Japanese Journal of Applied Physics 51 (2012) 011503 REGULAR PAPER

DOI: 10.1143/JJAP.51.011503

Role of Sintering Temperature on the Phase Stability and Electrical Properties

of 0.94(K0:5 Na0:5 NbO3 )–0.06(LiSbO3 ) Ceramics
Prakash Kumar Palei and Pawan Kumar

National Institute of Technology, Rourkela-769008, India
Received August 11, 2011; revised September 28, 2011; accepted October 31, 2011; published online January 5, 2012

Lead-free 0.94(K0:5 Na0:5 NbO3 )–0.06(LiSbO3 ) (KNN–LS) ceramics were prepared by conventional solid-state reaction route (CSSR). For single
perovskite phase formation the calcination was done at 850
C for 6 h. Whereas for obtaining dense morphology the sintering of KNN–LS ceramics
was carried out at 1060, 1080, 1100, and 1120
C temperatures for 4 h, respectively. The structural study revealed that with the increase in
sintering temperature the structure of the ceramic transformed from pure tetragonal to pseudocubic phase. Scanning electron microscopy (SEM)
micrographs indicated that the optimum sintering temperature of the ceramic was found to be 1080
C. The Curie temperature (Tc ) of the KNN–LS
ceramic was found to decrease at higher sintering temperature. The development of typical hysteresis loop confirmed the ferroelectric and
piezoelectric nature of the KNN–LS ceramics sintered at different temperatures. The KNN–LS ceramics sintered at 1080
C showed better
ferroelectric and piezoelectric properties i.e., remnant polarization ðPr Þ  17:2 C/cm2 , coercive field ðEc Þ  13:5 kV/cm, piezoelectric coefficient
ðd33 Þ  161 pC/N, coupling coefficient ðkp Þ  0:36 and remnant strain 0:06% were obtained. # 2012 The Japan Society of Applied Physics

These substitutions also enhance the piezoelectric and ferro-

1. Introduction
Lead oxide-based piezoelectric ceramics, such as
Pb(Zr0:52 Ti0:48 )O3 (PZT) and modified PZT ceramics, are
the most widely used piezoelectric materials until now,
because of having high piezoelectric response, large scale
production capability and the tailoring of their properties
through composition. The excellent properties of PZT
based ceramics are considered due to the presence of a
morphotropic phase boundary (MPB).1,2) However, because
of the toxicity of lead oxide, the use of lead-containing
ceramics cause serious environmental problems. Recently,
concerns about these issues have led to establish the
legislation on restriction of the hazardous materials (RoHS)
and end of life vehicle (ELV) by European Union (EU).3)
Environmental and safety concerns with respect to the
utilization, recycling, and disposal of Pb-based ferroelectric
materials have induced a new surge in developing lead free
ferroelectrics, particularly those with properties comparable
to their lead-based counter parts. The search for alternative
lead-free piezoelectric materials is now being focused on
systems in which a MPB occurs. In the past several years,
much attention has been paid to the K0:5 Na0:5 NbO3 (KNN)
based ceramics because of having high Curie temperature
(Tc ), good electrical properties and environmental friendly
nature.4–7) This KNN system also possesses a MPB similar
to PZT system in the vicinity of 50 : 50 ratio of Na/K.
However, the major drawback for KNN ceramics is the
difficulty of obtaining high density by the conventional
sintering in air because of the high volatility of alkaline
elements at higher processing temperatures.8,9) Oxygen
deficiency has been another problem in the preparation,
which results from high-temperature processing and gives
rise to electronic conductivity.10) In order to solve these
problems, various techniques have been utilized, such as hot
pressing and spark plasma sintering (SPS).11,12) However,
they are more expensive and complicated routes compared
to conventional sintering processes. Recently, researchers
have shown that additives in KNN system such as LiSbO3
(LS),13) BiFeO3 (BF),10) ZnO,14) LiNbO3 ,15) LiTaO3 16) can
help to improve the sintering behavior of KNN system.


