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Lead-free 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 powder

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surface treated against hydrolysis – a key for a successful

Cite this: J. Mater. Chem. C, 2013, 1,
4846 aqueous processing
Ajay Kaushal,* Susana M. Olhero and J. M. F. Ferreira

Received 19th April 2013
Accepted 4th June 2013
DOI: 10.1039/c3tc30741g
www.rsc.org/MaterialsC
The properties of functional ceramics and their performance in industrial applications are strongly affected
by the processing treatments. We report on long term stability of aqueous 0.5Ba(Zr0.2Ti0.8)O3–
0.5(Ba0.7Ca0.3)TiO3 (BZT–BCT) suspensions. The effects of aging time on pH and on the leaching extents
of Ba, Zr and Ca elements were systematically investigated for the naked, and the surface treated
particles against hydrolysis. Suspensions with solid loadings (F) up to 60 vol%, pseudoplastic flow
behaviours and long term colloidal stability could be achieved from the surface treated powder. A
fractal dimension (D) of
1.97 to 1.98 was estimated for the BZT–BCT suspensions from the yield stress
(sy) versus (F) dependence, suggesting a reaction limited cluster aggregation (RLCA) type of particle
aggregation with a substantial rearrangement occurring in the aggregates under shearing. The
maximum solid loading (Fm) z 61 vol% was determined. The concentrated and stable suspensions
represent a stride for successful processing of functional BZT–BCT ceramic components via various
aqueous colloidal shaping methods (slip casting, gel-casting, etc.) for large scale industrial applications.

Introduction ensuring enhanced industrial applications. The dispersion of

Electroceramics are proving to be most promising for miniature
devices in industrial and commercial applications because of
their unique properties, namely, high piezoelectric and electro-
mechanical coupling on poling and very high dielectric
permittivity in relaxor systems, and high pyroelectric and elec-
tro-optic coefficients.1 However, most of the commercially
available piezoelectric materials, e.g., Pb[ZrxTi1x]O3 (PZT), are
comprised of more than 60 weight percent (wt%) lead (Pb) and
are listed as toxic and hazardous, not only in the form of direct
pollutants originating from the waste produced during the
manufacturing process, but also because products containing
PZT based transducers are not recyclable.2 The highest piezo-
electric coefficient d33
620 pC/N has been recently reported
for the lead free BZT–BCT ferroelectric system.3
The fabrication of polycrystalline ceramics with functional
properties includes several processing steps that were well
summarized by Moulson and Herbert.4 The most critical steps
that determine the microstructure and the nal properties of
ceramic components are the synthesis and the processing of
powders. Most commonly, the synthesis is carried out by solid
state reaction that involves heat treatment of a precursor
powders' mixture at a suitable temperature to obtain the desired
phase. External contamination factors need to be minimized for
Department of Materials and Ceramic Engineering, CICECO, University of Aveiro,
3810-193, Aveiro, Portugal. E-mail: ajay.kaushal@ua.pt; jmf@ua.pt; Fax: +351-234-
370204; Tel: +351-234-370354
powders in suitable liquid media to obtain stable colloidal
suspensions with high solid loading is one of the most
demanding processing steps.5 They would enable consolidation
of bulk green shapes with homogeneous microstructures as
revealed in earlier reports on aqueous colloidal processing of
different materials,6,7 including PZT pillar arrays via an epoxy
gel-casting method.8
The aqueous dispersion of electroceramic powders containing
a large number of chemical components can be a very chal-
lenging task as there is a high probability of each component
reacting differently with water. This might lead to stoichiometric
deviations and degradation of the desired functional properties
of the products. However, to date, no study has been reported on
colloidal processing of BZT–BCT since research on this material
started in December 2009.3 But the well-known advantages of
colloidal processing routes (an effective break down of particle
agglomerates, the control of interaction forces between the
dispersed particles and a good packing ability) that enhance the
sintering ability at lower temperatures7 are expected to avoid
coarsening of the sintered microstructure, thus improving the
reliability and performance of nal products. Moreover, the non-
toxicity of BZT–BCT based materials coupled with their potential
functionalities stimulated us to investigate the synthesis and
aqueous processing ability of BZT–BCT powders.
The present study includes all the essential steps for
consolidating defect free green ceramic bodies from: (i) solid
state reaction synthesis of pure phase BZT–BCT; (ii) deag-
glomeration to obtain a ne powder; (iii) assessment of the

