Chemical Engineering and Processing 103 (2016) 12–20

Contents lists available at ScienceDirect

Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Influence of the synthesis method on the preparation of barium

titanate nanoparticles
L.R. Pradoa , N.S. de Resendeb , R.S. Silvac , S.M.S. Eguesa , G.R. Salazar-Bandaa,*
a
Instituto Tecnologia e Pesquisa/Programa de Pós-graduação em Engenharia de Processos, Universidade Tiradentes, C.P. 300, 49032-490 Aracaju, SE, Brazil
b
Programa de Engenharia Química/NUCAT, Universidade Federal do Rio de Janeiro/COPPE, Cidade Universitária, Centro de Tecnologia, Bloco G/115, CEP:
21945-970 Rio de Janeiro, RJ, Brazil
c
Grupo de Materiais Cerâmicos Avançados, Departamento de Física, Universidade Federal de Sergipe, Campus Universitário, C.P. 49.100-000 São Cristóvão, SE,
Brazil

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

Article history: Dielectric barium titanate nanoparticles are essential to develop reliable microelectronic devices.
Received 10 June 2015 However, their dielectric properties largely depend on the synthesis method used. Hence, we developed
Received in revised form 12 September 2015 BaTiO3 nanoparticles by various synthesis methods seeking to compare and evaluate their crystal
Accepted 17 September 2015
structure, size, and homogeneity. Syntheses were carried out by four distinct synthesis methods:
Available online 25 September 2015
polymeric precursor (Pechini), electrochemical, hydrothermal and microwave-assisted hydrothermal. X-
ray diffraction and Raman spectroscopy analysis revealed the formation of barium titanate in cubic and
Keywords:
tetragonal structures. The nanoparticles synthesized have BET superficial areas varying in the range 10–
Barium titanate nanoparticles
Hydrothermal method
15 m2 g
1. Pechini method propitiated the formation of smaller particles than the other methods, i.e.
Pechini method 44.0  15 nm. By the electrochemical synthesis method the particles were obtained with 67.0  20 nm of
Microwave-assisted hydrothermal method diameter, with large distribution in particle size. The use of hydrothermal methods conducted to various
Electrochemical synthesis particle size distributions; while particles of 180.0  60 nm were formed using conventional
hydrothermal synthesis, smaller particles (66.0  16 nm) were formed using the microwave-assisted
hydrothermal synthesis in lower reaction times (six fold). All four methods were effective to synthesize
crystalline BaTiO3 nanoparticles, with different sizes and structural characteristics. Thus, the choice of
the suitable synthesis method will depend on the desired properties of the BaTiO3 nanoparticles.
ã 2015 Elsevier B.V. All rights reserved.

1. Introduction Due to excellent piezoelectric properties (polarization occurs

Barium titanate (BaTiO3) was discovered in the 40s when its
high dielectric constant was reported worldwide [1]. The
BaTiO3belongs to the perovskite family, of the ABO3 type [2] and
its structure has a low Curie temperature of nearly 120  C, which
attributes to this material an elevated dielectric constant at
environmental temperature (e = 3600 at 25  C and 105 Hz). This
feature allows their use in high-capacity charge storage capacitors
[3,4]. The BaTiO3 presents different crystallographic structures
which frequently present distinctive dielectric properties. Three
phase transitions are possible in the BaTiO3, according to
temperature: rhombohedral to orthorhombic, transition that
occurs around
90  C; from orthorhombic to tetragonal, phase
transition that occurs around 5  C; and from tetragonal to cubic in
temperatures around 120  C [5].
* Corresponding author. Fax: +55 79 32182190.
E-mail address: gianrsb@gmail.com (G.R. Salazar-Banda).
after applying pressure), BaTiO3 is used in developments of
counters, data collectors, sound detectors, as well as in microelec-
tronic devices fabrication [6]. Moreover, the dielectric character-
istics of this material are important in the electronic industry for
the fabrication of multilayer ceramic condensation devices,
ceramic capacitors, supercapacitors, among other applications
[1,3,6]. BaTiO3 crystalline nanoparticles with high purity are
necessary for the fabrication of reliable microelectronic devices.
This application highly depends on the grain size, the smaller the
better, besides the good distribution and uniformity of the particles
[6,7].
Staedler et al. [8] developed BaTiO3 nanoparticles of particle
size 123 nm, with non-linear optical properties applied to
fluorescent probes for biological applications and multiphoton
microscopy. Biocompatibility studies of particles of barium
titanate, with sizes of 150 nm, on stem cells demonstrated the
possibility of application as nanovectors and enhancement of
osteogenic potential of mesenchymal stem cells (MSCs) for bone
regeneration [9,10].

