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Original Paper
a r t i c l e
i n f o
Article history:
Received 4 November 2011
Received in revised form 7 September 2012
Accepted 3 January 2013
Available online 4 February 2013
Keywords:
Powders
Solid-state reaction
Calcination
Niobates
Grain size
a b s t r a c t
Nanocrystalline powders of K0.5Na0.5NbO3 (KNN) and 0.9Na0.5K0.5NbO30.1Bi0.5Na0.5TiO3 (KNNBNT)
have been prepared using a low-temperature solid-state reaction. Phase development of the powders
incurred during various calcination temperatures was examined by X-ray diffraction (XRD). Crystallite
size and particle morphology of KNN powders were examined by XRD and transmission electron microscopy, respectively. Perovskite phase was formed at the temperature as low as 500 C, and the average
crystallite size of KNN powders depended on calcination temperature. In addition, the crystalline structure of KNN powders tended to change from tetragonal symmetry to orthorhombic symmetry with
increase in crystallite size. Similar results were obtained in KNNBNT system. The developed method
is well suited for the mass production of niobate nanocrystalline powders due to its simplicity and
low cost.
2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.
1. Introduction
Alkaline niobates, such as KxNa1xNbO3 based ceramics, are
considered to be promising lead-free piezoelectric materials [1].
However, KxNa1xNbO3 based ceramics present many drawbacks,
for example, volatility of alkaline elements [2], high sensitivity of
electrical properties to stoichiometry, difculty to control the
material composition, and complex densication processes [3]. In
order to reduce the inuence of these problems, nanocrystalline
powders of alkaline niobates are needed to improve the sinterability and to prepare dense piezoelectric ceramics. Nanocrystalline
K0.5Na0.5NbO3 (KNN) based compositions have been obtained
through various soft chemistry routes, such as co-precipitation,
solgel [4], Pechini [5] and microemulsion [6]. However, most of
the chemical methods are complex and expensive.
Solid-state reaction technique is a low-cost technique and
requires a simple processing and is well suited for mass production,
which also has been extensively used to prepare KNN-based ceramic powders. However, the calcined temperature of KNN-based
ceramic powders as high as 900 C are required [13]. Therefore,
development of a low-temperature solid-state reaction method
for the production of KNN-based ceramic powders should be very
important on economizing energy and reduction cost.
Corresponding author. Tel.: +86 7735896290; fax: +86 7735896671.
E-mail address: ljliu2@163.com (L. Liu).
0921-8831/$ - see front matter 2013 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
http://dx.doi.org/10.1016/j.apt.2013.01.001
909
kk
B cos h
Fig. 2. FT-IR spectra of the KNN initial mixture and the KNN initial mixture calcined
at different temperatures.
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Fig. 4. SEM micrographs of the calcined KNN powders: (a) 500 C, (b) 800 C.
Fig. 3. (a) XRD patterns of the KNN initial mixture calcined for 2 h at different
temperatures. (b) Detail of the XRD on the region corresponding to (0 0 1) and (1 0 0)
diffraction peaks. (c) Evolution of the crystallite size as a function of the calcination
temperature.
tem was selected. Fig. 6 presents XRD patterns of the KNNBNT initial mixture calcined at different temperatures. Similar results have
been obtained from pre-milled K2CO3, Na2CO3, Nb2O5, Bi2O3 and
TiO2 mixture. A small amount of Bi2O3 (JCPDS-ICDD 51-1161) can
be found in the pattern when the mixture is calcined at 500 C.
An impurity phase KTiNbO5 (JCPDS-ICDD 71-1747) presents for
thermal treatment at 1000 C due to volatilizations of bismuth
and sodium. Insert in Fig. 7 shows the increase of the crystallite
size as a function of the thermal treatment temperature. Average
crystallite size of the KNNBNT varied in the range of 2070 nm,
which is smaller than that of KNN. Generally, the formation temperature of BNT phase is higher than that of KNN, therefore, for
the same calcination temperature, the crystallite growth of KNN
BNT is slower than that of KNN. On the other hand, KNN and
BNT have different cell parameters, the valences of A site and B site
are different, therefore, the atomic diffusion in KNNBNT solid
solution should be slower than that in pure KNN, then leads to a
smaller crystallite size. The method of the low-temperature synthesized KNN and KNNBNT is better than mechanical activation
process [16]. Therefore, the developed method presented in this
paper will ensure low-temperature, low-cost and high-purity in
niobate products, and can be extended to the synthesis of niobate-titanate solid solution.
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Fig. 6. (a) Raman spectra of KNN powders calcined at different temperatures; (b1)
Magnied Raman spectra in the wavenumber range from 420 and 740 cm1 as a
function of the composition and Lorentzian ts of the individual peaks of the Eg (m2)
and A1g (m1) Raman modes. Evolution of Raman shift (b2) and FWHM (b3) of A1g
mode in function of calcination temperature are also shown.
Fig. 7. XRD patterns of the KNNBNT initial mixture calcined for 2 h at different
temperatures. Inset shows the evolution of crystallite size as a function of
calcination temperature.
4. Conclusions
Pure K0.5Na0.5NbO3 and 0.9K0.5Na0.5NbO30.1Bi0.5Na0.5TiO3
powders with a range of particle size from 20 nm to 80 nm were
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