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SrTiO3–BaTiO3 nanocomposites with temperature

independent permittivity and linear tunability
Cite this: J. Mater. Chem. C, 2017,
5, 9028 fabricated using field-assisted sintering from
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chemically synthesized powders

M. Airimioaei,a M. T. Buscaglia,b I. Tredici,c U. Anselmi-Tamburini,c C. E. Ciomaga,a
L. Curecheriu,a A. Bencan,d V. Buscaglia *b and L. Mitoseriu*a

SrTiO3–BaTiO3 nanocomposites with tailored microstructures exhibit enhanced dielectric properties in

Received 13th June 2017,
Accepted 3rd August 2017
DOI: 10.1039/c7tc02629c
rsc.li/materials-c
comparison to homogeneous ceramics with the same overall composition, including stable permittivity
(830  60) over a wide temperature range (150 to 50 1C), low losses (r3% between 150 to 150 1C),
small dc conductivity (o1010 S m1) and reasonable tunability (20% at 35 kV cm1) with almost linear
and weakly hysteretic behavior. The composites were fabricated from a SrTiO3–BaTiO3 powder synthesized
in situ using a multi-step aqueous solution process. The powder was consolidated using a high-pressure
rapid field-assisted sintering method. Good densification without grain growth and only partial interdiffusion
between the two perovskites was obtained. The enhanced dielectric properties largely originate from the
existence of local composition gradients which determine a distribution of the Curie temperature and,
consequently, the formation of a broad permittivity plateau. The fine-grained microstructure and the
composite effect further contribute to suppress the temperature dependence of dielectric permittivity
while retaining a reasonable tunability.

1 Introduction
The potential usefulness of ferroelectric materials in tunable high-
frequency electronic devices such as resonators and filters was
recognized about 50 years ago. A renewed interest has been
fostered in the last 15 years by the rapid growth of mobile
communication systems. Capacitors which show a variable capa-
citance with voltage bias (varactors) find application in phase
shifters, frequency filters, switches and antennas.1–3 Ferroelectrics
are attractive materials for varactor-based devices because of the
strong dependence of dielectric permittivity on electric-field and
the relatively low losses at high frequency. Moreover, the high
permittivity of ferroelectrics enables the miniaturization of such
devices. The dc electric field dependence of permittivity is com-
monly described by the tunability, n, and the relative tunability nr:
er ð0Þ er ð0Þ  er ðEÞ
n¼ nr ¼
er ðEÞ er ð0Þ
a
Faculty of Physics, Alexandru Ioan Cuza University, Blv. Carol I, nr.11, 700506,
Iasi, Romania. E-mail: lmtsr@uaic.ro
b
Institute of Condensed Matter Chemistry and Technologies for Energy,
National Research Council, Via de Marini 6, 16149, Genoa, Italy.
E-mail: vincenzo.buscaglia@ge.icmate.cnr.it
c
Dept. of Chemistry, University of Pavia, Viale Taramelli 12, 27100 Pavia, Italy
d
Electronic Ceramics Dept., Jozef Stefan Institute, Ljubljana 1000, Slovenia
The symbols er(0) and er(E) represent the relative permittivity
(real part) at zero field and at generic field E, respectively.
BaTiO3-based solid solutions such as Ba1xSrxTiO3, BaTi1xZrxO3
and BaTi1xSnxO3 are among the ferroelectric materials with
highest tunability, up to 80% at room temperature for an electric
field of 30 kV cm1.1–5 The dielectric properties can be controlled
to some extent by acting on the composition parameter x, which
determines the value of paraelectric/ferroelectric transition tem-
perature TC. The tunability is maximized around TC. However, the
material should be usually employed in the paraelectric state
above TC because of the lower losses, the absence of hysteresis
and the better reproducibility.
The above cited materials, commonly used as polycrystalline
ceramics thanks to the low cost and easy processing, suffer
from two main restrictions. Firstly, the strong temperature
dependence of permittivity typical of BaTiO3-based materials
limits the use of the device to a narrow temperature range. In
the paraelectric regime, the permittivity rapidly decreases with
temperature following the Curie–Weiss law. Secondly, the non-
linear field-induced variation of permittivity leads to a non-
linear relative tunability. Rather than looking for new materials,
a different strategy for improving the performances of tunable
ferroelectrics is to design specific microstructures starting from
a well-known and cheap compound such as Ba1xSrxTiO3. The
dielectric properties of BaTiO3-based ceramics and composites

