J Mater Sci: Mater Electron (2013) 24:411–417
DOI 10.1007/s10854-012-0765-y
Effect of La on piezoelectric properties
of Pb(Ni1/3Sb2/3)O3–Pb(ZrTi)O3 ferroelectric ceramics
C. M. Lonkar • D. K. Kharat • H. H. Kumar •
Sahab Prasad • K. Balasubramanian
Received: 14 February 2012 / Accepted: 16 May 2012 / Published online: 31 May 2012
Ó Springer Science+Business Media, LLC 2012
Abstract Piezoceramic compositions Pb1-zLaz(NiSb)0.05
[(Zr0.52Ti0.48)1-Z/4]0.95O3 with Z = 0.01–0.05 were syn-
thesized by mixed oxide route to study the effect of
Lanthanum (La) on crystal structure, microstructure, pie-
zoelectric and ferroelectric properties. Calcination was
performed at 1,060 °C and sintering at 1,270 °C for 1 h.
X-Ray diffraction pattern indicated the polycrystalline
microstructure along with co-existence of tetragonal and
rhombohedral perovskite phases. Dielectric constant (K3T )
was increased whereas piezoelectric voltage constant (g33)
was decreased with increase in lanthanum. Dense micro-
structure was observed for the composition containing
3 mol% of lanthanum. This was resulted in optimum
piezoelectric charge constant (d33 = 468 9 10-12 C/N),
electromechanical coupling factor (kp = 0.68), remanent
polarization (Pr = 24.65 lC/cm2) and displacement (D =
2,012 nm). Results indicated that the composition Pb0.97
La0.03(NiSb)0.05[(Zr0.52Ti0.48)0.9925]0.95O3 could be suitable
for actuator applications. The composition Pb0.98La0.02
(NiSb)0.05[(Zr0.52Ti0.48)0.995]0.95O3 resulted into moder-
ately high value of voltage constant (g33 = 39.3 9
10-12 V m/N) and optimum value of Figure of Merit
(d33 9 g33 = 16.2 9 10-12 C V m/N2) indicated the use-
fulness for sensor and power harvesting applications.
C. M. Lonkar (&)  D. K. Kharat  H. H. Kumar
PZT Centre, Armament R&D Establishment, Pune, India
e-mail: cmlonkar@gmail.com
S. Prasad  K. Balasubramanian
Defence Institute of Advanced Technology, Pune, India
1 Introduction
Lead Zirconate Titanate (PZT) based piezoceramic com-
positions are of great technological interest, particularly;
when Zr/Ti ratio is about 52/48 which corresponds to the
composition of the ferroelectric Morphotropic Phase
Boundary (MPB) separating the ferroelectric tetragonal
(FT) and ferroelectric rhombohedral (FR) phases [1, 2].
However, properties of interest can be tailored by adding
the suitable dopant. A material with higher piezoelectric
charge constant (d33) and dielectric constant (K3T ) is suit-
able for actuator application where as the material with
higher piezoelectric voltage constant (g33) is suitable for
sensor application [3]. Materials with higher g33 provides
higher voltage output [4–6] and higher product d33 9 g33
(Figure of Merit—FoM) offers higher energy output hence
is the essential criteria for the material intended to be used
for energy harvesting applications [7, 8].
When La3? (r = 1.22 Å) is substituted in PZT compo-
sition, it replaces Pb2? (r = 1.32 Å) [9] ions in the lattice
according to the relation Pb2? $ La3? ? e-. To maintain
the electrical neutrality, Pb vacancies are created in the
lattice making domain wall motion comparatively easier.
This in turn results in the enhanced dielectric constant
(K3T ), remnant polarization (Pr) and coupling factor (kp) of
the material [10–12]. Moreover, substitution of lanthanum
the increase the sinterability, retards grain growth and
decrease the grain size [13, 14].
[PbNiSb]x–[Pb(Zr1-yTiy)]1-xO3 is a ternary solid solu-
tion abbreviated as PNS-PZ-PT. It has been studied by some
of the researchers around the MPB of PNS-PZ-PT. Yu et al.
investigated the effect of MnO2 (0.0–0.2 wt%) in 0.12PNS–
0.40PZ-0.48PT system on properties viz’ dielectric constant
(K3T ), electromechanical coupling factor (kp), mechanical
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quality factor (Qm) and dielectric loss factor (tan d) [15]. were carried out using ‘‘TF analyzer-2000’’ Make Aixact.
Zahi et al. investigated the properties K3T , kp and curie The following standard empirical relations were used to
temperature (Tc) for the components sintered at 1,180 °C calculate K3T , g33, kp and Qm [17–19].
for 2 h [16]. Wang et al. studied density, kp and Qm [17]. Ct
The objective of the present work was to study the effect K3T ¼ ð1Þ
e0 A
of La on structural, piezoelectric, dielectric and ferro-
electric properties of compositions Pb1-zLaz(NiSb)0.05 d33
g33 ¼ ð2Þ
[(Zr0.52Ti0.48)1-Z/4]0.95O3 with Z = 0.01–0.05 and its K3T e0
optimization for sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
fa  fr
kp ¼ 2:51 ð3Þ
(a) values of piezoelectric charge constant (d33), piezo- fr
electric voltage constant (g33), product of piezoelec-  2 
tric charge constant and voltage constant (d33 9 g33) 1 fa
Qm ¼ ð4Þ
i.e. Figure of Merit so that it could be suitable for 2pfr Zm C fa  fr2 2