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Paper
solid/liquid interfacial reactions and how they can be
controlled/prevented through a suitable surface treatment of
the powder particles; (iv) preparation of high solid loading
suspensions; and (v) evaluating the effects of surface coating,
dispersant type and amount, solid volume fraction, and aging
time on rheology and colloidal stability. The solid/water inter-
facial reactions and the quality of dispersion were assessed by
monitoring the evolution of time versus pH, elemental
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concentrations of leached species for the non-treated and
surface treated BZT–BCT powders. The efficiency of different
dispersants was evaluated through sedimentation tests. Zeta
potential measurements coupled with XRD were used to assess
the effects of surface treatment and of the presence of selected
dispersant. The ow properties (viscosity versus shear rate) of an
aqueous BZT–BCT suspension with different solid loadings
were investigated by rheological measurements.
Experimental
Precursor and powder synthesis
Powder with the following molar ratios: 0.5Ba(Zr0.2Ti0.8)O3–
0.5(Ba0.7Ca0.3)TiO3 was synthesized by using conventional solid
state reaction from a precursor mixture of high purity BaCO3
(Sigma-Aldrich, Steinheim, Germany), ZrO2 (Sigma-Aldrich,
Steinheim, Germany), TiO2 (Riedel-de Haen, Sielze, Germany),
and CaCO3 (Sigma-Aldrich, Steinheim, Germany). The mixture
was rst prepared by dry ball-milling for 1 h, followed by wet
ball-milling in ethanol for 2 h to guarantee complete homoge-
nisation, and then dried at 100  C. The dried powder was
calcined at 1000  C for 4 h, reground by dry ball milling for 2 h,
and then heat treated at 1400  C for 4 h followed by 1 h dry ball
milling to destroy the coarser agglomerates formed upon heat
treatment. The as-obtained powder was then attrition milled for
10 h in ethanol at 700 rpm. The particle size of powder was
measured using a Coulter LS 230, Buckinghamshire, UK,
Fraunhofer optical model.
Selection of dispersant
Four different aqueous dispersant solutions of alkali-free
ammonium salts derived from: (i) polymethacrylic acid (Dolapix
CE 64); (ii) polyacrylic acid (Dispex A40); (iii) polyacrylate (Dura-
max D-3005); and (iv) polycarbonate (Targon 1128) were tested.
The efficiency of the dispersants was evaluated by sedimentation
tests using suspensions containing 5 wt% of BZT–BCT powder
and a xed added amount (0.5 wt%, relative to dry mass of solids)
of each different dispersant. The suspensions were kept under
magnetic stirring for 30 min and then transferred to graduated
cylindrical glass test tubes (25 mL volume). The height (H) of the
cloudy part of the suspension was recorded at regular time
intervals and the variation of the H/Ho ratio (where Ho is the total
height) as a function of time was calculated.
Preventing aging effects in aqueous media by surface
treatment
A surface treatment that revealed to be effective in preventing
hydrolysis of AlN,9,10 MgAlO4 spinel11 and BST12 powders was
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applied. It consisted of adding 100 g of the attrition milled BZT–
BCT powder to 200 cm3 of 2 wt% aqueous solutions of
aluminium di-hydrogen phosphate, Al(H2PO4)3, (Bindal A, TKI,
Hrastnik, Slovenia). The mixture was then kept at 60  C under
magnetic stirring for 30 minutes. Subsequently, the powders
were settled, the supernatants removed and the powders dried
at 80  C for 12 h. In order to assess the efficiency of the surface
treatment, aqueous suspensions containing 5 wt% of non-
treated (BZT–BCT–NT) and surface treated (BZT–BCT–ST)
powders were kept under magnetic stirring at room tempera-
ture and the pH variations as a function of time were monitored
for 7 days (168 h). Aer this period, the suspensions were ultra-
centrifuged (10 000 rpm, 20 min) to obtain clear supernatant
liquids, which were then analyzed by Inductively Coupled
Plasma – Optical Emission Spectroscopy analysis (ICPOES,
Jobin, Yvon, JY 70 plus, France) to determine the concentrations
of leached elements.
Preparation and rheological characterization of concentrated
suspensions
Aqueous slurries with different solid loadings in the range of
30–60 vol% were prepared with the help of Dispex A40 as
dispersant and de-agglomerated for 24 h in the polypropylene
bottles using alumina balls (the charge to balls ratio was 1 : 3).
The optimal concentration of dispersant was determined from
the minimum suspension viscosity for the suspension with
55 vol% solids. Viscosity measurements were performed using a
rotational Rheometer (Bohlin C-VOR Instruments, Worcester-
shire, UK) at shear rates up to 600 s1.
The structural phase orientations of the BZT–BCT samples
were studied by measuring X-ray diffraction (XRD) patterns
using a Rigaku X-ray diffractrometer with CuKa (1.54 Å) radia-
tion in a q–2q geometry.
Results and discussions
Synthesis, dispersion and stabilization of BZT–BCT powder
Fig. 1 shows the particle size distributions of the BZT–BCT
powders before (dry ball milled for 1 h) and aer wet attrition
milling (AM) for 10 h in ethanol. A trimodal distribution was
obtained for the powder dry milled for 1 h, revealing the pres-
ence of coarse (>10 mm in diameter) agglomerates. Attrition
milling destroyed the third population of agglomerates and
resulted in a bimodal particle size distribution. The volume
fraction of the rst population centred at
0.25 mm increased at
the expense of the second one centred at
1.6 mm resulting in
an overall decrease of average size from 3.4 to
0.3 mm. The
presence of two particle populations with different sizes is
expected to increase the particle packing ability in a suspension,
since the smaller particles can occupy the interstitial spaces
between the larger ones and release the liquid immobilised in
void spaces.8 In this way, bimodal particle size distributions are
expected to lower the viscosity of suspensions at a given solid
loading, or to enable higher solid volume fraction to be ach-
ieved for a given viscosity level, in comparison to suspensions
prepared from monomodal powders. Achieving high solid
J. Mater. Chem. C, 2013, 1, 4846–4853 | 4847