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are very sensitive to the microstructure (grain size, porosity,
geometry and arrangement of inclusions in composites) owing
to the redistribution of the electric field inside the material.6–8
Composites between Ba1xSrxTiO3 and a linear dielectric oxide,
such as MgO, have been extensively investigated because the
dielectric constant can be adjusted by changing the amount of
the linear dielectric and losses can be lowered while retaining a
reasonable tunability as also demonstrated by recent finite
element modeling.2,4,9–13 Nanostructuration is also quite effective;
we have recently shown that a tendency towards linearization of
the electric field dependence of permittivity of BaTiO3 ceramics
occurs when the grain size is reduced down to E100 nm.14,15
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The reduction of grain size has also a favorable effect on the
temperature dependence of permittivity as the sharp permittivity
peak at TC is replaced by a broad and rounded maximum.
Moreover, the reduction of the grain size determines an increase
of the breakdown field.14–16 However, the tunability of these
nanoceramics is rather low and not suitable for practical
applications. The temperature dependence of permittivity can
also be reduced by inducing the formation of local composition
gradients. Roughly speaking, a composition gradient determines
a distribution of the Curie temperatures and this will result in a
flattening of permittivity vs. temperature dependence, likewise
the behavior observed in multilayered Ba1xSrxTiO3 thick films
composed of several layers with different compositions.17 There-
fore it can be expected that tunable ferroelectric materials with
improved properties can be designed by combining and balancing
the composite, grain size and local composition gradient effects.
In this paper it is shown that ceramic nanocomposites with
linear and reasonable tunability as well as a flat temperature-
independent permittivity and low losses can be fabricated by
field-assisted rapid sintering starting from in situ prepared
SrTiO3–BaTiO3 composite particles using a multistep synthesis
method in aqueous solution.
2 Experimental
2.1 Synthesis of SrTiO3–BaTiO3 composite powder
The synthesis of the starting SrTiO3 particles is described
elsewhere and only some details closely related to the specific
conditions adopted in the present study are given.18 Particles of
strontium titanate with cubic morphology were prepared from
a Sr–Ti gel suspension obtained by hydrolysis of a SrCl2–TiOCl2
aqueous solution with 5 M NaOH. The Ti concentration was
0.0225 mol L1 and the Sr/Ti molar ratio was 1.1. Formation of
SrTiO3 occurred inside a tubular reactor consisting of a PTFE
tube with an inner diameter of 3 mm and a length of 10 m
where the suspension was heated to 55 1C by means of a thermo-
static bath. The residence time was 11 min. The resulting powder
was repeatedly washed with water until the disappearance of
chloride ions in the supernatant and finally freeze-dried.
A homogeneous mixture of SrTiO3 and BaTiO3 particles was
obtained by using a two-step process. First, the SrTiO3 particles
were suspended in a peroxotitanium solution at pH 9. Heating
to 95 1C determines the hydrolysis of the solution and formation
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of an amorphous hydrous titania coating.19 The resulting
SrTiO3@TiO2 particles were then suspended in a 0.2 M solution
of Ba(OH)2 and the suspension was kept at 95 1C for 2 h. This
treatment determined the transformation of the amorphous
titania shell into BaTiO3. The nominal composition of the final
product was Ba0.5Sr0.5TiO3.
2.2 Nanocomposite fabrication
The nanocomposite ceramics (denoted as ST–BT) were fabricated
