Materials Research Bulletin 46 (2011) 2543–2547

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Materials Research Bulletin

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Microwave-hydrothermal synthesis of perovskite bismuth ferrite nanoparticles

G. Biasotto b, A.Z. Simões a,*, C.R. Foschini b, M.A. Zaghete b, J.A. Varela b, E. Longo b
a
Universidade Estadual Paulista-Unesp, Faculdade de Engenharia de Guaratinguetá, Av. Dr. Ariberto Pereira da Cunha, 333, Bairro Pedregulho, CEP 12516-410,
Guaratinguetá, SP, Brazil
b
Laboratório Interdisciplinar em Cerâmica (LIEC), Departamento de Fı´sico-Quı´mica, Instituto de Quı´mica, UNESP, CEP 14800-900, Araraquara, SP, Brazil

A R T I C L E I N F O A B S T R A C T

Article history: Hydrothermal microwave method (HTMW) was used to synthesize crystalline bismuth ferrite (BiFeO3)
Received 10 February 2011 nanoparticles (BFO) in the temperature of 180 8C with times ranging from 5 min to 1 h. BFO
Received in revised form 27 June 2011 nanoparticles were characterized by means of X-ray analyses, FT-IR, Raman spectroscopy, TG-DTA and
Accepted 6 August 2011
FE-SEM. X-ray diffraction results indicated that longer soaking time was benefit to refraining the
Available online 24 August 2011
formation of any impurity phases and growing BFO crystallites into almost single-phase perovskites.
Typical FT-IR spectra for BFO nanoparticles presented well defined bands, indicating a substantial short-
Keywords:
range order in the system. TG-DTA analyses confirmed the presence of lattice OH groups, commonly
A. Ceramics
found in materials obtained by HTMW process. Compared with the conventional solid-state reaction
B. Chemical synthesis
B. Crystal growth process, submicron BFO crystallites with better homogeneity could be produced at the temperature as
C. X-ray diffraction low as 180 8C. These results show that the HTMW synthesis route is rapid, cost effective, and could be
D. Diffusion used as an alternative to obtain BFO nanoparticles in the temperature of 180 8C for 1 h.
ß 2011 Elsevier Ltd. All rights reserved.

1. Introduction satellite communications, optical filters and smart devices were

Bismuth ferrites, a large family that includes sillenite- and
perovskite-type compounds, have recently drawn much interest
due to their physical properties and technological applications
[1,2]. The sillenites, with the general formula Bi12MO20 (M = Ge, Ti,
Ga, Fe, V, etc.), exhibit various properties such as photorefractivity,
optical activity, photoconductivity, piezomodulus, and an en-
hanced velocity of ultrasound wave propagation; these properties
have potential applications in electro-optics, acoustics, and
piezotechnics [3,4]. More recently, the coexistence of ferroelec-
tricity and magnetic order has been observed in the perovskite
bismuth oxides with a noncentrosymmetric structure, such as
BiFeO3 and BiMnO3; hence, they have attracted considerable
attention [5–7]. The phenomenon of simultaneous ferroelectric
and magnetic order, that is, multiferroic behavior, presents not
only opportunities to study fundamental physics but also potential
applications in information storage, spintronics, and sensors [8,9].
Some other bismuth ferrites are also important functional
materials. For example, Bi2Fe4O9 is a good catalyst for oxidizing
ammonia to NO and a potential semiconductor gas sensor [10].
BiFeO3 (BFO) has a ferroelectric Curie temperature Tc of 850 8C and
an antiferromagnetic Neel temperature of 370 8C [11,12]. Howev-
er, potential applications of BFO in memory devices, sensors,
* Corresponding author. Tel.: +55 12 3123 2765.
E-mail address: alezipo@yahoo.com (A.Z. Simões).
greatly limited due to its low insulation resistance caused by the
reduction of Fe3+ species to Fe2+ and oxygen vacancies for charge
compensation [13,14]. Although great achievements have been
made for BFO thin films prepared by the pulsed-laser deposition
(PLD) method [15], it was hard to avoid generating impurity phases
by the conventional solid-state reaction in bulk materials. BFO
perovskites could only stabilize within a narrow ranged tempera-
ture. Up to date, the synthesis of single-phase BFO crystallites or
ceramics is still a challenging issue. In the solid-state route, nitric
acid leaching was required to eliminate the impurity phases, such
as Bi2Fe4O9 and Bi25FeO40, after the calcination of mixed bismuth
and iron oxides [16], which resulted in coarser powders and the
poor reproducibility. Most recently, Pradhan et al. [17] prepared
phase pure BFO ceramics by a rapid liquid-phase sintering
technique. The crystallization temperature of BFO in these
methods was required above the ferroelectric Curie temperature
Tc, which implied that the volatilization of bismuth was hard to
avoid. Moreover, Ghosh et al. [18] prepared pure phase bismuth
ferrite nanopowders by the tartaric acid based sol–gel method
coupled with the additional calcination process. However, few
works have been done to prepare BFO crystallites by using the
hydrothermal method and the formation mechanism has not been
clearly understood yet. The advantage of soft chemical routes was
that microcrystallines could be synthesized at a much lower
temperature, and also energy saving and cost effective. Among the
chemical methods, hydrothermal synthesis is often used due to its
simplicity, allowing the control of grain size, morphology and