power harvesting and sensor applications.

where K3T is the dielectric constant, C is the capacitance
(b) values of piezoelectric charge constant (d33), rema-
(F), eo is the permittivity of free space (8.854 9 10-12
nent polarization (Pr) and displacement (D) so that it
F/m), t is the thickness of the specimen (m), A is the area of
could be suitable for actuator applications.
specimen (m2), g33 is the piezoelectric voltage constant
(V m/N), d33 is piezoelectric charge constant (C/N) Zm is
impedance, fr is resonance frequency (kHz) and fa is the
2 Experimental anti-resonance frequency (kHz).
Microstructural analysis of chemically etched polished
The compositions Pb1-zLaz(NiSb)0.05[(Zr0.52Ti0.48)1-Z/4]0.95O3 samples was carried out using Scanning Electron Micro-
(hereafter abbreviated as PNS-PZT) with Z = 0.01–0.05 scope Make-FEI Netherlands (Model-Quanta 200 ESEM).
were synthesized using the oxides of elements in the powder
form. The raw materials used were PbO (Waldies Ltd.,
Kolkata, 99.5 %), ZrO2 (Loba Chemie, 99.37 %), TiO2 3 Results and discussions
(Travancore Titanium Products, 98.5 %), NiO (Acros,
97 %), Sb2O5 (Loba Chemie, 99 %) and La2O3 (Indian Rare X-Ray diffraction patterns of calcined powder are shown
Earths Ltd., 99.99 %). To minimize the pyrochlore phase, in Fig. 1 for the compositions Pb1-zLaz(NiSb)0.05[(Zr0.52
precursor Nickel Antimonite (NiSb2O6) was obtained in first Ti0.48)1-Z/4]0.95O3 with Z = 0.01–0.05. XRD patterns
stage. PNS-PZT compositions were prepared and processed show the polycrystalline nature. Formation of PZT perov-
through mixed oxide route. To compensate the lead loss skite phase for all compositions is indicated by intense
during calcination, 0.5 mol% excess quantity of PbO was peaks indexed [17, 20] and particularly by highest peak
taken. Powders were wet milled for 24 h in pure water intensity at (110) plane [21]. Co-existence of ferroelectric
medium (Millipore, Elix-10) and zirconia balls were used as tetragonal (FT) and ferroelectric rhombohedral (FR) phases
grinding media. Solid state reaction was carried out at
1,060 °C and further powder was ultra-fine ground to
1.0–1.2 lm. The compositional effect on crystal structure
was studied from X-ray diffraction (XRD) patterns recorded
for position 2h from 20° to 70° using Philips X’pert Pro. The
powders were pressed by semi-automatic die punch machine
to form discs of Ø17.2 9 1.7 mm thickness. The specimens
were sintered at 1,270 °C for 1 h. Sintered specimens were
lapped and subsequently electroded with silver paste. Poling
was performed by applying DC field of 35 kV/cm at 100 °C
for 30 min. Specimens were aged for 10 days and charac-
terized for piezoelectric and dielectric properties. Capaci-
tance(C), tan d, impedance (Zm), resonance frequency (fr)
and anti-resonance frequency (fa) using variable frequency
LCR meter (Hioki Hi Tester model 3532 and 3522). Piezo-
electric charge constant (d33) was measured using d33 Ber-
lincourt meter (CPDT 3330). Hysteretic ferroelectric studies Fig. 1 X-Ray diffraction pattern for La doped PNS-PZT