using home-made high-pressure field-assisted sintering (HP-FAST)
apparatus. Rapid sintering methods such as FAST and spark
plasma sintering (SPS) are quite effective to produce good
densification at lower temperatures and in a shorter time (usually
a few minutes) in comparison to conventional sintering thus
minimizing grain growth.20,21 In the home-made HP-FAST
apparatus used, heating was provided using a low-voltage AC
high-current power supplier. Recently FAST and SPS apparatus
has implemented a broad control on the current waveform,
including DC, AC, and pulsed currents, even though the actual
role played by the current waveform is still to be clarified.20,21 A
double-stage die as that shown in Fig. 3 of ref. 20 is used,
allowing pressures as high as 1 GPa to be easily obtained. The
high-pressure sections of the die, i.e. the pistons with smaller
diameters, are made out of silicon carbide, to withstand the
high pressures produced during the process.
The powder was put in a graphite die loaded in the HP-FAST
apparatus, which was evacuated to a pressure of 10 Pa. A
moderate initial uniaxial pressure (150 MPa) was applied.
The temperature was then increased with a heating rate of
200 1C min1. Once the sample reached the temperature of 900 1C,
the pressure was rapidly increased to the final value (540 MPa).
The samples (5 mm in diameter, E1 mm thick) were held under
these conditions for 5 min and then the pressure was quickly
released and the power was turned off. The temperature was
measured using a shielded K-type thermocouple inserted in the
lateral wall of the die. After sintering the samples were annealed
for 24 h in air at 700 1C. This treatment has a twofold purpose:
(i) remove the surface graphite residues originated from the die
and (ii) reoxidize the outermost part of the ceramic. In fact
the contact with the graphite die established local reducing
conditions during sintering resulting in oxygen loss from the
titanate lattice with the formation of oxygen vacancies and an
increase of the electronic conductivity and dielectric losses. The
annealing treatment below the sintering temperature preserves the
nanocomposite microstructure resulting from FAST densification
while improving the dielectric properties. A reference ceramic with
homogeneous composition and coarse microstructure (denoted
as BST) was obtained by annealing the nanocomposite for 24 h
in air at 1350 1C.
2.3 Characterization
The particle morphology was investigated using a scanning
electron microscope (SEM, LEO 1450VP) and a transmission
electron microscope (TEM, JEOL JEM-2010F) equipped with an
energy-dispersive spectroscopy (EDS) microprobe. The particle
size distribution of the starting SrTiO3 powder was determined
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by measuring a few hundred particles using SEM. The micro-
structure of ceramics was observed using a Jeol JSM-7600F field-
emission scanning electron microscope (SEM-FEG). SEM-FEG
images were obtained using backscattered electrons (BEs) at
15 keV. The phase composition was determined using X-ray
diffraction (XRD) with Cu Ka radiation (Panalytical CubiX). The
surfaces of the ceramic disks were polished and electroded
with silver for electrical measurements. Dielectric permittivity
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and electrical conductivity were measured at (150–150) 1C
and (100–106) Hz using an LCR meter (Concept Novocontrol
Technologies). High voltage (up to a field of 50 kV cm1)
dc-tunability measurements were performed at room temperature
on the ceramic disks immersed in a transformer oil bath, at an
oscillator frequency of 28 kHz and an amplitude of 0.5 V, by
using a function generator coupled with a TREK 30/20A-H-CE
amplifier.