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Fig. 1 Particle size distributions of the BZT–BCT powders before and after wet
attrition milling.
loading is a key point for successfully fabricating 3D micro-
components by direct consolidation techniques.
Colloidal processing routes using well stabilized suspen-
sions offer great advantages when aiming at consolidating
defect-free products with desired functional properties.
Furthermore, coagulation of the particles has to be prevented
through inter-particle repulsion and slowing down sedimenta-
tion by increasing viscosity of the continuous phase. Fig. 2
compares the H/Ho values measured in the sedimentation tests
performed in the presence of 0.5 wt% of different dispersants.
No sedimented layers could be detected with the naked eye in
all the suspensions. Just a gradient concentration cloudy part at
the bottom and a clear supernatant at the top could be distin-
guished. Accordingly, only the heights (H) of the cloudy parts
were recorded. The higher H values were found for the
Fig. 2 Dispersability of BZT–BCT powder in aqueous medium with added
0.5 wt% of different dispersants.
4848 | J. Mater. Chem. C, 2013, 1, 4846–4853
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suspension containing Dispex A40. Accordingly, Dispex A40 was
selected for its apparent better dispersion ability.
The evolution of pH versus time of aqueous suspensions
containing 5 wt% of non-treated (BZT–BCT–NT) and surface
treated (BZT–BCT–ST) powders within an aging period of 168 h
(7 days) under magnetic stirring at room temperature is shown
in Fig. 3. It can be seen that pH values uctuate within the range
of 8.3–9.4 for the BZT–BCT–NT suspension, whereas signi-
cantly smaller pH variations between 8.8 and 9.1 were registered
for the suspension containing the BZT–BCT–ST powder, which
presents an approximately constant pH value of
9 over the
entire aging period of 1 week. The aging experiments were also
conducted in the presence of dispersant to better understand
the role of its dissociation species in the leaching extents. The
pH variations reveal some sort of ionic leaching from the
surface of the particles, which apparently occur in a higher
extension for the non-treated powder. This hypothesis of ionic
leaching in aqueous media was conrmed by ICP analysis of
centrifuged supernatants derived from suspensions aged for
one week as shown in Fig. 4. This gure reveals some interesting
features: (i) the extent of leaching was 4–5 times higher for the
non-treated powder; (ii) the leaching process was somewhat
enhanced in the presence of dispersant; (iii) the leached
amounts of Ba are 15–16 times higher than those of Ca. This last
feature was expected from the Ba/Ca molar ratio in the planned
composition (0.85/0.15 ¼ 5.7). Even though, about one order
magnitude difference remains to be explained. The leaching Ba
and Ca ions from the BZT–BCT powder in water could be
schematized according to eqn (1):
(x + y)BZT–BCT(s) # xBa2+(aq) + yCa2+(aq)
+ (x + y)(BZT–BCT)2(aq) (1)
The preferential leaching of Ba2+ ions from the BZT–BCT
powder relative to Ca2+ can be understood considering the lower
Fig. 3 pH versus time evolution of aqueous suspensions of surface treated (ST)
and non-treated (NT) BZT–BCT powders.
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Fig. 4 ICP analysis showing Ba and Ca concentrations in centrifuged superna-
tants from 5 wt% aqueous solutions of BZT–BCT–ST and BZT–BCT–NT powder
kept for 1 week in water in the absence and in the presence of dispersant (D).
ionic eld strength of Ba2+ (1.11) in comparison to that of Ca2+
(2.04).13 The same reasoning also explains why the concentra-
tions of other constituent elements (Zr, Ti) with signicantly
higher ionic eld strength values were less than 0.1 mg L1
