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Dielectric and Ferroelectric

Properties of Ag Modified Lead Free
0.94[KNN]–0.06[LS] Ceramics
a a
P. Kumar & P. Palei
a
Department of Physics, National Institute of Technology, Rourkela,
769008
Published online: 20 Nov 2010.

To cite this article: P. Kumar & P. Palei (2010): Dielectric and Ferroelectric Properties of Ag Modified
Lead Free 0.94[KNN]–0.06[LS] Ceramics, Integrated Ferroelectrics: An International Journal, 121:1,
24-30

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 Integrated Ferroelectrics, 121:24–30, 2010
Copyright © Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2010.491766

Dielectric and Ferroelectric Properties of Ag

Modified Lead Free 0.94[KNN]–0.06[LS] Ceramics

P. KUMAR∗ AND P. PALEI

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Department of Physics, National Institute of Technology, Rourkela-769008

Lead-free 0.94[(K0.5 Na0.5 )0.98 Ag0.02 NbO3 ]-0.06(LiSbO3 ) (KNAN-LS) ferroelectric ce-
ramics, (a morphotropic phase boundary (MPB) composition), was synthesized by both
conventional mixed-oxide and microwave processing techniques. The KNAN-LS system
was calcined at 850◦ for 6 h for the formation of single perovskite phase where as the
conventional and microwave sintering was done at 1080◦ C for 4 h and 1050◦ C for 1 h,
respectively. SEM characterization of the microwave sintered ceramics revealed dense
and homogeneous packing of grains. The microwave sintered KNAN-LS samples showed
better dielectric and ferroelectric properties compared to conventional sintering route.

Keywords Perovskites; Dielectric properties; Ferroelectric Properties; Microwave

Sintering

Introduction
It is well-known that Lead Zirconate Zitanate (PZT) based piezoelectric ceramics play
a dominant role in current piezoelectric and ferroelectric applications such as transduc-
ers, actuators and sensors, owing to their excellent ferroelectric properties and very good
temperature stability [1]. A noticeable feature of PZT material is the occurrence of a mor-
photropic phase boundary (MPB) [1–4]. The compositions close to the MPB show excellent
piezoelectric and ferroelectric properties [5]. However, the high toxicity of lead oxide has
caused serious environmental problems. Therefore, investigations have been extensively
carried out to develop lead-free systems with potentially good piezoelectric and ferroelec-
tric properties [6]. There had been many attempts by researchers in the past to develop
alternative lead-free materials but the properties are nowhere nearer to the PZT system.
BaTiO3 (BT) was the first lead-free ceramics applied in piezoelectric devices. The low Curie
temperature (Tc ≤ 120◦ C) and the occurrence of multiple polymorphic phase transitions
limited their applications [7]. Recently, considerable attention for lead-free piezoelectric
ceramics has been focused on K0.5 Na0.5 NbO3 (KNN) based ceramics. Potassium Sodium
Niobate (KNN) is a solid solution of potassium niobate (KN) a ferroelectric and sodium
niobate (NN) an anti-ferroelectric systems. KNN system posses a MPB similar to PZT
system when the Na/K ratio is ∼50/50,it is expected that the MPB composition of KNN
system will also exhibit good piezoelectric, ferroelectric and electromechanical properties
[8]. However, a major problem concerning KNN system is difficulty in obtaining high den-
sity by conventional mixed oxide method. Therefore, hot pressing (HP) and spark plasma

Received December 13, 2009; in final form April 3, 2010.

∗
Corresponding author. E-mail: pawankumar@nitrkl.ac.in

[1192]/24
 Lead Free 0.94[KNN]–0.06[LS] Ceramics [1193]/25

sintering (SPS) have been used to obtain KNN ceramics with high densities [9, 10]. How-
ever, such processing techniques are not always appropriate for industrial use. More recent
researchers have shown that different additives in KNN materials, like Li+, LiNbO3 (LN),
LiTaO3 (LT), LiSbO3 (LS), SrTiO3 (ST) and BT [11–16], can help to improve the sintering
behavior of KNN system. These substitutions also enhance the piezoelectric and dielectric
properties when compared to pure KNN system. Among all the modified KNN systems the
LS modified KNN system near MPB composition is reported to have desirable dielectric
and piezoelectric properties [17–19]. It is also reported that microwave sintering (MWS) is
superior to conventional sintering (CS) due to its unique characteristics, such as rapid heat-
ing, enhanced densification rate and improved microstructure [20–25]. Microwave heating
is fundamentally different from conventional heating. In the microwave process, the heat
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is generated internally within the material instead of originating from external sources,
and hence there is an inverse heating profile. The heating is very rapid as the material is
heated by energy conversion rather than by energy transfer, which occurs in conventional
techniques.
In the present work, in order to further improve the ferroelectric and dielectric properties
of KNN-LS system, 2wt% Ag has been substituted into the K/Na-site of KNN-LS system.
The sintering of the Ag modified KNN-LS system has been done by conventional and
microwave techniques. The microstructural, dielectric and ferroelectric properties of the
system sintered by both microwave and conventional technique has also been studied and
compared in details.

