical coating. J Therm Anal Calorim. 2002;67(1):229–38.

    Article  CAS  Google Scholar 

  2. Moran-Pineda M, Castillo S, Asomoza M, Gomez R. Copper oxide on Cu/Al2O3–TiO2 catalysts TG, FTIR–CO absorption and catalytic activity in the NO reduction by CO. J Therm Anal Calorim. 2003;73:341–6.

    Article  CAS  Google Scholar 

  3. Costa CEF, Crispim SCL, Lima SJG, Paskocimas CA, Longo E, Fernandes VJ, et al. Synthesis and thermal characterization of zirconium titanate pigments. J Therm Anal Calorim. 2004;75:467–73.

    Article  CAS  Google Scholar 

  4. Ianculescu A, Bráileanu A, Zaharescu M, Guillemet S, Pasuk I, Madarász J, et al. Formation and properties of some Nb-doped SrTiO3-based solid solutions. J Therm Anal Calorim. 2003;72(1):173–80.

    Article  CAS  Google Scholar 

  5. Kuroiwa Y, Aoyagi S, Sawada A, Ikawa H, Yamashita I, Inoue N, et al. Structural study of perovskite-type fine particles by synchrotron radiation powder diffraction. J Therm Anal Calorim. 2002;69(3):933–8.

    Article  CAS  Google Scholar 

  6. Glazer AM, Mabud SA. Powder profile refinement of lead zirconate titanate at several temperatures. II. Pure PbTiO3. Acta Cryst. 1978;B34:1065–70.

    CAS  Google Scholar 

  7. Parvanova V. Thermal decomposition of lead peroxotitanate to PbTiO3. J Therm Anal Calorim. 2005;79(1):141–4.

    Article  CAS  Google Scholar 

  8. Zorel HE Jr, Crespi MS, Ribeiro CA. Attainment of lead titanate through the thermal decomposition of coprecipitated 8-hydroxyquinolinate precursors. J Therm Anal Calorim. 2005;75(2):545–50.

    Article  Google Scholar 

  9. Kwapulinski J, Pawelczyk M, Dec J. On the Pb thermal vibrations in PbHfO3 crystals. J Phys Condens Matter. 1994;6:4655–9.

    Article  Google Scholar 

  10. Kuroiwa Y, Fujiwara H, Sawada A, Aoyagi S, Nishibori E, Sakata M, et al. Distinctive charge density distributions of perovskite-type antiferroelectric oxides PbZrO3 and PbHfO3 in cubic phase. Jpn J Appl Phys. 2004;43(9):6799–802.

    Article  CAS  Google Scholar 

  11. Sani A, Hanfland M, Levy D. Pressure and temperature dependence of the ferroelectric–paraelectric phase transition in PbTiO3. J Solid State Chem. 2002;167:446–52.

    CAS  Google Scholar 

  12. Samara GA. A new pressure-induced phase in PbHfO3. Phys Lett. 1969;30A(8):446–7.

    Google Scholar 

  13. Samara GA. Pressure and temperature dependence of the dielectric properties and phase transitions of the antiferroelectric perovskites: PbZrO3 and PbHfO3. Phys Rev B. 1970;1(9):3777–86.

    Article  Google Scholar 

  14. Jaffe B, Roth RS, Marzullo S. Properties of piezoelectric ceramics in the solid-solution series lead titanate-lead zirconate-lead oxide:tin oxide and lead titanate-lead hafnate. J Res Natl Bureau Stand. 1955;55(5):239–54.

    CAS  Google Scholar 

  15. Frantti J, Fujioka Y, Eriksson S, Hull S, Kakihana M. Neutron powder diffraction study of Pb(HfxTi1-xO3) ceramics (0.10 ≤ x ≤ 0.5). Inorg Chem. 2005;44:9267–78.

    Article  CAS  Google Scholar 

  16. Bedoya C, Muller Ch, Baudour J-L, Bouree F, Soubeyroux J-L, Roubin M. Ferroelectric-paraelectric phase transition in PbHf0.2Ti0.8O3 studied by neutron powder diffraction. J Phys Condens Matter. 2001;13:6453–70.

    Article  CAS  Google Scholar 

  17. Muller C, Baudour J-L, Madigou V, Bouree F, Kiat J-M, Favotto C, et al. Temperature-dependent neutron powder diffraction evidence for splitting of the cationic sites in ferroelectric PbHf0.4Ti0.6O3. Acta Cryst. 1999;B55:8–16.

    CAS  Google Scholar 

  18. Sicron N, Stern EA, Yacoby Y. The relation between the local and the average structure of rhombohedral ferroelectric PbHf0.9Ti0.1O3. J Phys Chem Solids. 2000;61:243–9.

    Article  CAS  Google Scholar 

  19. Megaw HD, Darlington CNW. Geometrical and structural relations in the rhombohedral perovskites. Acta Crystallogr. 1975;A31:161–73.

    CAS  Google Scholar 

  20. Alonso RE, Errico LA, Peltzer y Blancá EL, López-García A, Svane A, Christensen NE. Theoretical study of pure and Ta-doped monoclinic hafnia (m-HfO2), Phys Rev. (2008); B78.

Download references

Acknowledgements

This work has been possible to the financing of the Spanish MEC (project MAT2007-66845-C02-02) and of the action 139/Q06 0915-110 financed by the CAM-UPM.

Author information

Authors and Affiliations

  1. Departamento de Física Aplicada a las Tecnologías de la Información, ETSI Telecomunicación (UPM), Universidad Politécnica de Madrid, Ciudad Universitaria s/n, 28040, Madrid, Spain

    M. A. de la Rubia & J. de Frutos

  2. Departamento de Electrocerámica, Instituto de Cerámica y Vidrio (CSIC), Kelsen 5, 28049, Madrid, Spain

    M. A. de la Rubia

  3. Departamento de Física, Fac. Cs. Exactas, Universidad Nacional de la Plata, Calles 115 y 49, 1900, La Plata, Argentina

    R. E. Alonso & A. R. López-Garcia

Authors
  1. M. A. de la Rubia
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. R. E. Alonso
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. J. de Frutos
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. R. López-Garcia
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. A. de la Rubia.

Rights and permissions

Reprints and permissions

About this article

Cite this article

de la Rubia, M.A., Alonso, R.E., de Frutos, J. et al. Phase transitions in PbTixHf1-xO3 determined by thermal analysis and impedance spectroscopy. J Therm Anal Calorim 98, 793–799 (2009). https://doi.org/10.1007/s10973-009-0111-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-009-0111-7

Keywords

Search

Navigation