(below the detection limit of the instrument).13 The eld
strength is dened as the charge of an ion divided by the square
of its ionic radius, being essentially a measure of the strength of
the electrostatic eld created by the ion (considered as a point
charge in space). The less extended leaching observed for the
surface treated powder shows that the efficiency of the surface
protection method against hydrolysis reported for other water
sensitive powders such as AlN9,10 and MgAl2O411 is also
conrmed for the BZT–BCT powder particles. It is suggested
that chemisorption of Al(HPO4)3 or Al(PO4)32 species onto the
surface of the particles hinders its direct contact with water
molecules, reducing hydrolysis and preferential ionic leaching.
On the other hand, the enhanced leaching process in the
presence of dispersant suggests that the poly-anionic species
(Dispex A40) are “removing” some Ba2+ and Ca2+ cations from
the solution, probably through the formation of monovalent
(Dispex A40–M2+)+ or neutral (Dispex A40–M2+–Dispex A40)
complexes, where M2+ stands for an alkaline earth metal ion
(Ba2+ or Ca2+). This sequestering process will favour the disso-
lution reaction, shiing the equilibrium of eqn (1) to the right.
Hydrolysis and non-stoichiometric dissolution reactions will
alter the composition of BZT–BCT powder. Fig. 5 presents the
XRD patterns of the BZT–BCT–NT powder, before (a) and aer
aging in water for one week (b), and of the BZT–BCT–ST powder
aer being in contact with water for the same time period (c). All
the diffraction peaks of the BZT–BCT–NT powder prepared by
solid state reaction could be indexed to the perovskite-type
tetragonal structure with a space group (P4mm) in agreement
with the respective Joint Committee on Powder Diffraction
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Fig. 5 XRD patterns of the BZT–BCT–NT powder before (a) and after aging in
water for one week (b), and of the BZT–BCT–ST powder after being in contact
with water for the same time period (c).
Standards (JCPDS) card no. 05-0626, in good consistency with
results reported elsewhere.14,15 However, the presence of some
extra impurity phase peaks corresponding to Ba(OH)2$H2O
(JCPDS card no. 00-026-0154) and BaZrO3 (JCPDS card no.
00-006-0399) was observed for the BZT–BCT–NT powder aged
for 1 week under constant stirring in water. This change from a
single perovskite-type tetragonal structure to a multiple phase
system conrms the occurrence of hydrolysis and degradation
of the original BZT–BCT–NT powder. Oppositely, the XRD
pattern of the surface treated powder (BZT–BCT–ST) does not
show any evidence of degradation. The absence of impurity
peaks and the close matching with the phase structure of as-
synthesized powder also suggest that no external contamina-
tion has been apparently introduced along the preceding pro-
cessing steps (deagglomeration/milling). These data suggest
that Bindal plays the exclusive role of a surface protective agent
against hydrolysis by chemisorbing at the surface of BZT–BCT
powder particles. To check if the Al and P elements that are
generated from the thermal decomposition of Bindal would
interfere with the perovskite structure of BZT–BCT, the a- and
c-axis lattice parameters were calculated from the XRD patterns
of BZT–BCT and BZT–BCT–ST materials with the tetragonal
phase structure. The values of a-axis were found to be equal to
4.0008 Å and 4.0036 Å for BZT–BCT and BZT–BCT–ST, respec-
tively, whereas the corresponding calculated c-axis values were
4.004 Å and 4.008 Å. According to these values, the calculated
c/a ratios are 1.0008 and 1.0011 for BZT–BCT and BZT–BCT–ST
materials, respectively. This small difference reveals that the
J. Mater. Chem. C, 2013, 1, 4846–4853 | 4849