Experimental Procedure
Lead free KNAN-LS system was prepared by conventional solid state sintering and mi-
crowave sintering techniques. Na2 CO3 (99%), K2 CO3 (99%), Li2 CO3 (99%), Ag2 O (99%),
Sb2 O5 (99%) and Nb2 O5 (99%) were used as starting materials. Stoichiometric weights
of all the powders were mixed and ball milled with acetone for 8 h, using zirconia balls
as the grinding media. After drying the slurry in oven, the calcinations of the powder was
carried out at 850◦ C for 6 h and single perovskite phase formation was confirmed by the
X-ray diffraction (XRD) technique. The calcined powder was mixed thoroughly with 2
wt% polyvinyl alcohol (PVA) and pressed into disks of diameter ∼10 mm and a thickness
∼1.5 mm under ∼60 MPa pressure. The conventional sintering of the sample was carried
out at 1080◦ C for 4 h in air with a heating and cooling rate of 5◦ C/min and the total cycle
time was about 15h.The microwave sintering of the sample was carried out at 1050◦ C for
1 h with a heating rate of 30◦ C/min by placing the pellets in the centre of a 4.4 kW, 2.45-
GHz multi mode microwave cavity. The microwave furnace temperature was recorded by
using a Raytek non-contact sensor (XRTG5). XRD analysis of the pellets were performed
on PW 3020 Philips diffractometer using Cu Kα (λ = 0.15405 nm) radiation in order to
examine the phases present in the material. The sintered microstructures were observed
using JEOL T-330 scanning electron microscope (SEM). Silver paste was applied on both
sides of the samples for the electrical measurements. Room temperature dielectric constant
(εr ) and dielectric loss (tanδ) were measured as a function of frequency using computer
interfaced HIOKI 3532–50 LCR-HITESTER. A conventional Sawyer–Tower circuit was
used to measure the polarization hysteresis (P–E) loop at 20 Hz frequency.

Results and Discussions

Figure 1 shows the room temperature X-ray diffraction (XRD) patterns of KNAN-LS
samples calcined at 850◦ C for 6 h, microwave sintered at 1050◦ C for 1 h and conventionally
 26/[1194] P. Kumar and P. Palei

(c)

Intensity (a.u.)
(b)
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(a)

20 30 40 50 60 70 80
2θ (degrees)

Figure 1. XRD patterns of KNAN-LS samples (a) calcined at 850◦ C (b) MWS at 1050◦ C/1 h and
(c) CS at 1080◦ C/4 h.

sintered at 1080◦ C for 4 h. The XRD peaks are found to be sharp and distinct indicating good
homogeneity and crystallinity of the samples [26]. The diffraction lines for the KNAN-LS
system sintered by conventional sintering and microwave techniques are indexed in different
crystal systems and unit cell configurations using a computer program package ‘Powdmult’.
Standard deviations, S.D, d = (dobs −dcal ), where ‘d’ is inter-plane spacing, is found to
be minimum for orthorhombic (CS) and monoclinic (MWS) structures. Structures and unit
cell parameters of KNAN-LS system sintered by different techniques are given in Table 1.
Figure 2 shows the SEM micrographs of KNAN-LS system sintered by microwave
and conventional sintering techniques, respectively. The microwave sintered KNAN-LS
samples shows uniform grain size and homogeneous microstructure. The average grain
size of the KNAN-LS samples is calculated by linear intercept method and it is found to
be ∼2.5 µm and ∼1.4 µm for CS and MWS samples, respectively. The formation of finer
and uniform grains in the case of MWS sample is due to the rapidity of microwave heating
which avoids the undesirable grain growth of the sample [20–25].
Figure 3(a) and (b) shows the room temperature frequency dependence of εr and
tanδ for both conventional and microwave sintered KNAN-LS samples. εr value of both
CS and MWS samples at 1KHz frequency is found to be ∼1117 and 1257 whereas tanδ
value is ∼0.08 and 0.04, respectively. It is evident here that εr of KNAN-LS samples
sintered by microwave and conventional sintering techniques decreases with the increase in