http://dx.doi.org/10.1016/j.cep.2015.09.011
0255-2701/ ã 2015 Elsevier B.V. All rights reserved.
 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20
Dielectric properties mainly depend on crystal structure, size,
stoichiometry, and homogeneity, and surface properties of BaTiO3,
that strongly depend on the synthesis method [11]. Conventional
barium titanate synthesis involves high temperatures (1200  C)
for the calcination of BaCO3 and TiO2 powders, that commonly
results in low purity and forms large particles (>1 mm) with non-
uniform distribution, which is due to both the high temperatures
and the reaction in heterogeneous solid phase [12,13].
However, researchers have focused on new synthesis methods
to prepare BaTiO3 particles with various sizes and morphologies,
using low temperatures [14]. Among them, hydrothermal synthe-
sis of crystalline BaTiO3 involves chemical reactions among a
concentrate solution of barium hydroxide and TiO2, or gels of Ba–Ti
acetate mixtures, at relatively low temperatures (<1200  C). This
method received attention due to the possibility to produce small
particles (1–1000 nm) with a more uniform size distribution [11].
Solid–fluid phase interaction allows control of the particle size
through tailoring of synthesis parameters, such as pH, reaction
temperature and heating time. Control of these parameters can
stabilize BaTiO3 particle formation and delay impurity formation.
Besides, the precursors for the BaTiO3 preparation by hydrother-
mal route are low cost and easy management, which establishes
this method as a simple and efficient route for BaTiO3 preparation
[11].
In this context, heating technologies by microwaves have been
applied in organic reactions since late 80s [15]. However, they are
scarcely used in material synthesis laboratories. Heating by
microwaves differ from those that occur by bath or heating plates,
where heating is done through conduction, irradiation and
convection. The action mechanisms of microwaves are the
dielectric heating, by dipole rotation and/or ionic conduction
[16]. The microwaves application to heating in the hydrothermal
synthesis occurs by interaction between microwaves and polar
substances of the reaction medium: radiation is absorbed by
reagent and the electromagnetic energy is converted into thermal
energy. Thus, heat is generated from the interior of the material,
which allows a reduction in process time and energy cost [17].
On the other hand, electrochemical route for nanoparticles
synthesis is of considerable interest due to the particle size control
obtained by adjusting the current density or the applied potential,
which is considered the most attractive goal for the synthesis in
this field. Extensive investigations were concentrated on metallic
particles electrochemically synthesized, particularly noble metal
particles. However, few studies were carried out for a synthesis of
inorganic compounds [18]. This method was used in the formation
of BaTiO3 film and BaTiO3 nanoparticles over metallic titanium by
the reaction of Ba(OH)2 or Ba(CH3COO)2 in alkaline aqueous
solution (NaOH) with pH 13. The process can be thermally
activated at moderate temperatures (T < 200  C, P < 106 Pa), or
activated by electric current between a titanium anode and a
platinum cathode [19].
The Pechini method, also known as a polymeric precursor
method, was proposed by Pechini in the 60s. This method involves
the formation of chelates from some hydro carboxylic organic
acids, on which the metalcations incorporated are homogeneously
distributed. The salt solution, in acid media, is mixed with a poly-
hydroxilated alcohol, under heating and agitation, leading to the
formation of an ester due to the condensation of alcohol and acid
chelate. The chelation reaction results from the capacity of some
carboxylic acids (as citric acid) to form polybasic chelates with
various cations, such as, titanium, zirconium, chrome, lead, cobalt,