Journal of Materials Chemistry C
tetragonality of the perovskite structure was not much dis-
torted. These features of the BZT–BCT–ST powder offer good
prospects for the subsequent colloidal processing steps.
Preparation and rheological characterization of concentrated
suspensions
Physical stability of suspensions is controlled by the addition of
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deocculating agents to enhance particle dispersion. Poly-
electrolytes are commonly used as dispersants. The dissociation
of the functional groups results in polyions that carry an elec-
trical charge, the adsorption of which onto the surface of the
suspended particles changes the electrical potential at the solid/
liquid interface, enhancing the repulsion among them. Particle
radius has a signicant bearing on suspension stability. For
submicron particles Brownian motion is usually signicant to
overcome the effect of gravity in suspensions. To maintain
stability through Brownian motion, one needs to prevent
particles sticking when they collide, which can be achieved by
increasing the charge associated with the particles.
Fig. 6 shows zeta potential measurements performed for BZT–
BCT–NT and BZT–BCT–ST particles in the absence and in the
presence of Dispex A40. Dispex A40 was added as a occulating
agent to enhance the particle dispersability as discussed in the
previous section. Dispex A40 was ionized in aqueous medium
and produced NH4+ cations together with polyanions. These
polyanions were adsorbed irreversibly to the powder particle
surfaces causing the particles to become negatively charged. The
adsorption caused two effects: the negatively charged surface
created an electric double layer resulting in electrostatic stabili-
zation; while the long chain of polycarboxylic anions introduced
an extra steric stabilization. The small amount of polycarboxylic
ammonium required to deocculate the suspensions fully can be
explained in terms of highly anionic nature of Dispex A40, its
high charge density when dissociated, and its extra steric effects.
This explains the drastic down shi of the entire electrophoretic
curve to negative values in the range of about 10 to 65 mV
observed for the BZT–BCT–ST particles in the presence of Dispex
Fig. 6 Zeta potential measurements performed for BZT–BCT–NT and BZT–BCT–
ST particles in the absence and in the presence of Dispex A40.
4850 | J. Mater. Chem. C, 2013, 1, 4846–4853
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A40 (sample BZT–BCT–ST + D). High zeta-potentials will promote
strong repulsive electrostatic interactions among the particles,
leading to well-dispersed suspensions. Considering that the
natural pH of the aqueous BZT–BCT–ST suspensions was
approximately constant (pH
9) over the whole aging period of
1 week (Fig. 3), the high zeta potentials measured in this pH
region suggest that Dispex A40 is well suited as dispersant for
BZT–BCT–ST powder suspensions.
The added amount of dispersant is another relevant
parameter. At the beginning, dispersion is enhanced with
increasing surface coverage. But when the surface becomes
saturated, further additions can only increase the concentration
of ionic and polymeric species in the solution, compressing the
electrical double layer and increasing the viscosity of the
dispersion medium. Thus, an excess addition of Dispex A40 can
promote an increase in plastic viscosity. This is conrmed by
the evolution of suspension viscosity versus percentage of
dispersant shown in Fig. 7 for an aqueous suspension con-
taining 55 vol% solids and added amounts of dispersant varying
from 0.3–2.5 wt%. There was an initial decrease in viscosity with
an increase in dispersant concentration of up to 0.5 wt% fol-
lowed by a gradual increase up to 1.5 wt% and a steep
increasing trend for further added amounts of dispersant. The
minimum in the viscosity curve versus dispersant concentration
conrms that 0.5 wt% is the optimum amount of dispersant
and justies its selection to evaluate the effect of solid loading
on the rheological behaviour in the present study.
_ depen-
Fig. 8 shows suspension viscosity (hs)–shear rate (g)
dence of the BZT–BCT–ST suspensions with different solid
loadings (F ¼ 30, 40, 44, 48, 51, 55 and 60 vol%) within the
range from g_ ¼ 0–600 s1. A pseudoplastic (or shear-thinning)
behaviour was observed for the suspensions with solid loading
greater than 44 vol%. Only the viscosity values measured along
the ramping up mode are shown here for clarity purposes. The
shear thinning ow behaviour reveals that particle aggregates in