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J Mater Sci: Mater Electron (2013) 24:411–417 413

Fig. 2 SEM photographs a La = 1 mol%, b La = 2 mol%, c La = 3 mol%, d La = 4 mol%, e La = 5 mol%

was indicated by the splitting in the peak intensity at triplet Figure 2a–e represents the effect of La substitution on
(002), (102), and (112) [17, 19–23]. However, peaks of microstructure of PNS-PZT. For 1 mol% La substitution
excess PbO were also seen [20]. (Fig. 2a), the grain size is distributed widely up to 12 lm.

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The grain size was measured by linear intercept method. polarisability of the material due to increase in domain wall
The average grain size was about 7.05 lm. Much of the movement. On further increasing it, kp was decreased to
grains were polygonal in shape and few ovals. Some pores 0.57 at 5 mol% of La. Since, kp alone can indicate the
were also seen. For 2 mol% La substitution (Fig. 2b) the strength of poling, it can be concluded that the composition
grain size and porosity was seen to be reduced; size dis- Pb1-zLaz(NiSb)0.05[(Zr0.52Ti0.48)1-Z/4]0.95O3 has maxi-
tribution was also narrowed down in comparison with mum polarisability when La substitution is 3 mol% at
earlier one. The average grain size was about 6.45 lm. In which comparatively dense and uniform microstructure
case of 3 mol% La substitution, the grains were reduced in was obtained. Maximum polarisability has resulted into
size (Fig. 2c). Grain size distribution was still narrowed minimum Qm and maximum kp.
down and dense microstructure was seen. Most of the Figure 4 shows the effect of La substitution on piezo-
grains were polygonal in shape with straight sides. Porosity electric charge constant (d33) and dielectric constant (K3T ).
at triple grain point was reduced. The average grain size d33 is the charge generating ability of the ceramic in direct
measured was about 5.35 lm. It is known that electrome- piezoelectric effect while it indicates the strain or dis-
chanical properties are greatly influenced by the grain size placement ability in converse piezoelectric effect. With the
[24]. Similarly, dense microstructure with optimum grain increase in the La from 1 to 3 mol%, d33 was increased.
size results in better piezoelectric properties [25]. On fur- For 3 mol% of La, optimum value of d33 (468 9 10-12
ther increasing the La substitution to 4 and 5 mol%, grains C/N) was obtained. This was attributed to the reduction in
were reduced dramatically in size to 1.2 lm (Fig. 2d) and the porosity and maximum polarisability for the composi-
1 lm (Fig. 2e) respectively where in fine microstructure tion containing 3 mol% La. The reductions in porosity
with increased porosity was seen. Over all, it was observed increase the polarization per unit volume [17] resulted into
that the grain growth was retarded as the La concentration
was increased. For 2 and 3 mol% addition of La, dense and
uniform microstructure with minimum porosity was seen.
Figure 3 shows the effect of La substitution on
mechanical quality factor (Qm) and electro-mechanical
coupling factor (kp). Qm is the power handling capacity
while kp is the energy conversion efficiency of the ceramic.
From the figure it is evident that as the La content was
increased from 1 to 3 mol%, Qm reduced from 272 to 75.
Reduction in Qm indicates the increase in domain wall
mobility due to creation of Pb vacancies in the lattice.
Further, dramatically decrease in grain size was seen.
Slight increase in Qm to 89 for 5 mol% of La due to
reduction in domain wall motion. On the other hand kp was
increased from 0.60 to 0.68 as the La substitution was
increased from 1 to 3 mol% indicating the increasing Fig. 4 Effect of La on d33 and K3T