nickel, barium, among others. In this method, the carboxylic acid is
esterified by alcohol molecules, producing water. These are
polyfunctional reactant, in the formation of a polymeric resin
with chelated cations divided by the entire length of the molecular
structure of the resin [20]. The thermal treatment of the resin is
13
carried out in atmospheric air normally in temperature over 500  C
generating metallic oxide crystallites, by oxidation, which is
adequate for the organic part elimination and achievement of the
desired stage. Some advantages of the Pechini method are, it allows
good chemical homogeneity, and presents a direct and precise
control of the stoichiometry in complex systems [21–23].
In this context, the goal of this study was to synthesize barium
titanate nanoparticles by four different routes: Pechini method,
electrochemical synthesis, hydrothermal synthesis and micro-
wave-assisted hydrothermal synthesis. These methods allowed the
achievement of materials with different particle size, granulo-
metric distribution, as well as structural characteristics.
2. Experimental
2.1. BaTiO3 synthesis by electrochemical method
Barium titanate synthesis by electrochemical method [24,25]
was conducted in a 200 mL electrochemical cell coupled to a
thermostatic bath (Nova Ética, Ultrathermostatic Bath) maintain-
ing a constant reaction temperature of 50  C, since the reaction is
exothermic. The reaction inside the cell was maintained under
magnetic agitation with electrodes connected to a double power
supply source 0–30 V, 3 A (ICEL Manaus PS-5000), working in
series, reaching a maximum potential of 60 V and a current of
around 3.25 A. These high potentials are needed to detach titanium
from the electrode and then form BaTiO3 in a 2 h reaction.
To prepare the electrolytic solution, 300 mL of ultrapure water
was previously boiled during 30 min to remove CO2 dissolved in
water, thus seeking to avoid barium carbonate formation as an
undesired byproduct. 200 mL of a 0.1 mol L
1 octohydrated barium
(Ba(OH)28H2O, from Synth1) solution and a 0.1 mol L
1 sodium
hydroxide 99% (NaOH, from Vetec1) solution were used as
electrolyte. Firstly, Ba(OH)2 was dissolved and then NaOH was
added under constant agitation. Afterwards, titanium electrodes
(7 cm length  2 cm width) were sanded, washed with acetone and
rinsed with distilled water.
Once the reaction completed, the solid particles precipitated
and the excess liquid (supernatant) was removed. The particles
were washed with distilled water and then vacuum filtered. Some
particles were also washed with 0.1 mol L
1 nitric acid (HNO3,
Vetec1) aqueous solution to remove barium carbonate probably
formed in the synthesis. Finally, particles were washed again with
ultrapure water and dried at 120  C.
2.2. BaTiO3 synthesis by Pechini method
Citric acid (C6H8O7) and barium acetate (BaC4H6O4), both from
Synth1, and ethylene glycol (C2H6O2) from Vetec1, were used for
the precursor solution preparation.
2.2.1. Barium citrate preparation with ethylene glycol
Initially 10.98 g of barium acetate was dissolved in 400 mL of
ultrapure water; simultaneously, 24.8 g of citric acid was dissolved
in ultrapure water. So both solutions were mixed and 16.5 g of
ethylene glycol were added, leaving the mixture under agitation
until complete dissolution.
2.2.2. Titanium citrate preparation with ethylene glycol
The titanium citrate solution was prepared dissolving 80.6946 g
of citric acid in 400 mL of distilled water. After this procedure, 20 g
of titanium isopropoxide was slowly added, with further addition
of 53.8 g of ethylene glycol under constant agitation until complete
dissolution. Finally, both prepared complexes were mixed and pH
adjusted to 9 using NH4OH. The mixture was left under magnetic
agitation and heated at 200  C, to form a yellow solution with
14 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20

