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Research and Development National Institute for Physics and Technology of Materials INCDFM, PO BOX MG7,
Str. Atomistilor 105 Bis, Magurele-Bucharest, RO-77125, Romania
b MADIREL, Universit
e de Provence/CNRS, Centre de St. Jerome, 13397 Marseille, France
c Istituto di Scienza e Tecnologia dei Materiali Ceramici ISTEC-CNR, Faenza, Italy
Received 27 April 2005; received in revised form 20 August 2005; accepted 3 September 2005
Available online 11 November 2005
Abstract
Barium titanate (BaTiO3 ) have been doped in situ with 5.5 mol% cerium by a solgel method using barium acetate, titanium (IV) isopropoxide,
and cerium (III) acetylacetonate as starting materials. The dried gel showed a microstructure consisting of nano-sized grains (140 nm) with great
tendency to agglomeration. Several thermal analysis techniques were used to study the decomposition process of the gel. The presence of hydroxyls
up to 720 C suggests a strong bonding Ti OH that is responsible for the existence of aggregates even at high temperatures. The as-prepared gel
powder was found to be amorphous, and then decomposes through oxides and barium carbonate around 500 C and crystallizes on the perovskite
structure of tetragonal BaTiO3 at 1100 C for 3h in air. A small influence of the frequency on the dielectric properties of the Ba0.945 Ce0.055 TiO3
ceramics was observed in 100 Hz to 1 MHz domain. At the Curie temperature point (22 C) the dielectric constant was 10130 at 100 Hz while the
dielectric loss (tan ) was 0.018.
2005 Elsevier Ltd. All rights reserved.
Keywords: BaTiO3 ; Solgel processes; Dielectric properties; Solgel methods
1. Introduction
Ferroelectric bulk ceramics have found wide applications as
electronic, acousto-optic and piezoelectric devices.1,2 Dielectric
ceramics of barium titanate doped with cerium present practical
interest because cerium decreases significantly the Curie temperature of BaTiO3 . Up to 8 mol% Ce concentration, a linear
decrease of the Curie point (Tc ) of 21 C per mol% Ce was
observed in bulk ceramics fired at 1350 C in air with equimolar
additives of TiO2 and CeO2 .3 Thus, we predict that the cerium
concentration of 5.5 mol% can decreases the Curie temperature
of BaTiO3 to near ambient temperature where this dielectric
material will be use as capacitors. According to Hwang et al.,4
the Curie temperature was systematically lowered when Ce3+
was incorporated into Ba2+ sites, whereas the substitution of
Ce4+ for Ti4+ sites does not change this parameter. The valence
states of cerium ions depend on the starting formula and sintering atmosphere. It is difficult to maintain cerium ions as Ce3+ in
Corresponding author. Tel.: +40 21 493 0047; fax: +40 21 493 0267.
E-mail address: mcernea@infim.ro (M. Cernea).
0955-2219/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jeurceramsoc.2005.09.039
3242
1.2 cm diameter and 0.2 cm thick as obtained were then sinterized at various temperatures from 1100 to 1250 C, for 2 h in
air. Samples with apparent densities of 94.8% from theoretical
density were obtained by sintering the pellets at 1250 C, for 2 h
in air.
Apparent densities of the sintered pellets were measured
by Arhimede method using a density balance. The thermal
behaviour of the gel was investigated by thermal analyses, IR
spectroscopy, scanning electronic microscopy (SEM) and X-ray
diffraction (XRD). The thermal gravimetry (TGA) and sample
controlled thermal (SCTA) Analyses were recorded by using
a TA Instrument, model Q500 and an apparatus home built,13
respectively. The totality of evolved gases is continuously analysed by a RIBER mass spectrometer coupled to the apparatus for
sample controlled thermal analysis. FT-IR spectra were recorded
on these samples using an EQUINOX 55 FTIR spectrometer.
The microstructure of the powders and ceramic (Ba, Ce)TiO3
was investigated using a Philips XL 30 scanning electron microscope. The structure of the gel powder was characterized by
X-ray diffraction using a Siemens D 5000 X-ray diffractometer. For powder diffraction we used Cu K1 radiation, a LiF
crystal monochromator and Bragg-Brentano diffraction geometry. The data were collected at 25 C with a step-scan interval of
0.020 and a step time of 10 s. For refinement we used a program
package DIFFRACplus from Bruker. The dielectric properties
of the bulk ceramics were measured with a Hewlett-Packard
impedance meter Model 4194. The electrical measurements
were carried out in the metal-ferroelectric-metal (MFM) configuration, where the electrodes M consist of a silver paste heated
at 650 C, 15 min.
3. Results and discussion
3.1. Thermal analyses
The thermal stability of the precursor-gel of (Ba, Ce)TiO3
was analysed using thermogravimetry (TG) at 10 C/min in a
flowing nitrogen (60 ml/min flow rate) environment (Fig. 1) and
sample controlled thermal analysis (SCTA) coupled with mass
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Step 1:
Step 2:
Step 3:
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(100 C)
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Fig. 8. Variation of loss tangent () of Ce doped-BaTiO3 ceramic with temperature and frequency.
3246
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