Fig. 1 Morphology of (a) SrTiO3 starting particles, (b) SrTiO3@TiO2 particles and (c and d) SrTiO3–BaTiO3 particles. (e) Magnification of the region
indicated by the rectangle in (d). (f) EDS spectra of representative particles. (a and c): SEM and (b, d and e): TEM. The inset in (a) reports the particle size
distribution.

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3 Results and discussion
3.1 Phase composition and microstructure
The morphology of the initial SrTiO3 powder is shown in
Fig. 1a. The particles have a cubic morphology with an edge
length in the range of 250–450 nm (inset of Fig. 1a) and an
average size of 330 nm. The XRD pattern (Fig. 2a) corresponds
to cubic SrTiO3 (S.G. Pm3% m) with traces of the side product
SrCO3. The hydrolysis of the peroxotitanium solution determines
the formation of an amorphous titania shell on the surface of
SrTiO3, as clearly visible in Fig. 1b. After transformation of the
titania coating in barium titanate by reaction with the Ba(OH)2
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solution, the diffraction pattern exhibits the peaks of SrTiO3 and
BaTiO3 (Fig. 2b). The absence of evident splitting or asymmetric
broadening of the BaTiO3 peaks denotes a pseudocubic structure,
typical of nanocrystalline barium titanate particles synthesized
under mild conditions. SEM and TEM observations (Fig. 1c–e)
have revealed two kinds of morphologies: cuboidal particles with
rounded edges and spheroidal agglomerates of nanocrystalline
cubic particles. According to EDS analysis (Fig. 1f), the squared
particles are Sr-rich whereas the round agglomerates are Ba-rich.
The presence of a BaTiO3 layer on the Sr-rich square particles is
not evident from TEM observations due to too thick, almost
un-transparent squared particles. However, a thin, Ba-rich shell on
many of the original SrTiO3 particles is clearly visible on the polished
cross-sections of the composite ceramic, as will be discussed later.
After HP-FAST densification a substantial modification of
the diffraction pattern is apparent. Doublets are still observed
(Fig. 2c) but their separation has decreased and the peaks are
broadened, meaning that partial interdiffusion between the
two perovskites has occurred. The fracture surface of the
composite (Fig. 3a) shows a dense microstructure composed
of cubic grains with sizes of 200–450 nm, an indication of
negligible grain growth. The polished cross-sectional BE-SEM
images shown in Fig. 3b and c correspond to the typical
Fig. 2 XRD patterns of: (a) SrTiO3 particles, (b) SrTiO3–BaTiO3 particles,
(c) ST–BT nanocomposite sintered at 900 1C and post-annealed at 700 1C,
and (d) homogeneous BST ceramic. The peaks of BST are indexed
%
according to the cubic perovskite structure (S.G. Pm3m).
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microstructure of the composite and show two different gray
levels. The brightness level is proportional to the average
atomic number of the phase and, consequently, the light grey
regions correspond to Ba-rich compositions whereas the dark-
gray regions correspond to Sr-rich compositions. Many grains
clearly show a core–shell microstructure, with an outer Ba-rich
layer of variable thickness (20–100 nm) around a square Sr-rich
core (diameter: 200–400 nm). Grains mainly composed of a
BaTiO3-rich phase are also observed. This composite micro-
structure together with the particle morphology shown in Fig. 1
indicates that the formation of BaTiO3 during the treatment
of the SrTiO3@TiO2 particles in hot Ba(OH)2 solution has
occurred by two concurrent pathways. The rounded polycrystal-
line particles (Fig. 1c and d) have originated from a dissolution–
precipitation process, whereas the thin shells visible in Fig. 3b
and c come from the in situ transformation of the TiO2 coating
(Fig. 1b) in BaTiO3. In addition to this dominant microstructure,
minor Sr-richer and Ba-richer regions were also observed. An
example of the microstructure of a Sr-rich region is shown in
Fig. 3d. Irrespective of the observed region, it is worth noting
that some grains clearly present a hole in their core region
(Fig. 3b–d). The origin of these voids is most likely related to the
Kirkendall effect and has been reported during interdiffusion
processes and solid-state reactions involving particles of metals,
oxides and chalcogenides.22–24 When interdiffusion involves the
migration of atoms/ions with different mobilities, such as Sr
and Ba in the present case, a net vacancy excess accumulates on
the side of the component whose atoms/ions have higher
mobility (i.e. the SrTiO3 core). If these vacancies are not efficiently
removed by the movement of dislocations, they rapidly accumulate
resulting in the formation of many small pores. Due to the
constrained geometry of the grains, the pores coalesce in a unique
larger pore. Moreover, in the present case, the polishing process
could have determined a further enlargement of such pores due
to the poor mechanical resistance of the material in the inner
porous region.
The use of a rapid sintering method such as HP-FAST is of
fundamental importance for obtaining dense and peculiar
microstructures shown in Fig. 3. The high pressure (540 MPa)
applied during sintering has certainly contributed to the
densification process. Plastic deformation and flow of the
BaTiO3-rich rounded aggregates of nanocrystalline particles
have likely occurred. A similar process has been reported for
BaTiO3–MgO composites.13 In contrast, the grain growth and
coalescence process reported after SPS at 950 1C of a mechanical
mixture of BaTiO3 and SrTiO3 nanoparticles were not observed.25
Conventional sintering requires much higher temperatures
(41200 1C) and longer times (a few hours) to produce good
densification. As a result, grain growth and composition homo-
genization take place in the sample. Prolonged annealing of the
nanocomposite at 1350 1C determines complete interdiffusion
with the formation of a homogeneous solid solution with a cubic
perovskite structure, as inferred from the sharp and narrow
single peaks of the corresponding XRD pattern (Fig. 2d). The
pattern was indexed according to the cubic Pm3% m symmetry, the
one expected at room temperature for the Ba0.5Sr0.5TiO3 nominal
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Fig. 3 (a–d) Microstructure (SEM-FEG) of the ST-BT nanocomposite. (a) Fracture surface. (b–d) Backscattered electron images of polished
cross-sections. Image (d) corresponds to a SrTiO3-richer region. (e) Fracture surface (SEM) of the homogeneous BST ceramic.

