Ceramic processing and microstructure/property relation in CaCu3Ti4O12


CaCu3Ti4O12 (CCTO) powders were produced at low temperatures by high-energy ball milling and its impact on the electrical properties of CCTO ceramics carried out. CCTO ceramics develop an internal barrier layer capacitance (IBLC) mechanism due to small changes in stoichiometry, which seems to start at intermediate processing temperatures (900.-.1100.oC). This project aims to decrease the calcination and sintering temperatures to retain the stoichiometric composition during processing of CCTO ceramics. The evolution of the CCTO phase was evaluated by X-ray diffraction and ceramics were prepared by conventional sintering at temperatures between 700 and 1100 oC. The samples were characterised by impedance spectroscopy at subambient and high temperatures. Ceramics sintered at 1100 oC were characterised by SEM and EDS. The results show that high-energy ball milling permits the production of CCTO powder at lower temperature, 700.oC, compared to conventional solid state reaction (950.-.1100.oC). Impedance spectroscopy measurements show that ceramics sintered at a temperature of 700.oC, the stoichiometric composition of CCTO is retained and consists of insulating grains with a resistivity > 1 MΩ cm at 523 K. The relative density is, however, rather low, 57 %, and the IBLC mechanism is not present in this sample as usually observed for CCTO ceramics. When the sintering temperature increases, the insulating grains start to transform into semiconducting and the IBLC mechanism starts to appear, accompanied by a significant drop on the resistivity by at least six orders of magnitude for ceramics sintered at 1000 oC. At intermediate sintering temperatures, 800 - 900.oC, the grains are electrically heterogeneous containing both insulating and semiconducting phases. When samples are sintered at 1000 oC, the grains are totally semiconducting with resistivity of ~ 40 Ω cm and grain boundary resistivity of ~ 530.Ω.cm at 523 K. Ceramics sintered at 1100 oC exhibit semiconducting grains surrounded by insulating grain boundary with resistivity of ~ 65 kΩ cm at 523 K, and this seems to be responsible for the high effective permittivity at radio frequencies for dense ceramics. The EDS analysis shows CCTO ceramics sintered at 1100 oC to be Cu-deficient and it contributes to the increase of the bulk conductivity. The transformation of the resistive into semiconducting grains and the evolution of the IBLC mechanism may be, therefore, linked to the diffusion and eventual volatilisation of copper at elevated processing temperatures.




Sara isabel Rodrigues Costa

nossos autores


Jorge Ribeiro Frade; Derec Sinclair, University of Sheffield, UK


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