viscous aspect. Further, this solution was calcined for 5 h at 600  C
under a heating rate of 2  C min
1. Thus, a very thin white powder
was obtained, which was then macerated and stored.
2.3. BaTiO3 synthesis by hydrothermal method
Synthesis was carried out in molar ratio of Ba:Ti (1:2), using
octohydrated barium hydroxide (Ba(OH)28H2O, Synth1) and TiO2
P-25 particles (Degussa) as precursors. Initially, barium hydroxide
was dissolved in ultrapure water (all water used in this study was
purified by a Milli-Q system) and then the titanium dioxide was
added. The mixture was kept under agitation for 2 h, obtaining a
suspension, later transferred to a Teflon1 container inside a
threaded steel autoclave, heated to up to 150  C and submitted to
autogeneous pressure. The incubator, equipped with a rotating
axis, was kept under agitation (56 rpm) for 20 or 24 h. After cooling
down, the suspension was rinsed in sequence with HNO3, Vetec1
(0.1 mol L
1), solution and distilled water and then vacuum
filtrated. The solid obtained was dried at 120  C.
X-ray diffraction (XRD) was used to determine crystalline
structure and identify crystallographic phases of particles. The XRD
equipment used was a Rigaku model Miniflex TG, using a CuKa
(30 kV and 15 mA) source, in the gap of 20 < 2u < 80 , with a 0.02
step, and a measurement time of 1 s. The identification of the
phases was carried out using the standard from the data bank of
the Joint Committee on Powder Diffraction Standards (JCPDS). The
crystallite size of the powders was determined using the Scherrer
equation (Eq. (2)) [30].
0:94  l
D¼ ð2Þ
b  cosu
where D is the crystallite size in nanometers, l is the wavelength of
the X-rays radiation (0.1548 nm for CuKa radiation) and b is the
width at half peak height (FWHM).
3. Results and discussion
3.1. X-ray diffraction analysis