composition. The homogeneous BST ceramic has a relative
density of 98% and grains with a size of 2–5 mm, as shown by
the representative fracture surface of Fig. 3e.
3.2 Dielectric properties
The real part of the dielectric permittivity and the loss tangent
are comparatively shown in Fig. 4 for the nanocomposite
(Fig. 4a and b) and the homogeneous ceramic with the same
overall composition (Fig. 4c and d). The latter shows a sharp
permittivity peak at the Curie temperature TC of 15 1C (258 K),
close to the value expected for the Ba0.5Sr0.5TiO3 composition
(243–248 K).2,4 The sharp and high permittivity peak is indicative
of the compositional homogeneity of the solid solution as
suggested by previous studies.2 The evolution of TC with x in
Ba1xSrxTiO3 has been reported in detail and thus the effective Sr
atomic fraction in the samples can be estimated to be 0.45–0.47.
A less pronounced permittivity peak which can be assigned to the
rhombohedral to tetragonal transition can be observed at about

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Fig. 4 Dielectric permittivity (a and c) and loss tangent (b and d) of the (a and b) ST–BT nanocomposite and (c and d) BST homogeneous ceramic.
80 1C (193 K). In the temperature region corresponding to
ferroelectric behaviour, the permittivity ranges between 2500 and
7000. Above TC, the ceramic displays low losses (o2%) up to
160 1C for frequencies Z10 kHz. However, the losses rapidly
increase at temperatures 440 1C at lower frequencies probably as
a result of space charge effects. The loss tangent is slightly higher
(2–4%) in the ferroelectric region, as expected and related to the
presence of ferroelectric domain walls. In the paraelectric state,
the permittivity of the BST ceramic exhibits a Curie–Weiss
behavior, with a Curie constant of about 1  105 K.
Conversely, the nanocomposite presents a remarkably broad
permittivity plateau between 150 and 50 1C, where the permittivity
variation is within 7% of the average value of E830 (Fig. 4a) for all
the reported frequencies. The plateau can be qualitatively described
as the superposition of two broad permittivity peaks, one
corresponding to BaTiO3-rich compositions and the second
one to SrTiO3-rich compositions. The broadening effect can
be attributed to: (i) the existence of local composition gradients
and the corresponding distribution of Curie temperature and
(ii) the nanostructure of the composite. The progressive broad-
ening and flattening of the permittivity peak with decreasing
grain size is a well-known phenomenon in BaTiO3 and BST
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ceramics.14,26,27 The lower permittivity of the nanocomposite
(E800) in comparison to that of the homogeneous ceramic is
also a direct consequence of the above mentioned effects.
Furthermore, a certain redistribution of the electric field in
the composite is likely to occur because in the investigated
temperature range Sr-rich compositions (x 4 0.7) have lower
permittivity than Sr-poor compositions. Field redistribution
means that the local field is different from the applied field
and this can significantly affect the effective permittivity (see
ref. 15 as an example). However, the importance of this effect is
hardly estimated. The permittivity peak corresponding to the
ferro/para transition of pure BaTiO3 at 125–130 1C is not
observed, further confirming that partial interdiffusion has
occurred. The loss tangent is reduced by comparison with the
homogeneous ceramic, ranging between 0.004 and 0.016 at
(1–1000) kHz in the whole temperature range. At lower frequencies
a relaxation peak is observed at E20 1C. This relaxation is likely to
be determined using an interfacial polarization process, again
related to the existence of local concentration gradients.
The improved dielectric properties of the nanocomposite
ceramic are also demonstrated by the conductivity vs. frequency
dependencies comparatively shown in Fig. 5. The homogeneous
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Fig. 5 Frequency dependence of the electrical conductivity at different
temperatures. (a) ST–BT nanocomposite. (b) BST homogeneous ceramic.
ceramic presents a temperature-activated relaxation at room
temperature superimposed on the typical linear-like behavior
in the log–log scale described using Jonscher’s universal power
law s(o) E on (s: conductivity, o: frequency).28 In contrast, the
nanocomposite shows predominantly linear characteristics with
n E 0.9 at frequencies 4102 Hz. This means that the conductivity