E-mail address: pawankumar@nitrkl.ac.in
011503-1
electric properties compared to pure KNN system. Among
all the modified KNN systems the 0.94(K0:5 Na0:5 NbO3 )–
0.06(LiSbO3 ) (KNN–LS) system is reported to have desir-
able ferroelectric and piezoelectric properties. Though there
are few studies on the various compositions of KNN–LS
system however, none of the study has been devoted to
confirm the phase stability of the 0.94KNN–0.06LS system
at higher sintering temperature. It was reported that alkali
oxides are volatile in nature, hence at higher sintering tem-
perature (>800  C) evaporation of these elements can take
place. The loss of alkali elements changes the stoichiometry
of the system which may also affect the phase stability of
the system. The phase stability of a system is very important
for high temperature applications.
Therefore, in the present study we have synthesized the
KNN–LS system by conventional solid state reaction route
(CSSR). The variation of sintering temperature on the phase
stability, dielectric, ferroelectric and piezoelectric properties
are discussed in detail.
2. Experimental Procedure
0.94KNN–0.06LS ceramics were synthesized by CSSR.
Sodium carbonate (Na2 CO3 , 99.9% purity), potassium
carbonate (K2 CO3 , 99.9% purity), niobium pentoxide
(Nb2 O5 , 99.9% purity), lithium carbonate (Li2 CO3 , 99.9%
purity) and antimony pentoxide (Sb2 O5 , 99.9% purity) were
used as starting precursors. Stoichiometric weights of all the
powders were mixed and ball milled with acetone for 8 h,
using zirconia balls as the grinding media. The calcination
of the powder was carried out at 850  C temperature for 6 h
and single perovskite phase formation was confirmed by X-
ray diffraction (XRD) technique. The calcined powder was
mixed thoroughly with 2 wt % poly(vinyl alcohol) (PVA)
binder solution and then pressed into disks of diameter of
10 mm and a thickness of 1:5 mm under 60 MPa pres-
sure. The sintering of all the samples was carried out at
1060, 1080, 1100, and 1120  C for 4 h in air, respectively
with a heating rate of 5  C/min. In order to examine the
phases present in the system, XRD analysis of the sintered
KNN–LS ceramics was performed on a PW 3020 Philips
diffractometer using Cu K ( ¼ 0:15405 nm) radiation.
The structure and unit cell parameters were calculated by
# 2012 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 51 (2012) 011503
Fig. 1. (Color online) XRD patterns of KNN–LS ceramics calcined at
 