Table 1
Structure and Lattice Parameters of KNAN-LS Ceramics

Lattice Parameter
Sintering
Technique a(A◦ ) b(A◦ ) c(A◦ ) Structure
MWS 6.5997 5.6445 9.2293 monoclinic
CS 3.94732 3.9962 7.9873 Orthorhombic
 Lead Free 0.94[KNN]–0.06[LS] Ceramics [1195]/27
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Figure 2(a) and (b). SEM micrographs of CS and MWS sample.

frequency.This decreasing behavior of εr with the increase in frequency can be explained on

the basis of dispersion of polarization with frequency. Dielectric polarization in a material is
the sum total of the different polarization mechanisms; such as electronic, ionic, dipolar and
interfacial polarization [26].The mechanisms of polarization have varying time response
dependence on the frequency of the applied field and the net contribution of polarization to
the εr is therefore frequency dependent. At lower frequency all the polarizations respond
easily to the time varying electric field but as the frequency of the field increases different
polarizations are filtered out, as a result the over all polarizations of the material decreases
which leads to the decrease in the value of  r . It is also observed from the Fig. 3 that with the
increase in frequency tanδ value of both CS and MWS samples initially decreases and then
again increases. The initial decrease of tanδ with the increase in frequency can be explained
in terms of domain wall motion and space charge polarization. Like all the polarization
mechanisms, the domain wall and space charge polarization not only contribute to the net  r
but also to tanδ. It is known that domain wall motion plays an important role in ferroelectric
materials and contributes to the overall dielectric loss. At the lower frequency region the

2200 0.20
1600 0.18
2000 0.18
Conventionally Sintered Microwave Sintered
1800 1400 0.16
0.16
1600 1200 0.14
0.14
1400 0.12
1000
0.12
tanδ
tanδ
εr

1200
εr

0.10
0.10 800
1000
0.08
800 0.08 600
0.06
600 400
0.06
400 0.04
0.04 200
2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0
log10 f (Hz) log10 f (Hz)
(a) (b)

Figure 3. (a) frequency dependence of εr and tanδ of CS sample; (b) frequency dependence of εr
and tanδ of MWS sample.
 28/[1196] P. Kumar and P. Palei

10
8
MWS
6 CS
4
Pr (µC/cm2) 2
0
-2
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-4
-6
-8
-10
-30 -20 -10 0 10 20 30
E (kV/cm)
Figure 4. PE loops of MWS and CS sample.

domain wall motion is able to follow the changing of the field and hence its contribution
to net tanδ is low [27]. The higher value of tanδ at ∼100 Hz can be attributed due to the
relaxation of the space charge polarization. This suggests that the relaxation frequency of
space charge polarization is below and near to 100 Hz.The further increase of tanδ with the
increase in frequency in case of both CS and MWS samples may be due to relaxation of the
domain wall pinned at defects in the crystal [28]. As can be seen from Fig. 1, XRD peaks
of secondary phases are also observed in KNAN-LS samples sintered by CS and MWS
techniques. These secondary phases can also contributes to the overall dielectric loss of the
KNAN-LS system [29].
Figure 4 shows the polarization versus electric field (PE) loops of both CS and MWS
samples. It is observed that coercive field (Ec ) is slightly higher for MWS sample, which
may be due to the smaller grain size restraining the domain switching. In a ceramic material,
each grain is mechanically clamped by its surroundings and this clamping effect in case of
smaller grains is maximum [30]. Hence, the Ec of microwave sintered KNAN-LS system
increases. The remnant polarizations (Pr ) of conventional and microwave sintered KNAN-
LS sample are found to be ∼4.06µC/cm2 and ∼4.33µC/cm2 whereas the coercive fields
(Ec ) are found to be ∼11.5 kV/cm and ∼11.8 kV/cm respectively.

Conclusions
KNAN-LS system with improved dielectric and ferroelectric properties were achieved by
microwave technique with lower sintering temperature and reduced soaking time. The
process was also energy efficient and cost effective. Uniform and fine grains were observed
in case of MWS samples compared to CS. The MWS samples shows higher εr , low tanδ,
high Pr and high Ec than the CS samples. The above results confirm that MWS technique
enhanced the microstructure, ferroelectric and dielectric properties of KNAN-LS system.
 Lead Free 0.94[KNN]–0.06[LS] Ceramics [1197]/29

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