in the nanocomposite is characterized by a single mechanism
while the solid solution shows other thermally activated dis-
persion conductivity phenomena which are also responsible for
the rise of the loss tangent at room temperature and at low
frequency (Fig. 4d). The origin of the conductivity dispersion
mechanism might be related to the level and mobility of
the oxygen vacancies, as commonly observed in ferroelectric
perovskites, with possible differences related to the micro-
structural and compositional characteristics of the present
ceramic samples. In any case, the conductivity of the nano-
composite changes with a frequency of less than one order of
magnitude in the range of 150 to 150 1C and takes overall
values one order of magnitude lower than those of the homo-
geneous ceramic. A low frequency plateau corresponding to the
dc conductivity is not observed down to 1 Hz, in both samples.
This means that the dc conductivity will be quite low
(o1010 S m1) in the whole temperature range.
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The room temperature dc field dependent dielectric properties
of the ST–BT nanocomposite and of the BST homogeneous
ceramic are compared in Fig. 6. The data were collected after a
few dc field loops to ensure a reproducible behaviour. It is
worth noting that the maximum applied field was limited by
the measurement instability of the ceramic sample under high
voltages. With respect to this, the nanocomposite can hold the
application of slightly higher dc fields than the homogeneous
solid solution (50 and 40 kV cm1, respectively), and this can be
related to the above mentioned improvement of dielectric loss
and reduced conductivity in the nanocomposite.
Fig. 6a shows er(E) measured over a complete decreasing/
increasing electric dc field loop. Fig. 6b reports the tunability
n(E) measured while decreasing the dc field. Very limited
hysteretic behaviour is evident for both materials. Although
strongly reduced due to the nanostructure and the local
compositional gradients, at 35 kV cm1 the nanocomposite
still preserves a reasonable tunability of 1.19 (nr = 20%) in
comparison with the higher tunability of 1.58 (nr = 39%) of the
homogeneous solid solution. The difference between the non-
linear character of the two materials can be better illustrated by
comparing the field dependence of polarization P(E) obtained
in the quasi-static regime by integration of er(E) (Fig. 6a) over a
complete field cycling, as shown in Fig. 6c (only the first quadrant
is reported). Although the homogeneous solid solution is in the
paraelectric state (TC = 15 1C) and the hysteretic character is
strongly reduced, P(E) dependence shows a non-linear character,
as the electric field may induce the formation of ferroelectric
domains and/or polar regions. The nonlinear character of P(E)
and hysteresis are strongly reduced in the nanocomposite,
which shows a sub-switching Rayleigh-type dependence (lack
of switching and saturation). Although the BaTiO3-rich regions
of the composite are expected to be ferroelectric, the movement of
the domain walls and domain switching are strongly suppressed
by the reduced grain size, a typical feature of polar nanoceramics.29
As a result, above 10 kV cm1, the permittivity vs. field dependence
of the nanocomposite is almost linear, as predicted and observed
in fine ceramics.14,15
Overall the results demonstrate that composites with enhanced
dielectric properties, such as the lack of hysteresis, acceptable
tunability level and permittivity below 1000 together with high
thermal stability of the dielectric constant, can be obtained by
tailoring the composition and microstructure. The use of a
rapid sintering technique such as HP-FAST guarantees high
densification with only partial interdiffusion between the two
perovskites while grain growth is practically suppressed. The
aqueous solution synthesis of the precursor powder was of
fundamental importance to obtain an intimate mixture of BaTiO3
and SrTiO3 and thus a uniform densification and interdiffusion
in the whole ceramic body. The microstructure of the composite
shows features with a size from a few tens to a few hundred
nanometers. The reduced grain size determines a broadening
and flattening of the permittivity peak which superimposes on
the effect of the local composition gradient, thus leading to the
observed temperature insensitive dielectric constant. According
to the literature,2 SrTiO3-rich regions are expected to have a lower
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4 Summary and conclusions