the suspensions are gradually broken down into smaller ow
units by the applied forces, so that the resistance to ow is
Fig. 7 Influence of the added amounts of dispersant in the range of 0.3–2.5 wt%
on viscosity of an aqueous BZT–BCT–ST suspension containing 55 vol% solids.
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Fig. 8 Viscosity (h) versus shear rate (g) _ dependence of the BZT–BCT–ST
suspensions with different solid loadings (F).
reduced leading to the lower viscosity as the shear rate
increases. The particles become less and less interactive as the
solid volume fraction decreases and the reduction in viscosity
has apparently levelled off for solid loadings F # 44 vol% over
most of the shear-rate range examined. This suggests that the
liquid media fully exist among the particles in a ‘continuum’
form, so that the contribution from the particle interactions to
the overall colloidal viscosity became minimal. Powdered
suspensions in shear thinning regime can be thought of as a
two-dimensional ordered arrangement with particles separated
from each other at high shear-rate, thus reducing the inter-
particle attractions and, in turn, facilitating the suspension
ow.16
Relative viscosity of the suspensions (hr) may be dened as
the suspension viscosity (hs) divided by the viscosity of the
carrier medium (ho), and is plotted against F at a constant shear
rate, g_ ¼ 100 s1 (Fig. 9). An exponential increase of hr
with increasing F is observed, which was tted to the equation:
hr ¼ (0.324  0.1)e(0.140.01)F (correlation factor R2 ¼ 0.98). This
suggests the particle interactions (or more specically, the
attractive interparticle potential) became more pronounced as
F is increased, resulting in the exponential increase of relative
viscosity. The suspensions began to ow so long as the
applied stress exceeded a certain critical level, i.e., the yield
stress (sy). Various empirical rheological models were used to
estimate sy:17–19
Bingham model: s ¼ sy,b + hsg_ (2)
pffiffiffi pffiffiffiffiffiffiffi pffiffiffiffiffiffiffi
Casson model : s ¼ sy;c þ hs g_ (3)
Herschel–Bulkley model: s ¼ sy,h + kg_ n (4)
where, sy,b, sy,c, and sy,h are the yield stress values determined
from Bingham, Casson and Herschel–Bulkley model ttings,
respectively; k is the consistency index, and n is the power law
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Fig. 9 The exponential dependence of relative viscosity (hr) of BZT–BCT–ST
suspensions with different F at a constant shear rate, g_ ¼ 100 s1.
index. Fig. 10(a–c) show shear stress (s) versus shear rate (g) _
dependence of the BZT–BCT–ST suspensions of different solid
loadings in the range from F ¼ 30–60 vol% with Bingham,
Casson and Herschel–Bulkley model ttings, respectively. The
values of sy obtained by tting the data to various opted theo-
retical models were found to increase with the corresponding
increase in F and are illustrated in Table 1. The determined
values of sy were considered as model parameters with
approximate sy rather than true material properties due to the
difference in values obtained from various model ttings. The
values of sy obtained showed more signicance when used to
understand particle aggregation phenomena in the BZT–BCT
colloidal suspension. The sy variation with F can be used to
evaluate the colloidal structure of suspensions under near rest
conditions. A self-similar structure of the interconnected
network and the geometry of the aggregates can be described by
fractal analysis of suspension occulates.20 The suspension
yield stress relationship with solid loading is given as follows:21
sy ¼ GFm (5)
where G is a constant and the exponent value m can be evalu-
ated by tting sy versus F plot. The value of m is further related
to fractal dimension (D) of the occulated network by an
equation:
m ¼ (d + X)/(d  D) (6)
where d and X are the Euclidean dimension and backbone of
clusters respectively. Fig. 11 shows sy–F dependence for BZT–
BCT–ST suspensions containing different solid loadings where
sy values were estimated using various existing theoretical
models (Table 1). The plot depicts best tting of sy values with
exponent values of 3.89  0.2, 3.92  0.6 and 3.88  0.6 corre-
sponding to Bingham, Casson and Herschel–Bulkley models,
respectively. Considering the fractal geometry as three dimen-
sional and hence the Euclidean dimension d ¼ 3, we calculated
the value of D ¼ 1.97, 1.98 and 1.97 z 2 for Bingham, Casson
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Table 1 Yield stresses of BZT–BCT suspensions with different solid loadings

