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Calorimetric study of CaCu3Ti4O12, a ceramic with giant permittivity

Published online by Cambridge University Press:  31 January 2011

Andrey A. Levchenko ,
Loïc Marchin ,
Yosuke Moriya ,
Hitoshi Kawaji ,
Tooru Atake ,
Sophie Guillemet-Fritsch ,
Bernard Durand  and
Alexandra Navrotsky
Andrey A. Levchenko
Affiliation:
Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture, and Technology-Organized Research Unit (NEAT ORU), University of California at Davis, Davis, California 95616
Loïc Marchin
Affiliation:
Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux (CIRIMAT/LCMIE), Université Paul Sabatier, Bât. 2R1, 31062 Toulouse Cedex 9, France
Yosuke Moriya
Affiliation:
Materials and Structures Laboratory, Tokyo Institute of Technology, Midori-ku, Yokohama, 226-8503 Japan
Hitoshi Kawaji
Affiliation:
Materials and Structures Laboratory, Tokyo Institute of Technology, Midori-ku, Yokohama, 226-8503 Japan
Tooru Atake
Affiliation:
Materials and Structures Laboratory, Tokyo Institute of Technology, Midori-ku, Yokohama, 226-8503 Japan
Sophie Guillemet-Fritsch
Affiliation:
Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux (CIRIMAT/LCMIE), Université Paul Sabatier, Bât. 2R1, 31062 Toulouse Cedex 9, France
Bernard Durand
Affiliation:
Centre Interuniversitaire de Recherche et d’Ingénierie des Matériaux (CIRIMAT/LCMIE), Université Paul Sabatier, Bât. 2R1, 31062 Toulouse Cedex 9, France
Alexandra Navrotsky
Affiliation:
Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture, and Technology-Organized Research Unit (NEAT ORU), University of California at Davis, Davis, California 95616
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Abstract

We conducted an investigation into the thermodynamic properties of two stoichiometric CaCu3Ti4O12(CCTO) samples prepared by solid-state reaction and soft chemistry methods to probe the stability of the material relative to simpler oxide constituents (e.g., CaO, CuO, and TiO2) over a wide temperature range. Thermodynamic functions (i.e., heat capacity, formation enthalpies, entropies, and Gibbs free energies) have been measured from near absolute zero to 1100 K using calorimetric methods, including drop solution, low-temperature adiabatic relaxation, and differential scanning calorimetry. In addition, the thermodynamic characteristics of the magnetic-phase transition from the antiferromagnetic to the paramagnetic state are reported. It has been shown that CCTO is very stable relative to constituent oxides and calcium titanate at room temperature and higher, independent of the synthesis route. The enthalpic factor is dominant in the thermodynamics of CCTO, with the entropic factor having almost no effect on the stability of the compound relative to other oxide assemblages. The recommended values for the standard molar enthalpy of formation from constituent oxides and from elements at 298.15 K are −122.1 ± 4.5 and −4155.7 ± 5.2 kJ/mol−1, respectively. The mean of the third law entropy at 298.15 K is 368.4 ± 0.1 J/mol−1/K−1. Based on the thermodynamic data reported, the study confirms the possibility of CCTO decomposition in a reducing atmosphere or CO2 under conditions recently observed in experiments.

Keywords

Debye temperatureDielectricPhase equilibria
Type
Articles
Information
Journal of Materials Research , Volume 23 , Issue 6 , June 2008 , pp. 1522 - 1531
Copyright
Copyright © Materials Research Society 2008

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