2.4. BaTiO3 synthesis by microwave-assisted hydrothermal method
The suspension was obtained following the same methodology
used for hydrothermal method. However, in this case, the
suspension was introduced into a mono-mode microwave reactor
from CEM, Discover model, where the reactions were carried out in
batches.
This equipment has a single cavity with seven different
microwaves emission points, a maximum potency of 300 W and
a glass recipient, with volumes of 10 or 35 mL. The mixture was
kept at constant temperature (170  C) under constant agitation
during 4 h using a 2.45 GHz frequency. After cooled, the suspension
was rinsed in sequence with a 0.1 mol L
1 HNO3 solution and
Fig. 1 displays XRD patterns taken at the nanoparticles
synthesized by Pechini method, electrochemical synthesis, hydro-
thermal synthesis and microwave-assisted hydrothermal meth-
ods. The peaks identified in the pattern of samples synthesized by
electrochemical route are characteristics of BaTiO3 in the cubic
structure according to data base JCPDS 75-0461. The crystallite size
estimated by the Scherrer equation were approximately 35, 33, 21
and 20 nm for the hydrothermal, hydrothermal via microwave,
electrochemical and Pechini synthesis methods, respectively, can
be seen in Table 1. Thus, it is demonstrated that the nanoparticles
(110)
(A)

(211)
distilled water and finally vacuum filtered. The solid obtained was
(200)
BaCO3
(111)

dried at 120  C.

(220)

(310)
(100)

(311)
(210)

(221)
2.5. Physical characterization (a)
Intensity (a.u)

N2 physisorption measurements at 77 K were used to determine

textural characteristics of the particles, where specific superficial (b)
area was obtained from adsorption isotherms by BET method.
Physical adsorption analysis of pure nitrogen were carried out in (c)
Micromeritics equipment model ASAP 2000. The samples were
pre-treated under vacuum for 2 h at 200  C. The average particle (d)
size, D, was estimated from specific surface area data measured by
20 30 40 50 60 70 80 90
BET and it was calculated by the following equation:
2θ
6
DBET ¼ ð1Þ
r  SBET (B)
where r is the density (6.014 g cm ) of BaTiO3 and SBET is the