0025-5408/$ – see front matter ß 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2011.08.010
2544 G. Biasotto et al. / Materials Research Bulletin 46 (2011) 2543–2547

degree of crystallinity by easy changes in the experimental

procedure. A variation of this method, microwave assisted
hydrothermal synthesis, has the advantage of lower processing
temperature and time, and an uniform nucleation of the powders
in suspension [19–21].
In this study, we have investigated the conditions required for
the crystallization of BFO under microwave-hydrothermal condi-
tions to obtain homogeneous nanoparticles with uniform particle
size and low nitrate content.

2. Experimental procedures

BFO was synthesized from an equimolar mixture of Bi(NO3)3

and Fe(NO3)3
9H2O in 40 ml using KOH as mineralizer and
deionized water as a reaction medium. All chemicals source are
analytical grade. The mixture was ultrasonically dispersed for
15 min, transferred into a sealed Teflon autoclave and then placed
in a microwave furnace CEM Corp. (Matthews, NC) model MARS-5
with frequency of 2.45 GHz and variable power up to 300 W. The
temperature inside the vessel was controlled through an optical
fiber sensor model EST-300 (CEM Corp.). The hydrothermal
treatment was performed at the same temperature for different
Fig. 1. (a) X-ray diffraction pattern of BFO nanoparticles synthesized at (a) 180 8C for
soaking times. The reactions were carried out for 5, 30 min and 1 h 1 h, (b) 180 8C for 30 min and (c) 180 8C for 5 min in the HTMW method.
at temperature of 180 8C.
After the hydrothermal reaction, the autoclave was cooled
naturally to room temperature. The resulting powders, insoluble in Table 1
Index refinements for BiFeO3 nanoparticle obtained at 80 8C for 1 h in the HTMW
water, were separated by centrifugation and washed with de-
method.
ionized water in sequence to remove all soluble salts, and then
dried in an oven at 80 8C for 24 h in air. The obtained powders were Parameters BFO
characterized by X-ray powder diffraction (XRD) using a (Rigaku- Refinement index Rwp (%) 24.2
DMax/2500PC, Japan) with Cu Ka radiation (l = 1.5406 Å) in the 2u Rexp 20.2
range from 20 to 808 with 0.028 min 1. For Rietveld analyses, X-ray S 1.2