determined

Yield stress, sy (Pa)

Solid loading, F Bingham Casson Herschel–Bulkley

(vol%) model model model

30 1.58  0.1 1.44  0.01 0.51  0.1

40 5.89  0.3 3.24  0.01 1.16  0.1
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44 8.86  0.3 4.41  0.02 5.32  0.2

48 15.78  0.4 14.82  0.1 11.58  0.2
51 19.51  0.9 16.81  0.2 14.19  0.3
55 26.14  1.3 21.16  0.2 16.52  0.3
60 33.54  1.5 26.01  0.2 20.68  0.5

Fig. 11 The sy–F dependence for BZT–BCT–ST suspensions of different F. The

fitted lines and their equations are shown in the figure for sy values determined
from the various empirical models indicated.

form a cluster. We hence suspect that the investigated BZT–

_ dependence of the BZT–BCT–ST
Fig. 10 Shear stress (s) versus shear rate (g)
suspensions of different F for (a) Bingham, (b) Casson and (c) Herschel–Bulkley
model fittings.
and Herschel–Bulkley models, respectively, assuming the
fractal dimension of the backbone of the clusters X equals unity.
In colloids, clusters meet other clusters through random
motion. If they stick together with near unity probability, the
process is called diffusion limited cluster aggregation (DLCA)
because the rate limiting step is the diffusive motion of
the clusters and leads to fractal dimensions on the order of
D z 1.75 to 1.8.20 However, reaction limited cluster aggregation
(RLCA) regime is entered with D z 2 to 2.222 where the sticking
probability is less as a smaller number of collisions is needed to
BCT–ST powder suspension structure may be of the RLCA type
with a substantial rearrangement occurring in the aggregates
under shearing since the value of D determined in our model
suspension (i.e. D z 2) is reasonably close to that of the RLCA
model predicts.22 To get further insight into the investigated
results, the maximum solid concentration (Fm) was estimated
from 1  hr1/2 versus F plot (Fig. 12). An extrapolation of the
linear tted line of 1  hr1/2 versus F curve on 1  hr1/2 / 1
gave the value of theoretical maximum solid loading concen-
tration (Fm) of the colloids.23 The observed value of Fm for the
examined BZT–BCT–ST suspension was found to be approxi-
mately
61 vol% (as shown in Fig. 12), estimated from the
resulting tted equation 1  hr1/2 ¼ (0.59  0.04) + (0.0066 
0.0008)F (R2 ¼ 0.99). The high Fm ¼ 61 vol% obtained for BZT–
BCT–ST suspensions suggests that the achieved 60 vol% is the
optimized solid loading for colloidal processing (slip casting,
gelcasting, or other direct consolidation methods) of BZT–BCT–
ST powder, which would result in highly compact, least porous,
three-dimensional networks.

4852 | J. Mater. Chem. C, 2013, 1, 4846–4853 This journal is ª The Royal Society of Chemistry 2013