3

specific surface area of the solid material [26]. (a)

Raman spectroscopy measurements were carried out using a
Intensity (a.u)

spectrometer from JobinYvon, model HR-UV 800, equipped with a (b)

CCD (Charge Coupled Device) detector cooled at
70  C and coupled
with an OLYMPUS BX microscope. Samples were submitted to He–
Ne laser with a 632 nm excitation and submitted to a potency of (c)
less than 5.5 mW.
Scanning electron microscopy (SEM) measurements were (d)
carried out in an electronic microscope by field emission gun 44 45 46
(FEG), model Quanta 400 from FEI Company, operated between 10 2θ
and 20 kV, equipped with microanalysis by EDS. No pre-treatment
with sputtered gold was necessary. The average particle size was Fig. 1. (A) XRD patterns of the samples synthesized by: (a) microwave-assisted
estimated from SEM-FEG images (counting about 600 particles in hydrothermal, (b) Pechini, (c) hydrothermal and (d) electrochemical methods. (B)
The angular regions of the X-ray powder diffraction 2u = 45 : (a) microwave-
each image) by using the image analysis software Solutions Meter assisted hydrothermal, (b) Pechini, (c) hydrothermal and (d) electrochemical
Size 1.1. methods.
 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20
Table 1
Summary of the results of particles sizes estimated XRD, SEM and BET.
Sample Crystallite size estimated by XRD
(nm)
Electrochemical 21.0
Pechini 20.5
Hydrothermal 44.7
Microwave 33.6
are formed by nanocrystals. Small amounts of barium carbonate
(JCPDS 05-0378), in witherite phase, were also formed from
atmospheric CO2.
The samples synthesized by Pechini method also present the
formation of barium carbonate (Fig. 1), but no cleansing treatment
was applied for its removal from the sample. Similarly, Chen and
Chen [27] synthesized barium titanate by hydrothermal method
and observed the formation of BaCO3 (JCPDS: 41-0373) with no
cleaning method, then they washed the sample with formic acid
and removed all the undesired phase. BaTiO3 in the cubic structure,
according to data base JCPDS 31-0174, was also identified in this
sample. In Fig. 1(b) it may be noted that no peak was split in
2u = 45 corresponding to the tetragonal phase BaTiO3. The peak
of the division is the position of the Bragg reflections in the plane
(2 0 0), forming a reflection signal in the lower angle indexed as
(0 0 2) [11,28].
Only pure barium titanate cubic perovskite structure (according
to JCPDS 75-0461) was identified in samples synthesized by the
hydrothermal method, since the powder was rinsed with nitric
acid solution (0.1 mol L
1). Thus revealing that nitric acid is
efficient for BaCO3 removal.
As the rinsing with nitric acid solution was effective for barium
carbonate removal from the synthesized samples by hydrothermal
and microwave-assisted hydrothermal method (Fig. 1), the same
rinsing procedure was carried out for samples synthesized by
Pechini and electrochemical methods. The XRD data can be
observed in Fig. 2(a) and (b), respectively.
Although the results have shown cubic crystal structure,
tetragonal crystal structure could exist and not be detected.
According to Uchino et al. [29] the particle sizes below 120 nm
cannot be identified by XRD, so the formation of both structures,
cubic and tetragonal, cannot be excluded.
3.2. Specific superficial area (BET)
Table 2 summarizes the results of the specific superficial area of
the nanoparticles synthesized by the various methods. It is
observed that the materials have specific area lower than
Intensity (a.u)
20 30 40 50 60 70
2θ
Fig. 2. XRD patterns of the synthesized samples by: (a) Pechini, (b) electrochemical,
after rinsing with nitric acid (0.1 mol L
1).
15
Particle size estimated by SEM Particle size estimated by BET
(nm) (nm)
67.0  20 73.9
44.0  15 66.5
180.0  60 332.0
66.0  17 83.1
15 m2 g
1, obtained for Pechini synthesized nanoparticles. Mandal
[30] synthesized barium titanate by Pechini method using similar
conditions and obtained nanoparticles with an average specific
superficial area of 15–20 m2 g
1. Hydrothermal methods generated
the lowest specific areas. The nanoparticles synthesized by
microwave-assisted hydrothermal method displayed a superficial
area of 12 m2 g
1. Specific superficial areas of 7.6–11.2 m2 g
1 have
been found for barium titanate particles prepared using TiO2 (P-25
Degussa) as precursors and hydrothermal synthesis conditions of
85–180  C for 24 h [31]. Nyutu et al. [32] synthesized barium
titanate nanoparticles using BaCl22H2O and titanium isoprop-
oxide by microwave-assisted hydrothermal method, using a
2.45 GHz frequency and 170  C for 10 h, and obtained particles
with 12 m2 g
1. It is noteworthy that in our study it was used only
4 h of reaction at the same temperature, thus proving the efficiency
of microwave-assisted hydrothermal method. Despite BET data
show little differences in the specific superficial area for the
synthesis methods, it is clear that the highest surface area
(15 m2 g
1) showed by the barium titanate synthesized by Pechini
method is due to the lowest particle size (66.5 nm), displayed in
Table 1, followed by electrochemical, microwave and hydrothermal
methods, respectively. Similar observations have been made by
Kolen’ko et al. [33] when synthesized nanosized particles of
barium titanate by solvothermal method. The smaller particles size
the larger the surface area.
3.3. Scanning electron microscopy
Fig. 3(a) shows the SEM-FEG images of the samples synthesized
by electrochemical method where some dense rods are identified.
According to Lopez et al. [34] these rods are probably constituted of
barium carbonate, confirming the previous findings by XRD for the
non-rinsed HNO3 samples (Fig. 1). The BaTiO3 nanoparticles with
heterogeneous shapes are agglomerated and the particle size was
statistically estimated with diameters of 67  20 nm.
The SEM-FEG images of samples synthesized by the Pechini
method at pH 9 are displayed in Fig. 4(a) and also show several
particles and some rods forming agglomerates.
According to Silva et al. [22] the pH greatly influences the
morphology of the nanoparticles and when pH > 7 the tendency is
to produce more homogeneous and less agglomerated particles.
Particles synthesized by Pechini method presented dimensions of
44  15 nm, which are smaller than the ones synthesized by
remaining methods in this study. Barium titanate particles of
20 nm were synthesized by Vinthotini et al. [35] using Pechini
method; they had cubic structure with some traces of hexagonal
structure.
(a)
Table 2
Specific superficial area of the BaTiO3 nanoparticles.
(b)
Synthesis method SBET (m2 g
1)
80 90
Electrochemical 13.5
Pechini 15.0
Hydrothermal <10.0
Microwave-assisted hydrothermal 12.0
16 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20