(a) 850 C, sintered at (b) 1060, (c) 1080, (d) 1100, and (e) 1120 C.
X’pert High Score Plus 2.0 software. The sintered micro-
structures were observed using a scanning electron micros-
cope (SEM; JEOL JSM-6480LV). The experimental den-
sities (dex ) of the samples were measured by the Archimedes
method. Silver paste was applied on both sides of the
samples and fired at 500  C for 30 min for the electrical
measurements. Dielectric constant ("r ) and dielectric loss
(tan ) were measured as a function of temperature using
a computer interfaced Hioki 3532-50 LCR-Hitester. The
polarization vs electric field (P–E) hysteresis loops and
mechanical strain vs electric field (S–E) loops were
measured by using Precision Premier II, a standard ferro-
electric testing machine (Radiant Technology). The samples
for the piezoelectric property measurements were poled
by corona poling unit at room temperature by applying a
dc electric field of 5 kV/mm for 20 min. The d33 values
of the samples were measured by using a d33 meter (APC
International YE2730A). The electromechanical coupling
coefficients were measured by resonance and anti-resonance
method using Hioki 3532-50 LCR-Hitester.
3. Results and Discussion
Figure 1 shows the XRD patterns of the 0.94KNN–0.06LS
ceramics calcined at 850  C and sintered at four different
temperatures. It can be seen that the shape of the peaks are
found to vary with the increase in sintering temperature.
Single perovskite phase is retained in all the KNN–LS
ceramics sintered below 1120  C. However, at 1120  C
sintering temperature, a small amount of secondary phase is
developed. The formation of secondary phase at higher
sintering temperature may be due to the evaporation of
volatile alkali (Na,K) elements. All the prominent reflection
peaks of the sintered XRD patterns of the KNN–LS ceramics
are indexed and the lattice parameters are calculated
by X’pert Highscore Plus 2.0 software. It is found that
with the increase in sintering temperature the structure of
the ceramics changes from pure tetragonal to pseudo cubic
phase. The unit cell parameters of the sintered ceramics
are shown in Fig. 2. The c=a ratio of the ceramics is found
to decrease significantly and approaches 1 as the sintering
011503-2
P. K. Palei and P. Kumar
Fig. 2. (Color online) Unit cell parameters of the KNN–LS ceramics at
different sintering temperatures.
Table I. Unit cell volume and bulk density of KNN–LS ceramics at
different sintering temperatures.
Sintering temperature ( C)
1060 1080 1100 1120
 3)
Unit cell volume (A 62.52 62.57 62.06 61.86
Bulk density  (g/cm3 ) 4.21 4.28 4.23 3.86
temperature increases to 1120  C. This confirms the forma-
tion of pseudo cubic phase with the increase in sintering
temperature. The unit cell volume of the KNN–LS ceramics
are listed in Table I. It is found that with the increase in
sintering temperature above 1080  C, the unit cell volume
decreases. This may be due to the creation of oxygen
vacancies with the evaporation of more and more alkali
elements at higher sintering temperature.10) It is reported that
during high temperature processing (>800  C) of KNN
based ceramics cation vacancies are generated because of
the volatile nature of the alkali elements (Na/K). Therefore,
in order to maintain the charge neutrality oxygen vacancies
are also generated.12,13) These oxygen vacancies leads to
the shrinkage of the unit cell.14) Figure 3 shows the SEM
micrographs of the sintered KNN–LS ceramics. The average
grain size of the ceramics is found to increase with the
increase in sintering temperature. Maximum bulk density ()
is obtained in case of the KNN–LS ceramics sintered at
1080  C. The SEM micrographs of the KNN–LS ceramics
sintered at 1100 and 1120  C show the development of liquid
phase in the grain boundary regions which may be due to the
low melting points of alkali carbonates and Sb2 O5 (marked
in red line circles in Fig. 3).13) As can be seen in Fig. 3 the
grain boundaries are well resolved in KNN–LS ceramics
sintered at 1060 and 1080  C, whereas the grain boundaries
are not well resolved in KNN–LS ceramics sintered at
1100 and 1120  C. This is supported by XRD study, which
confirmed the development of secondary phase peaks at
1120  C sintering temperatures. The temperature depend-
ence of dielectric constant ("r ) of all the sintered KNN–LS
ceramics are shown in Fig. 4(a). It can be seen that similar to
the structure, the Curie temperature (Tc ) of the KNN–LS
# 2012 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 51 (2012) 011503 P. K. Palei and P. Kumar

Fig. 3. (Color online) SEM micrographs of the KNN–LS samples sintered at (a) 1060, (b) 1080, (c) 1100, and (d) 1120  C.

ceramics changes with the variation of sintering temperature.

