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Materials Letters 146 (2015) 81–83

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Enhanced piezoelectric constant and remnant polarisation


in K-compensated sodium potassium bismuth titanate
M. Veera Gajendra Babu a, S.M. Abdul Kader a, M. Muneeswaran b, N.V. Giridharan b,
D. Pathinettam Padiyan a, B. Sundarakannan a,n
a
Department of Physics, Manonmaniam Sundaranar University, Tirunelveli 627012, India
b
Advanced Functional Materials Laboratory, Department of Physics, National Institute of Technology, Tiruchirappalli 620015, India

art ic l e i nf o a b s t r a c t

Article history: The influence of volatility of potassium on piezoelectric constant of lead-free 0.8(Na0.5Bi0.5)TiO3–0.2
Received 14 November 2014 (K0.5Bi0.5)TiO3 (NKBT20) is investigated. An excess of 0.8 mol% of K2CO3 compensates the loss of
Accepted 31 January 2015 potassium due to volatility. Piezoelectric constant (d33) of K-compensated NKBT20 is 215 pC/N, which
Available online 11 February 2015
is greater than that have been reported in literature. Splitting of (111) and (200) peaks confirms that the
Keywords: sample is of morphotrophic phase boundary composition with coexistence of rhombohedral and
Piezoelectric materials tetragonal phases. Remnant polarisation and coercive field are 56.7 mC/cm2 and 39 kV/cm respectively.
Ferroelectrics Increase in piezoelectric constant and remnant polarisation is attributed to the fine tuning of
Ceramics rhombohedral and tetragonal phase fractions by optimum compensation of loss of potassium. Present
Volatility
work provides reproducible preparation procedure to enhance piezoelectric and ferroelectric properties.
& 2015 Elsevier B.V. All rights reserved.

1. Introduction piezoelectric constant. Zhang et al. have reported much better


piezoelectric constant for Bi-compensated NBT–KBT ceramics
Electromechanical properties close to Morphotrophic Phase compared to that of uncompensated ceramics [7]. Further, opti-
Boundary (MPB) of (Na0.5Bi0.5)TiO3 (NBT)-based lead-free solid- mum excess amount for the compensation of loss of bismuth is
solutions suggest that they could be potential alternative to lead- 1 mol% [7]. The objective of present work is to find the optimum
based systems [1]. Among the NBT-based solid-solutions, (1 x) excess amount of pure K2CO3 needed for compensation of the
NBT–xKBT exhibits a MPB between rhombohedral and tetragonal volatility loss of potassium.
phases but the composition (x) of it has been reported differently
[2–12]. Piezoelectric constant is greater for compositions close to
MPB because eight domain variants of rhombohedral phase added 2. Materials and methods
to six domain variants of tetragonal phase. Therefore, fine tuning
of the phase fractions of rhombohedral and tetragonal phases is Stoichiometric amount of oxides and carbonates, Bi2O3(99.9%),
tantamount to that of piezoelectric constant. Na2CO3(99.5%), TiO2(99.8%) from Sigma-Aldrich and K2CO3(99.997%)
Among the reported piezoelectric constants [3–12], the highest from Alfa-Aesar, were mixed and hand ground using mortar and pestle.
value is 207 pC/N and the lowest value is 85 pC/N. Such a huge Two series of NKBT20 pellets were prepared with; (i) an excess amount
difference in the d33 values of NBT–KBT solid-solution could be (6–12 mol%) of K2CO3 and (ii) an excess amount (0.6–2.0 mol%) of
from the following reasons (i) mole fraction (ii) sintering condi- K2CO3. For the first series, K2CO3 was not heated before calcinations
tion, (iii) poling condition, (iv) loss of Bi2O3, K2O and Na2O at high while for the second series, K2CO3 was heated at 450 1C for 1 h.
temperature through volatilisation and (v) loss of starting materi- Powders were calcined at 850 1C for 3 h and subsequently com-
als due to incorrect weight measurement of hygroscopic reactants, pacted into pellet using a PVA binder under a pressure of 5 t. Pellets
K2CO3 and Na2CO3. Both volatility and hygroscopic nature lead to were sintered at 1150 1C for 3 h. Relative densities of the ceramics
non-stoichiometric ceramics which necessitates the formation of were above 97%. Poling field (Ep) of 33 kV/cm was applied on well-
defects for charge compensation and this prominently affects the polished pellets, without Ag electrode on both surface, at room
temperature using high voltage D.C. power supply (H5KO2N, APLAB
Ltd., India). Static dielectric permittivity (εr) and dielectric loss
n
Corresponding author. Tel.: þ 91 9487410736. (tan δ) were measured on sintered pellets at room temperature
E-mail address: sundarakannan@msuniv.ac.in (B. Sundarakannan). using a digital LCR meter (PLCR 8C, PACIFIC). Piezoelectric constants