Fig. 3 Effect of La on Qm and kp Fig. 5 Effect of La on g33 and FoM

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a b

c d

Fig. 6 Hysteretic response a La = 1 mol%, b La = 2%, c La = 3 mol%, d La = 4 mol%, e La = 5 mol%

increase in the d33. On further increasing the La, d33 was
slightly decreased attributed to the increase in porosity and
reduced polarisability. It is seen that on increasing the La
substitutions, the dielectric constant (K3T ) was increased to
2,571 for 5 mol% of La. This may be due to the redistri-
bution of electrons in the defective areas occurring on
substitution of La for Pb atom in PZT, which promotes the
covalent bonding in Ti–O and in Zr–O. Increase in cova-
lent nature has improved the K3T [26]. This could also be
the reason for drastic reduction in grain size for the com-
position containing 4 and 5 mol% of La.
Figure 5 shows the effect of La substitution on piezo-
electric voltage constant (g33) and on product d33 9 g33 i.e.
Figure of Merit (FoM). As indicated by Eq. 2, g33 is
directly proportional to d33 and inversely proportional
toK3T . With increase in La content to 2 mol%, g33 slightly
decreased from 41.5 to 39.3(9 10-12 V m/N). Further it
reduced substantially to 26.4(9 10-12 V m/N) at 3 mol%
and to 19.4(9 10-12 V m/N) at 5 mol% of La. In general,
it was observed that increase in La content has reduced the
sensitivity and voltage generation ability of the composi-
tion. Though the value of g33 was slightly higher for the