Initially with increase in sintering temperature from 1060 to
1080  C the Tc of the ceramic has increased from 355 to
367  C however with further increase in sintering tempera-
ture Tc decreases. The initial increase of Tc can be explained
on the basis of increment in the value of c=a ratio. It is well
known that c=a ratio is the direct reflection of tetragonallity.
The decrease of Tc with the increase in sintering temperature
above 1080  C is may be due to the decrement in c=a ratio.17)
The increment in Tc with the increase in sintering tem-
perature from 1060 to 1080  C may also be explained in
terms of the content of the alkali elements. At higher proc-
essing temperature (800  C), both Na and K are volatile
however Na is more volatile than K. With the increase of
sintering temperature, the percentage of Na loss becomes
more than that of K. This fact makes the K content relatively (a)
higher in an individual sample, hence increases the Tc . As it
is known that the Tc of KNbO3 is 420  C, whereas the Tc of
NaNbO3 is 355  C. Hence the increase in the concentration
of K increases the Tc .18,19) The larger ionic radius of Kþ
 than that of Naþ (0.97 A)
(1.33 A)  also gives rise to the
eventually increased crystal parameters. Again, with further
increase in sintering temperature the evaporation of both
Na/K becomes more hence decrement in Tc .20) The
maximum value of "r at 1 kHz frequency for the KNN–LS
ceramics sintered at 1080  C near Curie temperature (Tc )
is found to be 5118. The maximum value of "r at Tc can
be explained as follows: in perovskite type materials,
ferroelectric to paraelectric phase transition occurs due to
the instability of temperature dependent lowest frequency
optical soft mode.21,22) At Tc , the lowest frequency soft mode
tends to zero and the lattice displacement associated with (b)
it becomes unstable. This leads to phase transition from
ferroelectric to paraelectric region with max. "r at Tc , which Fig. 4. (Color online) Temperature dependence of (a) "r and (b) tan  of
can be explained by Lyddane–Sachs–Teller (LST) relation. KNN–LS ceramics sintered at different temperatures.
The LST relation is given by
Here static dielectric constant ["ð0Þ] increases when the
!2T "ð1Þ
¼ : ð1Þ transverse optical (!T ) phonon frequency decreases. There-
!2L "ð0Þ fore, the higher values of "r near Tc is due to the con-
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Jpn. J. Appl. Phys. 51 (2012) 011503
Fig. 5. (Color online) Polarization vs electric field (P–E) hysteresis loops
of KNN–LS ceramics sintered at different temperatures.
densation of soft mode frequency (!T ! 0).23) The higher
value of "r near Tc is also supported by the Curie weiss
relation. The temperature dependence of dielectric loss
(tan ) is shown in Fig. 4(b). The behavior of tan  is very
much similar to "r . It is observed that higher value of tan  is
obtained with increasing temperature which may be due to
the increase in the mobility of ions and imperfections in
the material.24) It can also be seen that the temperatures
of peak dielectric loss and peak dielectric constant do not
coincide. Kramers–Kronig relation indicates that this can
be the consequence of temperature dependent relaxation
near Curie temperature.25) The value of tan  at Tc in case of
KNN–LS ceramics sintered at 1080  C is very low compared
to the other ceramics. The better dielectric properties ob-
tained in case of the ceramics sintered at 1080  C may be
attributed to the high bulk density ðb Þ  4:28 g/cm3 .
Figure 5 shows the polarization vs electric field (P–E)
hysteresis loops of KNN–LS samples sintered at different
temperatures. The development of well saturated hysteresis
loops for the KNN–LS samples sintered below 1120  C
confirms the ferroelectric nature of the ceramics. Maxi-
mum value of remnant polarization (Pr  17:2 C/cm2 ) and
minimum value of coercive field (Ec  13:5 kV/cm) is
obtained for the KNN–LS ceramics sintered at 1080  C. It is
found that initially with the increase in sintering temperature
from 1060 to 1080  C, there is an increment in the value
of remnant polarization (Pr ). This can be attributed to
the increase in grain size and density with the increase
in sintering temperature. The increase in Pr for the KNN–LS
sample sintered at 1080  C can be associated with the
increase in domain wall motion with the increase in grain
size which helps in switching the domains and hence affects
the polarization.26) With further increase in sintering tem-
perature the value of Pr is found to decrease, which may be
due to the decrease of bulk density. Figure 6 shows the
bipolar field-induced strains of KNN–LS ceramics sintered
at 1060, 1080, and 1100  C. The development of typical
butterfly-shaped loop indicates a ferroelectric order in all
the sintered ceramics. The remnant strain (%) is found to
increase initially with the increase in sintering temperature
up to 1080  C, however with further increase in sintering
011503-4
P. K. Palei and P. Kumar
Fig. 6. (Color online) Strain vs electric field loops of KNN–LS ceramics
sintered at 1060, 1080, and 1100  C.
Fig. 7. (Color online) Frequency dependence of impedance jZj in planar
mode of resonance of KNN–LS ceramics sintered at different temperatures.
temperature the value of remnant strain decreases in KNN–
LS ceramics. Maximum strain 0:20% and remnant strain
(0:06%) is developed in KNN–LS ceramics sintered at
1080  C. The strain developed in case of KNN–LS ceramics
is higher among the reported values in KNN based ceramics.
The higher remnant strain obtained in case of KNN–LS
ceramics sintered at 1080  C is may be due to the higher bulk
density and better microstructure observed in the ceramics.
Figure 7 shows the room temperature frequency dependence
of modulus of impedance/jZj of KNN–LS ceramics sintered
at different temperatures. The electromechanical coupling
coefficient (kp ) and longitudinal coupling coefficients (k31 )
of the samples were calculated from the resonance ( fr ) and
anti-resonance ( fa ) frequencies using the equations:
  