http://dx.doi.org/10.1016/j.matlet.2015.01.152
0167-577X/& 2015 Elsevier B.V. All rights reserved.
82 M. Veera Gajendra Babu et al. / Materials Letters 146 (2015) 81–83

were measured using d33 meter (YE2730A, APC International, USA).


Thermo Gravimetric Analysis (TGA) and Differential Scanning
Calorimetry (DSC) measurements were performed using a simulta-
neous thermal analyser (STA 449F3, Netzsch, Germany) with a
heating rate of 10 1C/min in alumina crucible and static air. Powder
X-ray diffractions were recorded using Cu-Kα radiation in a dif-
fractometer (PANalytical Xpert PRO, Netherland). Bragg profiles of
Cu-Kα2 were stripped by Highscore Plus software of Panalytical.
Ferroelectric hysteresis loop was measured using a P–E loop tracer
(Radiant Technologies, USA).

3. Results and discussion

The variation of piezoelectric constant of NKBT20 with the


excess amount of K2CO3 is shown in Fig. 1(a) and (b). Piezoelectric
constant gradually increases to 178 pC/N up to 10 mol% (Fig. 1(a))
and decreases thereafter. This suggest that 10 mol% of excess K2CO3 Fig. 2. TGA and DSC thermograms of potassium carbonate.
compensates the combined loss incurred primarily due to hygro-
scopic nature and volatility. To delineate the loss due to hygroscopic
nature from that of volatility, TGA and DSC thermograms are shown (Fig. 1(b)) was obtained for the sample compensated with 0.8 mol%.
in Fig. 2. An endotherm at 118 1C with a concurrent weight loss Piezoelectric constant of the same sample further improved to 215 pC/
of 6.7% corresponds to removal of moisture. Another narrow N when it was poled with Ag conductive paint on the surfaces. Since
endotherm at 907 1C corresponds to melting and the following piezoelectric constant is the greatest for 0.8 mol% of K2CO3 (Fig. 1(b))
weight loss of 2.7% is decomposition of potassium carbonate. added sample, it is concluded as the optimum amount required for
Further, Lehman et al. have reported a significant volatilisation of compensation of potassium loss. And, this sample is referred to as
potassium carbonate below melting through decomposition model K-compensated NKBT20. Piezoelectric constant reduced to 185 pC/N
and γ to β transition at 421 1C [13]. Therefore, potassium carbonate (not shown) for K-compensated sample when K2CO3 was heated at
was heated at 450 1C for 1 h in the present work. Thus, loss of the 200 1C for 1 h instead of 450 1C.
starting material due to hygroscopic nature of K2CO3 is prevented. X-ray diffraction pattern of K-compensated NKBT20, shown
Now, to find optimum excess amount for compensation of loss due in Fig. 3(a), is indexed to pseudocubic indices and absence of
to volatility, 0.6–2 mol% of K2CO3 was added to the stoichiometric un-indexed reflections suggests phase purity. Enlarged view of both
starting material. A maximum piezoelectric constant of 196 pC/N (111) and (200) peak profiles are presented in Fig. 3(a) as subplots.
Both the peaks split into three peaks and each peak is identified using
the ICDD data of end members, namely rhombohedral-NBT (36-0340)
and tetragonal-KBT (36-0339). Hexagonal indices (36-0340) are
converted to rhombohedral indices using the formula; (hkl)H ¼(1/3)
(2hþkþ l hþkþl h 2kþl)R [14]. NBT has two peaks at 39.8891
and 40.261 with intensities of 9% and 35%, respectively, while KBT has
single peak at 39.5241 with intensity of 26% in the 2θ range from 39.31
to 40.31. All the three peaks are marked as vertical lines in bottom of
the subplot corresponding to (111) peak. Two rhombohedral (R) peaks
of K-compensated NKBT20 shifted to lower side of 2θ compared to
that of NBT indicating increase in cell volume due to larger ionic
radius K þ (1.64 Å) substitution in place of Na þ (1.39 Å). On the other
hand, single tetragonal (T) peak shifted to higher side of 2θ compared
to that of KBT indicating decrease in cell volume due to lower ionic
radius Na þ substitution in place of K þ . Similarly, three peaks in the
subplot corresponding to (200) peak are identified and peak shifts can
be explained. Therefore, splitting of (111) and (200) peaks emphati-
cally ascertains that K-compensated NKBT20 is MPB composition with
a coexistence of rhombohedral and tetragonal phases. Further,
rhombohedral cell volume increased while tetragonal cell volume
decreased.
P–E hysteresis loop for all the samples of Fig. 1(b) are shown
in Fig. 3(b). Ferroelectric nature of the sample is illustrated by well-
saturated loop. Remnant polarisation and coercive field are improved
by the addition of excess K2CO3 up to 0.8 mol% and the values are
listed in Table 1. Remnant polarisation and coercive field for 0.8 mol%
are 56.7 mC/cm2 and 39 kV/cm respectively. Ferroelectric properties
of K-compensated NKBT20 are relatively improved than the reported
values of NBT–KBT ceramics [4,10]. Table 1 summarises the experi-
mental densities as well as electrical properties of K-compensated
NKBT20 ceramics. Variations in the dielectric permittivity, remnant
Fig. 1. Piezoelectric constant of NKBT20 ceramics as a function of excess K2CO3
polarisation and piezoelectric coefficient show a similar trend with
(a) without heat treatment (b) with a heat treatment of K2CO3 at 450 1C for 1 h.
respect to excess K2CO3.
M. Veera Gajendra Babu et al. / Materials Letters 146 (2015) 81–83 83