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Table 1 Hysteretic properties of PNS-PZT as function of La content
La content Remanent Coercieve Displacement/
(mol%) polarisation, field, Ec strain,
Pr (lC/cm2) (V/mm) D (nm)
1 19.01 1,040 837
2 24.03 976 1,681
3 24.65 956 2,012
4 21.33 969 1,307
5 20.07 1,017 1,217
composition containing 1 mol% of La, d33 was minimum. This
led to the lesser value of FoM (10.8 9 10-12 C V m/N2).
With the increase in the La content to 2 mol%, FoM was
increased to 16.2 9 10-12 C V m/N2 which was its opti-
mum value. Such composition could be useful for the
sensor and power harvesting applications. Further increase
in La content FoM was reduced linearly as shown in Fig. 5.
Figure 6a–e shows the effect of La doping on polari-
zation and displacement or strain, on the application of
electric field. The values for the coercive field, remanent
polarization, and displacement obtained are shown in
Table 1. Defect produced due to La substitution at ‘A’ site,
minimizes the local stresses, and makes the domains
remarkably mobile under the electric field [27]. Such
materials show highly symmetric P-E hysteresis loops with
low coercivity, higher polarisability, and good squareness
[1, 28, 29]. As La content was increased from 1 to 3 mol%,
remnant polarization (Pr), and strain i.e. displacement
(D) were improved. This was attributed to a better align-
ment of domains and enhanced domain wall motion [10,
30]. Upon further increasing the La, these properties were
reduced attributing to the decrease in domain wall motions.
This fact was well supported by the similar trends followed
by Qm, kp and d33.
4 Conclusions
Piezoceramic composition Pb1-zLaz(NiSb)0.05[(Zr0.52-
Ti0.48)1-Z/4]0.95O3 where Z = 0.01–0.05 has been studied.
Compositions have shown polycrystalline nature and the
co-existence of FT and FR phases indicated by XRD pat-
terns. Increase in La from 1 to 5 mol%, increased the K3T
may be attributed to the increase in Ti–O and Zr–O
covalent bonding nature encouraged by La. PNS-PZT
composition containing 2 mol% of La resulted into mod-
erately higher value of g33 (39.3 9 10-12 V m/N) and
optimum value of FoM (16.2 9 10-12 C V m/N2). Such
composition could be useful for sensor and power har-
vesting applications. Presence of 3 mol% of La in PNS-
PZT leads to dense and uniform microstructure which was
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J Mater Sci: Mater Electron (2013) 24:411–417
resulted in optimum d33 (468 9 10-12 C/N), kp (0.68), Pr
(24.65 lC/cm2) and strain/displacement (D = 2,012 nm).
This indicates that, this composition could be suitable for
actuator applications.
Acknowledgments Authors would like thank to Director, Arma-
ment Research and Development Establishment (ARDE), Pune for
encouragement and permission to publish this paper. Thanks are also
due to Director, Naval Materials Research Laboratory, Mumbai for
XRD facility and Director, High Energy Materials Research Labo-
ratory, Pune for extending the SEM facility.
References
1. G.H. Haertling, Ferroelectric ceramics: history and technology.
J. Am. Ceram. Soc. 82, 797–818 (1999)
2. B. Jaffe, W.R. Cook Jr, H. Jaffe, Piezoelectric Ceramic (Aca-
demic, New York, 1971), pp. 135–140
3. J.F. Tressler, A. Sedat, R. Newnham, Piezoelectric sensors and
sensor materials. J. Electroceram. 2(4), 257–272 (1998)
4. F. Mohammadi, A. Khan, R.B. Cass, Power generation from
piezoelectric lead zirconate titanate fiber composites. Proc.
Mater. Res. Soc. Symp. 736, D5.5.1–D5.5.6 (2003)
5. C. Green, K.M. Mossi, R.G. Bryant, in Scavenging Energy from
Piezoelectric Materials for Wireless Sensor Applications. Pro-
ceedings of ASME International Mechanical Engineering Con-
gress and R&D Expo (2005)
6. A. Mathers, K.S. Moon, Y.A. Jingang, Vibration-based PMN-PT
energy harvester. IEEE Sens. J. 9, 731–739 (2009)
7. H.W. Kim, S. Priya, K. Unchino, R. Newnham, Piezoelectric
energy harvesting under high pre-stressed cyclic vibrations.