diffraction data were collected under the following experimental Atomic positions A1 0; 0; 0.06722
conditions: 40 kV, 30 mA, 208  2u  80, D2u = 0.028, lCu Ka A2 0; 0; 0.21091
monocromatized by a graphite crystal, divergence slit = 2 mm, B1 0; 0;
B2 0; 0; 0.37099
reception slit = 0.6 mm, step time = 10 s. The Rietveld analysis was O1 ;;0
performed with the Rietveld refinement program DBWS-941 1. O2 ;;
The profile function used was the modified Thompson-Cox- O3 0; 0; 0.43786
Hasting pseudo-Voigt, in which h (the Lorentzian fraction of the O4 0; 0; 0.32536
O5 ; ; 0.11165
function) varies with the Gauss and Lorentz components of the full
width at half maximum. TG-DTA analyses were carried out with a SOcc Bi (A1) 1.00000
Netzsch-409 STA apparatus with a heating rate of 20 8C min 1 O 0.91700
under flowing air. The FT-IR spectra were recorded with a Bruker Lattice parameter a (Å) 5.5806 (3)
Equinox-55 instrument. Raman spectra were collected using a c (Å) 13.8699 (7)
Bruker RFS-100/S Raman spectrometer with Fourier transform. A V (Å3) 431.951
t 0.915
1064 nm YAG laser was used as the excitation source, and its
power was kept at 150 mW. Microstructural characterization was Perovskite (mol%) 96.03  0.5
performed by field emission scanning electron microscopy (Supra Stoichiometry BiFeO3
Refinement BiFeO2.6
35-VP, Carl Zeiss, Germany). XANES spectra were collected at the Bi
and Fe K edges being measured with a Si (2 2 0) monochromator in
the D04B-XAFS1 beam line at the Brazilian Synchrotron Light
Laboratory (LNLS). Data were collected at room temperature using annealed at lower soaking times. An eventual peak splitting of the
energy steps of 2 eV and an integration time of 3 s. reflections cannot be resolved due to overlapping on the (1 1 6)/
(1 2 2), (2 0 8)/(2 2 0) and (1 3 1)/(0 3 6)/(3 1 2) planes.
3. Results and discussion In this study, we have adopted the Rietveld refinement
technique to investigate the crystal structure of the BFO powder
Fig. 1 shows XRD patterns of BFO powders synthesized at 180 8C (Fig. 1(b) and Table 1). The data were collected from the powders
at several times using an initial KOH concentration of 4 M. obtained at 180 8C for 1 h. Rwp, Rexp, and S indexes, as well as the
Diffraction peaks that come from BFO powders synthesized with lattice parameters (a and c) were determined. The refinement
time of 1 h can be indexed mainly by BFO according to the powder resulted in Rwp = 24.2%; Rexp = 20.2%, RBragg = 4.1%, space group
data of JCPDS card no. 86-1518. This revealed that BFO crystallites R3cH, with unit cells of a = 5.5806(3) Å and c = 13.8699(7) Å. The
had the perovskite structure belonging to the polar R3c space atomic positions obtained by Rietveld analyses belong to the ICSD
group [22,23] indicating that hydrothermal technique was card (86-1518). For the impurity (Bi2Fe4O9), we have obtained
successfully used to produce almost pure crystalline nanoparticle. from the refinement RBragg = 20.4%, space group Pbam with unit
However, the presence of impurity phase, such as Bi2Fe4O9 was cells equal to a = 7.939(5), b = 8.520(6) and c = 6.007(4). The
detected in addition to the major BFO phase for specimens quantitative phase analyses of powders for the orthorhombic
 G. Biasotto et al. / Materials Research Bulletin 46 (2011) 2543–2547 2545

Fig. 2. TG/DTA curves of BFO nanoparticle synthesized at 180 8C for 1 h in the

HTMW method.
Fig. 3. FT-IR spectra of BFO nanoparticle synthesized at 180 8C for 1 h in the HTMW
method.