nature and volatility of K2CO3 also influence piezoelectric and


ferroelectric properties prominently. To remove hygroscopic nat-
ure, heating of K2CO3 at 450 1C for 1 h is required. To compensate
volatility an excess amount of 0.8 mol% needs to be added prior to
calcination. Such a preparation procedure gives enhanced piezo-
electric constant reproducibly. Improvement of piezoelectric con-
stant and remnant polarisation is attributed to fine changes of
phase fractions of rhombohedral and tetragonal phases through
variation of excess amount of K2CO3. Variation of piezoelectric
constant with the phase fractions of rhombohedral and tetragonal
phases close to MPB has been reported for NBT-BT solid-solutions
[15]. Further work is required for a quantitative correlation of
phase fraction with piezoelectric constant.

4. Conclusions

An excess addition of 0.8 mol% of K2CO3 compensates the


volatilisation loss of potassium. Heating the potassium carbonate at
450 1C for 1 h removes moisture. Adoption of such a preparation
procedure gives enhanced piezoelectric constant and remnant polar-
isation reproducibly. The present work unlocks the difficulty, incon-
sistency in the reported d33 values, in working with potassium-based
piezoelectric ceramics. Optimal excess amount required to compen-
sate the Bi-volatilisation has been reported [7] while the present
work reports the optimal excess amount required to compensate
the K-volatilisation. Sodium is more volatile at high temperature
and therefore compensation of it needs to be investigated. The MPB
composition needs to be freshly identified on Bi, K and Na compen-
sated NBT–KBT solid-solution whose piezoelectric constant is
expected to increase further from the highest value of 215 pC/N
obtained in this work.

Acknowledgement
Fig. 3. (a) Powder XRD pattern of K-compensated NKBT20. Subplots are expanded
view of (111) and (200) peaks. Vertical lines are ICDD of NBT and KBT respectively. The research investigation was carried out with the financial
(b) Polarisation–electric field hysteresis loop of K-compensated NKBT20. support of a Major Research Project (F. No. 39-476/2010 (SR)) of
University Grants Commission, New Delhi.

Table 1
Density and electrical properties of K-compensated NKBT20 ceramics. References

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