Paper
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Fig. 12 The 1  hr1/2 versus F dependence of BZT–BCT–ST suspensions at a
shear rate of g_ ¼ 100 s1. The extrapolation of 1  hr1/2 / 1 corresponds to the
theoretical maximum achievable solid loading (Fm) of the suspension colloids.
Conclusions
Suspensions with solid loadings up to 60 vol% could be
successfully prepared in aqueous media from the powder surface
treated (BZT–BCT–ST) with di-hydrogen phosphate. The surface
treatment prevented hydrolysis and leaching of ionic species
(Ba2+, Zr2+ and Ca2+) into the aqueous media. Rheological
analysis of colloidal suspensions revealed that an addition of
0.5 wt% Dispex A40 enabled optimal dispersion to be achieved.
An accentuation of the pseudoplastic character of suspensions
with F $ 44 vol% is due to an increasing trend for particle
structuration under near rest conditions. This increased degree
of particle interactions is translated by an exponential increase of
relative viscosity (hr) of suspensions with increasing F, following
the equation: hr1/2 ¼ (0.324  0.1)e(0.140.01)F. A fractal dimen-
sion close to 2 was estimated from all tested rheological models
(Bingham, Casson and Herschel–Bulkley), suggesting that the
structure of a highly concentrated suspension reaction is mostly
determined by limited cluster aggregation. A theoretical
maximum achievable solid loading, Fm ¼ 61 vol%, determined
from a linear 1  hr1/2  F relationship means that the practi-
cally achieved one (60 vol%) corresponds to optimal processing
conditions.
The present study disclosed a method of protecting lead
free BZT–BCT powders against hydrolysis and also revealed
how aqueous suspensions with long term colloidal stability
and high solid loadings can be prepared. These ndings are
likely to foster the fabrication of lead free electroceramic
materials via various colloidal methods (slip casting, tape
casting, gel-casting, etc.) and the commercialization of func-
tional devices.
This journal is ª The Royal Society of Chemistry 2013
View Article Online
Journal of Materials Chemistry C
Acknowledgements
The authors are thankful to the Foundation for Science and
Technology of Portugal (FCT) for the nancial support under
the project PTDC/CTM/099489/2008, and the post-doc grants of
S.M. Olhero SFRH/BPD/87486/2012 and A. Kaushal (SFRH/BPD/
77598/2011). The support from CICECO, University of Aveiro, is
also acknowledged.
Notes and references
1 B. Jaffe, W. R. Cook Jr and H. Jaffe, Piezoelectric ceramics,
Academic press, New York, 1971.
2 W. Yugong, H. Zhang, Y. Zhang, M. Jinyi and X. Daohua, J.
Mater. Sci., 2003, 38, 987.
3 W. Liu and X. Ren, Phys. Rev. Lett., 2009, 103, 257602.
4 A. J. Moulson, and J. M. Herbert, Electroceramics, Materials,
Properties, and Applications, Chapman and Hall, London, 1990.
5 G. H. Haertling, J. Am. Ceram. Soc., 1999, 82, 797.
6 I. Ganesh, G. Sundararajan, S. M. Olhero, P. M. C. Torres and
J. M. F. Ferreira, Ceram. Int., 2010, 36, 1357.
7 S. M. Olhero and J. M. F. Ferreira, Powder Technol., 2004, 139,
69.
8 S. M. Olhero, L. G. Gancedo, T. W. Button, F. J. Alves and
J. M. F. Ferreira, J. Eur. Ceram. Soc., 2012, 32, 1067.
9 M. Oliveira, S. M. Olhero, J. Rocha and J. M. F. Ferreira, J.
Colloid Interface Sci., 2003, 261, 456.
10 S. M. Olhero, S. Novak, K. Krnel, T. Kosmac and
J. M. F. Ferreira, J. Mater. Res., 2004, 19(3), 746.
11 S. M. Olhero, I. Ganesh, P. M. Torres and J. M. F. Ferreira,
Langmuir, 2008, 24(17), 9525.
12 S. M. Olhero, A. Kaushal and J. M. F. Ferreira, Fabrication of
barium strontium titanate (Ba0.6Sr0.4TiO3) 3D micro-
components from aqueous suspensions, J. Am. Ceram. Soc.,
2013, submitted.
13 John Graeme Pepin (US), Thermal shock resistant multilayer
ceramic capacitor termination compositions, EP0589242,
patent, 1994.
14 Joint Committee on Powder Diffraction Standards (JCPDS)
card no. 05-0626.
15 V. S. Puli, A. Kumar, D. B. Chrisey, M. Tomozawa, J. F. Scott
and R. S. Katiyar, J. Phys. D: Appl. Phys., 2011, 44, 395403.
16 H. A. Barnes, J. Rheol., 1989, 33, 329.
17 E. C. Bingham, Fluidity and plasticity, McGraw-Hill, New
York, 1922.
18 N. Casson, Rheology of disperse systems, ed. C. C. Mill,
Pergamon Press, Oxford, 1959.
19 W. H. Herschel and R. Bulkley, Kolloid Zeitschri, 1926, 39,
291.
20 P. Meakin, Phys. Rev. Lett., 1983, 51, 1119.
21 A. G. Marangoni, Trends Food Sci. Technol., 2002, 13, 37.
22 W. J. Tseng and C. H. Wu, Acta Mater., 2002, 50(15), 3757.
23 D. M. Liu, J. Mater. Sci., 2000, 35, 5503.
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