phase were calculated according to the reference of Young et al. the high frequency electromagnetic radiation interacts with the
[24]. The obtained results confirmed that the BFO powder permanent dipole of the liquid (H2O), which initiates rapid heating
crystallized in the orthorhombic phase and no changes occurred from the resultant molecular rotation. Likewise, permanent or
in the refinement. It was observed that annealing at 180 8C for a induced dipoles in the dispersed phase cause rapid heating of the
long soaking time causes a structural distortion of BFO lattice due particles. These result in a reaction temperature in excess of the
the covalent interaction, which originates from the strong surrounding liquid-localized superheating [32]. The band at
hybridization between Fe 3d and O 2p orbitals. From the low S around 830 cm 1 was due to the presence of traces of trapped
values (S = Rwp/Rexp = 1.2%) it can be assumed that the refinement NO3 ions in the BFO nanoparticle [33].
was successfully performed with all the investigated parameters Raman scattering has proven to be a valuable technique to
close to literature data [25]. obtain information about local structures within materials Raman
Having in mind that BFO powder obtained at 180 8C for 1 h spectra is illustrated in Fig. 4. The presence of Raman-active modes
contains slight traces of impurity, we have performed TG-DTA can be used to evaluate the structural order degree at short-range.
analyses (Fig. 2). The existence of three stages corresponding to the The modes located at 212, 316, 377, 445, 537 and 635 cm 1 are
weight and energy change can be observed. The first region (25– caused by internal vibration of FeO6 octahedra, whereas below
200 8C) corresponds to the loss of physisorbed water; the second 200 cm 1 must be addressed to different sites occupied by bismuth
between 200 and 350 8C corresponds to the loss of surface within the perovskite units. The bands located at 97, 120 and
hydroxyl groups, and finally, the weight loss above 500 8C is due to 145 cm 1 are related to Bi atoms of perovskite layer and
the decomposition of nitrate species. DTA curve shows a strong corresponds to a rigid layer. These modes are probably due to a
exothermic peak around 270–350 8C, correlated to a weight loss, distortion in the A site caused by the bismuth ion. This distortion
that must be considered as the crystallization of the residual
amorphous phase.
The FTIR spectra of crystalline BFO powders derived from the
hydrothermal reaction is shown in Fig. 3. The broad band at 3000–
3600 cm 1 arose from the antisymmetric and symmetric stretch-
ing of bond H2O and OH groups, while a band at 1630 cm 1
corresponded to the bending vibrations of H2O [26,27]. The band at
around 830 cm 1 was due to the presence of traces of trapped
NO3 ions in the BFO nanoparticle [28]. Specifically, the strong
absorptive peaks at 400–600 cm 1 was attribute to the Fe–O
stretching and bending vibration, being characteristics of the
octahedral FeO6 groups in the perovskite compounds. The
formation of perovskite structure can be confirmed by the
presence of metal–oxygen band [29,30]. Residual water and
hydroxy group are usually detected in the as grown samples and
further heat treatment is necessary for their elimination. It is well
known that the hydroxylation of metal ions and the deprotonation
can be accelerated by raising the solution temperature or pressure
[31]. The crystallized nanoparticle was found to have OH ions due
the alkali used under the present reaction conditions. Furthermore,
the hydroxyl content was found to decrease with the increasing of
soaking time. This could be due the vigorous action of microwaves
to remove such groups at elevated temperature during the Fig. 4. FT-IR spectra of BFO nanoparticle synthesized at 180 8C for 1 h in the HTMW
hydrothermal process. In hydrothermal-microwave processing method.
2546 G. Biasotto et al. / Materials Research Bulletin 46 (2011) 2543–2547
Fig. 5. Xanes spectra of BFO nanoparticle synthesized at 180 8C for 1 h in the HTMW
method.
into the A site of the perovskite-enhances the Jahn–Teller
distortion of FeO6 octahedra. On the other hand, Raman modes
located above 200 cm 1 are responsible for distortions and
vibrations of FeO6 octahedral. Raman results are in agreement
with XRD data.
Fig. 5 shows the Fe K-edge XANES spectra of the BFO powders.
For the purpose of comparison, the XANES spectrum of FeO and
Fe2O3 powders are also shown. The iron atoms present a 3+ valence
state in the BFO system once its curve is quite similar to Fe2O3
phase. Peak A corresponds to the 1s–3d electric dipole-forbidden
transition, whereas peak C signifies the dipole-allowed transition
(empty orbital 4p). Peak B known as a shoulder peak is caused by
the shakedown process in which 2p electron in the oxygen 2p band
partially transfers to the Fe 3d orbital, so called ligand-to-metal