J. Electroceramics. 15, 27–34 (2005)
8. A.J. Moulson, J.M. Herbert, Electroceramics, 2nd edn. (England,
Wiley, 2003), p. 384
9. V. Raghvan, Materials Science and Engineering, 3rd edn (Pre-
ntice Hall of India Pvt Ltd., New Delhi, 1995), pp. 401–402
10. A.Govindan, A. Sharma, A.K. Pandey, S.K. Gaur, Piezoelectric
and pyroelectric properties of lead lanthanum zirconate titanate
(PLZT) ceramics prepared by sol gel derived nano powders.
Indian J. Phys. 85, 1829–1832 (2011)
11. A.R. James, J. Subramanyam, Processing and structure property
relation of fine-grained PLZT ceramics derived from mechano-
chemical synthesis. J. Mater. Sci. Mater. Electron. 17, 529–535
(2006)
12. R. Laishram, O.P. Thakur, D.K. Bhattacharya, Harsh, Dielectric
and piezoelectric properties of La doped lead zinc niobate–lead
zirconium titanate ceramics prepared from mechano-chemically
activated powders. Mater. Sci. Eng. B 172, 172–176 (2010)
13. T. Li, H. Li, Y. Xu, Dielectric behavior and Raman spectra of
lanthanum-doped lead magnesium niobate ceramics. J. Mater.
Sci: Mater. Electron. 22, 1188–1194 (2011)
14. M.D. Durruthy-Rodrı́guez, F. Calderón-Piñar, C. Malfatti, L.D.
Pérez-Fernández, Sintering kinetics of soft-doped PZT (54/46)
systems. J. Mod. Phys. 2, 416–420 (2011)
15. S. Zahi, R. Bouaziz, N. Abdessalem, A dielectric and piezo-
electric properties of PbZrO3–PbTiO3–Pb(Ni1/3,Sb2/3)O3 ferro-
electric ceramic system. Ceram. Int. 29, 35–39 (2003)
16. C. Sheng Yu, H.L. Hsieh, Piezoelectric properties of Pb(Ni1/3,
Sb2/3)O3–PbTiO3–PbZrO3 ceramics modified with MnO2 addi-
tive. J. Eur. Ceram. Soc. 25, 2425–2427 (2005)
17. M.C. Wang, Sintering and piezoelectric properties of Pb(Ni1/3
Sb2/3)O3-PbZrO3-PbTiO3 ceramics. J. Mater. Sci. 37, 663–668
(2002)
J Mater Sci: Mater Electron (2013) 24:411–417
18. T.L. Jordan, Z. Ounaies, Piezoelectric Ceramics Characterization,
ICASE Report No. 2001-28, NASA/CR-2001–211225 (2001)
19. V. Singh, H.H. Kumar, D.K. Kharat, S. Hait, M.P. Kulkarni,
Effect of lanthanum substitution on ferroelectric properties of
niobium doped PZT ceramics. Mater. Lett. 60, 2964–2968 (2006)
20. R. Tipakontitikul, S. Anantha, A modified two-stage mixed oxide
synthetic route to lead zirconate titanate powders. Mater. Lett. 58,
449–454 (2004)
21. B. Praveenkumar, H.H. Kumar, D.K. Kharat, B.S. Murty,
Investigation and characterization of La-doped PZT nanocrys-
talline ceramic prepared by mechanical activation route. Mater.
Chem. Phys. 112, 31–34 (2008)
22. R.S.Nasar, M.Cerqueira, E.Longo, J.A.Varela, A.Beltran, Exper-
imental and theoretical study of the ferroelectric and piezoelectric
behavior of strontium doped PZT. J. Eur. Ceram. Soc. 22,
209–218 (2002)
23. A. Boutarfafia, Investigations of co-existance region in lead zir-
conate titanate solid solutions: X-ray diffraction studies. Ceram.
Int. 26, 583–587 (2000)
24. H. Kungl, J.H. Michael, Effects of sintering temperature on
microstructure and high field strain of niobium-strontium doped
417
morphotropic lead zirconate titanate. J. Appl. Phys. 107, 054111
(2010)
25. M. Chen, X. Yao, L. Zhang, Grain size dependence of dielectric
and field–indiced strain properties of chemical prepared
(Pb,La)(Zr,Sn,Ti)O3 antiferroelectric ceramics. Ceram. Int. 28,
201–207 (2002)
26. A. Stashans, F. Maldonado, A quantum mechanical study of
La-doped Pb(Zr,Ti)O3. Phys. B. 392, 237–241 (2007)
27. M.H. Lentea, J.A. Eiras, 90° domain reorientation and domain
wall rearrangement in lead zirconate titanate ceramics charac-
terized by transient current and hysteresis loop measurements.
J. Appl. Phys. 89, 5093–5099 (2001)
28. L.E. Cross, Ferroelectric Ceramics: Tailoring Properties For
Specific Applications (Birkhauser Verlag, Basel, 1991), pp. 65–66
29. X. Zeng, X. Hea, W. Chenga, X. Zhenga, P. Qiu, Dielectric and
ferroelectric properties of PZN–PZT ceramics with lanthanum
doping. J. Alloys. Compd. 485, 843–847 (2009)
30. D. Damjanovic, in The Science of Hysteresis, vol. 3, ed. by
Mayergoyz, G. Bertotti (Elsevier, 2005), pp. 353–355
123