Well dispersed, homogeneous and spherical particles were
obtained by the hydrothermal method at 150  C, as seen in Fig. 5(a).
In this method the temperature of synthesis is very important and
temperatures near 200  C lead to an increase in particle size [11]. In
this work, particle size distribution resulted in 180  60 nm mean
diameter particles, as can be seen in Fig. 5(b). According to Chen
and Chen [31], the particle size of the Ti precursor also influences in
the size and morphology of barium titanate particles. They used

Fig. 3. SEM-FEG images of the nanoparticles synthesized by electrochemical

method with a 50,000  zoom (a) and with a 100,000  zoom (b). Particle size Fig. 4. SEM-FEG images of the nanoparticles synthesized by Pechini method with a
distribution (c). 50,000  zoom (a) and with a 100,000  zoom (b). Particle size distribution (c).
 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20 17

TiO2 (P-25 Degussa) (average particle size of 21 nm), Ti(OH)4 and
TiO2 particles from Merck (average particle size of 200 nm) as Ti
source, obtaining barium titanate particles of nearly 130 nm for the
first two precursors and 250 nm for the latter one. Here we used
TiO2 (P-25 Degussa) as Ti precursor.
Fig. 6(a) presents barium titanate particles synthesized by
microwave-assisted hydrothermal method. The SEM-FEG images
show well-dispersed spherical particles, with particle mean
diameter of 66  17 nm according Fig. 6(b). Komameri and Katsuki

Fig. 5. SEM-FEG images of the nanoparticles synthesized by hydrothermal method Fig. 6. SEM-FEG images of the nanoparticles synthesized by microwave-assisted
with a 20,000  zoom (a) and with a 50,000  zoom (b). Particle size distribution hydrothermal method with a 50,000  zoom (a) and with a 100,000  zoom (b).
(c). Particle size distribution (c).
18 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20

185

143
136 155 (a)

310
Intensity (a.u)

515

Intensity (a.u)
185

308
136 155

732

185
518

832

308
1064

515
636
718 Electrochemical

1061

400

638
712
Pechini
0 200 400 600 800 1000 1200
-1
Wavenumber (cm )
0 200 400 600 800 1000 1200
Fig. 7. Raman spectra of the samples synthesized by electrochemical and Pechini -1
methods.
Wavenumber (cm )

141
(b)
[36] studied barium titanate synthesis under microwave irradia-

241
185
tion with similar conditions used in this work, temperatures of

308
150–200  C at 4 h reaction time, and obtained particles around

Intensity (a.u)

515
30 nm. The size of the particle, as well as, their crystallite size
determined by BET SEM and XRD methods (Table 1), follows the
same increasing order: Pechini, electrochemical, microwave
assisted hydrothermal, and hydrothermal.