SrTiO3–BaTiO3 nanocomposites with local composition gradients
were fabricated using HP-FAST starting from a mixed powder
synthesized in situ using a multi-step aqueous solution process.
SrTiO3 cubic particles with a mean size of 330 nm obtained using a
precipitation-like method were first coated with an amorphous
titania layer and then the titania was converted to BaTiO3 by
reaction with a hot Ba(OH)2 solution. The short sintering time
(5 min) and the relatively low sintering temperature (900 1C)
together with the high heating rate (200 1C min1) and the high
pressure (540 MPa) determined good densification without
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grain growth and only partial interdiffusion between the two

perovskites.
According to XRD, a BaTiO3-rich phase and a SrTiO3-rich
phase coexist in the nanocomposite, meaning that inter-
diffusion has occurred to some extent. The SEM observation
shows a dense microstructure in which SrTiO3-rich grains (size:
0.2–0.4 mm) are preferentially surrounded by a BaTiO3-rich
phase. The existence of pores at the centre of many grains is
interpreted as a result of the Kirkendall effect.
The nanocomposite exhibits stable permittivity (830  60)
over a wide temperature range (150 to 50 1C) accompanied by
small dielectric losses (tan d r 3% between 150 to 150 1C and
102–106 Hz) and low dc conductivity (o1010 S m1). These
remarkable dielectric properties are a direct consequence of its
peculiar microstructure and the presence of local composition
gradients producing a broad distribution of the Curie temperature,
as inferred by comparison with the behaviour of a homogeneous
ceramic with the same overall composition. Despite the lower
permittivity, the nanocomposite preserves a reasonable tunability
(20% at 35 kV cm1) with almost linear and only weakly hysteretic
behaviour above 10 kV cm1.
The same approach described above can be extended to
other systems to tailor the dielectric and, more generally,
functional properties by the fabrication of (nano)composites
whose components show a significant reciprocal solubility. The
final properties can be adjusted by acting on different experimental
parameters such as the size and shape of the starting particles,
geometry of the two-phase arrangement, sintering temperature and
time, and post-sintering annealing treatment. The use of chemical
synthesis methods largely facilitates the preparation of precursor
particles with a controlled morphology. The use of field-assisted
rapid sintering methods is essential for controlling the micro-
structure evolution and the extent of interdiffusion.

Fig. 6 Field-dependent nonlinear dielectric properties of the ST–BT

nanocomposite and BST homogeneous ceramic: (a) permittivity vs. field Conflicts of interest
for field increasing/decreasing from 50 kV cm1 to 50 kV cm1, (b) dc
tunability determined under field decrease, (c) first quadrant quasi-static There are no conflicts of interest to declare.
P(E) loops determined by integration of er(E) dependence.

Notes and references

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