charge transfer process. That indicates that iron atoms have
different symmetries.
SEM images of specimens synthesized at 180 8C for 1 h are
shown in Fig. 6(b) with different magnifications. According to the
image, most of the grains of BFO powders are homogeneous in the
submicron range. However, BFO powders reveal few large
particles with the irregular shape. The variation of grain
morphologies may be an evidence of the formation of impurity
Fig. 6. FE-SEM images of BFO nanoparticles synthesized at 180 8C for 1 h in the HTMW method at different magnifications (a) 20,000 and (b) 50,000.
phases. The submicron and isotropy BFO crystallites obtained in
our work are quite different from the previous work, where BFO
powders agglomerated into the cubic with the side size of 45 mm
under the hydrothermal conditions [34]. The growth of large
cubic grains was usually preferred for the hydrothermal lead
zirconate titanate (PZT) particles [35]. In the hydrothermal
process, the presence of alkaline medium was found to be
essential. In our case, there existed a critical annealing tempera-
ture above which the formation of impurity phases was favored,
and the formation of pure BFO was tightly dependent on it. The
‘‘dissolution and crystallization’’ process can be utilized to
describe the hydrothermal reaction [36]. During the hydrother-
mal treatment, Bi3+ and Fe3+ hydroxides underwent an attack of
KOH to dissolve and react at high temperatures and pressures,
and then precipitated as insoluble ceramic oxide particles from
the supersaturated hydrothermal fluid. If the temperature and
pressure conditions were carefully maintained during the
duration of the experiment, neither etching of BFO crystals nor
the formation of a second phase would be observed. Therefore,
the dissolution and crystallization process continued in super-
saturated fluid in such a way that the system was self-stabilizing.
We conjectured that the dissociation of bismuth and iron
hydroxide and the formation of ionic complexes might prevent
the growth of BFO crystallites and limit the size of BFO particles to
the submicron range. The agglomeration process was attributed
to Van der Waals forces. To reduce the surface energy, the
primary particles have a tendency to form nearly spherical
agglomerates, in a minimum surface to volume ratio and hence
reducing surface free energy [37]. This type of grain structure is
common in oxide, ferrite and titanate ceramics [38–45]. This is a
result of an abnormal/discontinuous grain growth and also called
an exaggerated grain growth. In the abnormal growth, some
grains grow faster than others with increasing sintering
temperature. The abnormal grain growth may results from: (1)
the existence of second phase precipitates or impurities, (2)
materials with high anisotropy in interfacial energy and (3)
materials in high chemical in equilibrium [46]. In hydrothermally
derived BFO which crystallizes in an orthorhombic structure it
can be assumed that the abnormal grain growth comes from
factors (1) and (3) because the existence of two-phase structure.
At intermediate temperatures, a higher degree of agglomeration
was noted. This could be due to the favored nucleation process at
higher OH concentration with no separation of particles because
of low reaction temperature.
 G. Biasotto et al. / Materials Research Bulletin 46 (2011) 2543–2547
4. Conclusions
BFO perovskite crystallites have been prepared by using the
hydrothermal method. Compared with the conventional solid-state
reaction process, submicron BFO crystallites with better homoge-
neity could be produced at the temperature as low as 180 8C. Longer
soaking time was benefit to refraining the formation of any impurity
phases and growing BFO crystallites into almost single-phase
perovskites. The hydrothermal reaction to grow BFO crystallites was
described by the dissolution–crystallization process. Rietveld
refinement reveals an orthorhombic structure while Xanes spectra
evidenced iron atoms in a 3+ valence state. SEM analyses have
shown a homogeneous size distribution of submicron BFO powders.
TEM analyses indicate that the BFO nanoparticles are uniform
indicating very few structural defects. HTMW is interesting not only
for the short treatment time and low temperature used, but also for
the possibility to control the morphological and structural proper-
ties. Therefore, the HTMW method is undeniably a genuine
technique for low temperatures and short times in comparison
with the above mentioned methodologies. The observed magnetism
of the BFO crystallites can be achieved with the decrease to a
nanometer scale in particle size.
Acknowledgements
The financial support of this research project by the Brazilian
research funding agencies CNPq and FAPESP is gratefully
acknowledged.
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