711
3.4. Raman spectroscopy analysis

Fig. 7 shows the Raman spectra between 100 and 1200 cm
1 for
the samples synthesized by (a) electrochemical and (b) Pechini
0 200 400 600 800 1000 1200
method. The samples presented a peak in 1064 cm
1 (electro- -1
chemical method) and 1061 cm
1 (Pechini method) referred to the Wavenumber (cm )
vibration of symmetric stretch of BaCO3 [37,38]. The presence of Fig. 8. Raman Spectra of samples synthesized by (a) hydrothermal method and (b)
BaCO3 in the samples synthesized through electrochemical and microwave-assisted hydrothermal method.
Pechini routes was observed by XRD and SEM-FEG data, previously
discussed. Likewise, the two peaks around 136 and 155 cm
1 can 241 and 141 cm
1 (microwave-assisted hydrothermal) character-
be attributed to orthorhombic BaCO3 according to Shiratori et al. istics of the Ti–O–Ti vibration was also observed, indicating that
[39]. the reaction was incomplete and there is remnant TiO2 Ohsaka
According to Fontana et al., [40], Venkateswaran et al. [41] and et al. [45]. Peaks referred to symmetric stretch of BaCO3 are not
Begg et al. [42], the bands at nearly: 715, 515, 310, and 185 cm
1are seen between 1054 and 1069 cm
1, as previously pointed out for
related to the tetragonal structure of barium titanate. These peaks the particles obtained by electrochemical and Pechini method. This
were seen in both samples in Fig. 7. Barium titanate obtained observation confirms that barium carbonate was completely
through electrochemical method showed peaks at 732, 515, 310 removed with the nitric acid rinsing.
and 185 cm
1, and Pechini samples showed peaks at 718, 518, 308 For all the synthesis methods studied, the main crystalline
and 185 cm
1. A small peak at 832 cm
1 is observed only for the phases detected by XRD were cubic while by using Raman
sample obtained by electrochemical method and points out the spectroscopy the crystalline phases were tetragonal.
cubic structure of barium titanate. According to Freire and Katiyar [46] all optical modes of BaTiO3
In samples synthesized by hydrothermal and Pechini the with perfect cubic symmetry should be inactive for Raman
appearance of a shoulder around 636 cm
1 can be observed, this spectroscopy, because of the isotropic distribution of the
result is consistent with the work of Dutta et al. [43] who carried electrostatic forces around the Ti4+ ions within each octahedron.
out the synthesis of barium titanate precursors using oxalate under The same occurs for polymorphs, while the tetragonal and
heat treatment, the process was monitored using Raman orthorhombic polar are active in Raman spectroscopy.
spectroscopy, they found that the small shoulder around In this sense, the contradictory results between XRD (cubic
631 cm
1 is related to stretches of carbonate ion peaks in this phase) and Raman spectroscopy (tetragonal phase) data are
region resembles an amorphous solid obtained by mixing Ba(OH2) common in the literature [46] for barium titanate nanocrystals
and gel TiO2 (hydrothermal synthesis) and is attributed to Ti–O–Ti prepared by hydrothermal reaction. Chávez et al. [28] besides
bond of barium titanate amorphous. The second possibility is combined the Raman spectroscopy supported by density func-
related to the study by Kumar et al. [44] reported that a band tional theory calculations and measurement of the ferroelectric
636 cm
l in the Raman spectrum during the thermal decomposi- behavior to confirm the formation of a tetragonal phase.
tion of a metal organic resin to form BaTiO3 (Pechini synthesis).
Fig. 8 shows Raman spectrum for the samples synthesized by 4. Conclusions
(a) hydrothermal and (b) microwave assisted-hydrothermal
routes, respectively. The characteristic peaks of tetragonal barium This study describes the synthesis of barium titanate nano-
titanate around 711, 515 and 308 cm
1 were noted. In addition, particles by: Pechini method, electrochemical synthesis, hydro-
peaks at 638, 400 and 143 cm
1 (hydrothermal synthesis) and at thermal synthesis and microwave assisted-hydrothermal method.
 L.R. Prado et al. / Chemical Engineering and Processing 103 (2016) 12–20
The studied methods yielded different particle sizes, i.e.:
44  15 nm (Pechini), 67  20 nm (electrochemical), 180  60 nm
(hydrothermal) and 66  17 nm (microwave-assisted hydrother-
mal). Thus, Pechini method produces smaller particles than the
other methods which also presented a more uniform grain size
distribution. All methods synthesized particles with BET superfi-
cial area values in the range of 10–15 m2 g
1, which are similar to
those found in the literature for this kind of nanoparticles. XRD
analysis and Raman spectroscopy identified mainly overall crystal
structure of tetragonal barium titanate and local structure of cubic
barium titanate, and from these results it can be concluded that
both structures coexist in the synthesized samples. While, for the
hydrothermal and microwave-assisted hydrothermal methods
barium titanate in tetragonal structure was produced, but with
the presence of remnant TiO2.
For all methods, the removal of undesired barium carbonate it is
necessary by rinsing the barium titanate nanoparticles with a
0.1 mol L
1 nitric acid solution after syntheses.
The formation of particle agglomerates when synthesized by
Pechini method was seen, which was occasioned by the high
synthesis temperature, though for the hydrothermal and micro-
wave-assisted hydrothermal methods the particles were not
agglomerated due to agitation carried out during synthesis.
Comparing the four synthesis methods, the introduction of
microwave irradiation to hydrothermal method strongly dimin-
ished the reaction time (six fold) and presented easier operational
conditions. Pechini method was able to form the smallest particles;
the electrochemical method uses the smaller reaction time and
temperatures; whereas the hydrothermal method was able to form
the less agglomerated particles. Thus, all four methods were
successful to synthesize barium titanate nanoparticles with
tetragonal and/or cubic crystalline structures.
Acknowledgments
The authors thank the National Council of Technological and
Scientific Development-CNPq of Brazil (grant 303630/2012-4), the
Brazilian Federal Agency for Support and Evaluation of Graduate
Education-CAPES and Foundation of Support to Research and
Technological Innovation of the State of Sergipe-FAPITEC for the
scholarships and financial support for this work.
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