fa  fr 1=2
kp ¼ 2:51  ; ð2Þ
fr
 
2 1
k31 ¼  kp2 ; ð3Þ
2
where fr and fa are resonant and anti-resonant frequencies
(Hz), whereas kp and  are planar mode coupling coefficients
and Poisson’s ratio. At fr and fa frequencies, the electrical
# 2012 The Japan Society of Applied Physics
Jpn. J. Appl. Phys. 51 (2012) 011503
Fig. 8. Variations in d33 , k31 , and kp values of KNN–LS ceramics sintered
at different temperatures.
impedance modulus of Z exhibits a strong variation with a
minimum value at fr and a maximum value at fa . The planar
mode electromechanical coupling coefficient (kp ) and length
extensional coefficient (k31 ) are calculated by putting the
values of fr and fa in eqs. (2) and (3).
Figure 8 shows the variation of d33 , k31 , and kp values of
KNN–LS ceramics as a function of sintering temperature. It
is observed that values of d33 , kp , and k31 increases with the
increase in sintering temperature up to 1080  C and then
decreases with the further increase in sintering temperature.
The initial increase of d33 , kp , and kt values may be
attributed to the increase in bulk density which enhances the
poling process in KNN–LS ceramics.27,28) Maximum value
of d33 , kp , and k31 is obtained in case of KNN–LS ceramics
sintered at 1080  C. Figure 9 shows the frequency de-
pendence of the resonance spectrum at different tempera-
tures of the poled KNN–LS ceramics sintered at 1080  C.
It was found that at low temperature a typical resonance
spectrum is obtained. However, with the increase in
temperature the separation between the fr and fa decreases,
which indicates that the piezoelectric properties of the
KNN–LS ceramics decreases with increase in temperature.
The peaks of both fa and fr nearly vanishes when the tem-
perature reaches 350  C. This may be related to the
increase in the domain wall motion at higher temperature,
which randomizes the domain alignment. Hence, it is clear
that as the temperature approaches the Tc the coupling
coefficient (kp ) approaches 0.
4. Conclusions
The phase stability and electrical properties of Li/Sb-
codoped lead-free (Na,K)NbO3 ceramics with a nominal
composition of 0.94(K0:5 Na0:5 NbO3 )–0.06(LiSbO3 ) sintered
at different temperatures were studied in detail. The struc-
tural study revealed the transformation of teragonal phase
to pseudo-cubic phase of KNN–LS ceramics at 1120  C
sintering temperature. The Tc of the ceramic was found to
vary with sintering temperature. The KNN–LS ceramics
sintered at 1080  C showed better bulk density, ferroelectric
and piezoelectric properties i.e. b  4:28 g/cm3 , Pr  17:2
C/cm2 , d33  161 pC/N, kp  0:36, and k31  0:21. The
011503-5
P. K. Palei and P. Kumar
Fig. 9. (Color online) Frequency dependence of impedance jZj at
different temperatures of KNN–LS ceramics sintered at 1080  C.
results in this study indicated that the KNN–LS ceramics
sintered at 1080  C can be a suitable replacement of the
effective lead based piezoelectric ceramics.
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