Journal of Materiomics 5 (2019) 372e384

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Journal of Materiomics
journal homepage: www.journals.elsevier.com/journal-of-materiomics/

Oxygen octahedron tilting, electrical properties and mechanical

behaviors in alkali niobate-based lead-free piezoelectric ceramics
Zhi Tan a, 1, Shaoxiong Xie b, 1, Laiming Jiang a, Jie Xing a, Yu Chen a, c, Jianguo Zhu a, *,
Dingquan Xiao a, Qingyuan Wang b, c, **
a
College of Materials Science and Engineering, Sichuan University, Chengdu, 610064, China
b
Key Laboratory of Deep Underground Science and Engineering (Ministry of Education), School of Architecture and Environment, Sichuan University,
Chengdu, 610065, China
c
School of Mechanical Engineering, Chengdu University, Chengdu, 610106, China

a r t i c l e i n f o a b s t r a c t

Article history: In this work, we present a new piezoelectric solid solution consisting of two typical alkali niobate-based
Received 20 August 2018 materials, K0.5Na0.5NbO3 (KNN) and Li0.15Na0.85NbO3 (LNN). Although KNN and LNN have the same
Received in revised form perovskite structure, they exhibit extremely different electrical properties and mechanical behaviors. The
25 January 2019
phase structures, electrical and mechanical evolutions of the new lead-free piezoelectric materials with
Accepted 8 February 2019
different ratios of KNN and LNN are comprehensively and theoretically investigated. According to the X-
Available online 14 February 2019
ray diffraction patterns and curves of permittivity versus temperature, a series of complicated phase
transitions can be found with varied LNN content. Rietveld refinement results based on XRD patterns
Keywords:
Lead-free
reveal an oxygen octahedron tilting in the LNN-rich crystal structure, and simultaneously the reasons for
Piezoelectric ceramics octahedron tilting are discussed. The distorted crystal structure is accompanied by extremely decreased
Crystal structure electric properties but increased mechanical properties, which reveals electrical and mechanical prop-
Electrical properties erties of alkali niobate-based piezoelectric ceramics strongly depend on their inner structures, and the
Mechanical behaviors enhancement of intrinsic hardness results in the deterioration of piezoelectric properties. Our work
exhibits the detailed evolutions of structure, electrical and mechanical properties from KNN to LNN,
which provides experimental and theoretical basis for development of new alkali niobate-based
piezoelectric materials.
© 2019 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction develop environmentally friendly lead-free piezoceramics [2e6]. In

Piezoelectric materials have been widely used in various de-
vices, such as acoustics sensors, transducers, actuators, etc [1e4].
Presently, lead-based piezoceramics and their solutions, repre-
sented by lead zirconate titanate [Pb(Ti, Zr)O3, PZT], dominate the
commercial application market due to their excellent piezoelectric
properties [2e4]. However, with the increasing demands for envi-
ronment and human health, there is an intensified requirement to
* Corresponding author.
** Corresponding author. Key Laboratory of Deep Underground Science and En-
gineering (Ministry of Education), School of Architecture and Environment, Sichuan
University, Chengdu, 610065, China.
E-mail addresses: nic0400@scu.edu.cn (J. Zhu), wangqy@scu.edu.cn (Q. Wang).
Peer review under responsibility of The Chinese Ceramic Society.
1
These authors contributed equally to this work and should be considered co-
first authors.
this case, alkali niobate-based lead-free piezoelectric materials
have been extensively identified as one of the potential sub-
stitutions for lead-based ones because of their comparable piezo-
electricity and higher Curie temperature (TC) [6].
Although alkali niobate-based piezoceramics have been devel-
oped for a long time, further development still need to be carried
out. One of the most concerning subjects on alkali niobate-based
piezoceramics is the relationship between macroscopic perfor-
mance and microstructure. The piezoelectric properties are mostly
determined by the structural characteristics of piezoelectric ma-
terials [4e7]. Taking the lead-based piezoceramics as an example,
their piezoelectric properties can be greatly improved through
construction of morphotropic phase boundary (MPB) for more
possible polarization directions at phase boundaries [7,8], and high
consistent orientation of polarization directions could be achieved
under the external DC electric field [7,8]. Analogously,
K0.5Na0.5NbO3-based (KNN) ceramics, as the most widely studied

https://doi.org/10.1016/j.jmat.2019.02.001
2352-8478/© 2019 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
alkali niobate-based piezoelectric materials, can form the ferro-
ferroelectric phase boundaries at room temperature via ion
doping and component substitution [4,6,9e14]. Specifically, a very
high piezoelectric constant of d33 ~ 570pC/N was reported in
modified KNN-based ceramics [15], which is several times larger
than that of pure KNN ceramics (d33 ~ 80 pC/N). Meanwhile,
Li0.12Na0.88NbO3-based (LNN) ceramics, as one of the alkali niobate-
based piezoelectric materials, possess low piezoelectric constants
but relative high mechanical quality factor (Qm) as well as better
mechanical properties [16e18]. Qiang Chen et al. reported a kind of
Sb-modified LNN ceramics with d33 of 45 pC/N and high Qm of 1560,
which is very suitable for frequency resonator [16]. Although these
two kinds of piezoelectric materials have similar chemical
component, their perovskite structures are crystallized in different
inner space symmetries with different states of oxygen octahedral
tilting or rotation. When KNN and LNN are mixed together to form
KNN-LNN solid solution, structural evolutions of KNN-LNN will be a
very worthy research topic. What's more, many researches have
proved that structural distortions are directly related to diverse
functionalities such as ferroelectricity, dielectricity, electro-
conductivity and so on [19e22].
In this work, we prepared the mixture of KNN and LNN ceramics
via conventional solid-solution method with the chemical
component of (K0.48Na0.52)1-x (Li0.15Na0.85)xNb0.98Sb0.02O3
-0.03Bi0.5Na0.5ZrO3-0.02CaTiO3 (abbreviated as KNNS-xLNNS-BNZ-
CT) (x ¼ 0, 0.2, 0.4, 0.5, 0.6, 0.8, 1). We have experimentally iden-
tified the evolutions of phase structure, dielectricity, ferroelec-
tricity, piezoelectricity, and mechanical behaviors in these ceramics
with varied compositions. In addition, the discussed mechanism
will help us to further understand the relationship between crystal
structure and electrical/mechanical properties in alkali niobate-
based lead-free piezoelectric materials.
2. Experimental procedure
2.1. Preparation of ceramics
KNNS-xLNNS-BNZ-CT lead-free piezoelectric ceramics are syn-
thesized via a conventional solid reaction process. Na2CO3 (99.8%),
Li2CO3 (98%), Nb2O5 (99.5%), Sb2O3 (99%), Bi2O3 (99%), K2CO3 (99%),
ZrO2 (99%), TiO2 (98%) and CaCO3 (99%) are used as raw powders,
weighed according to stoichiometric ratio of the ceramics. The
powders are mixed in ethanol for 12 h by planetary ball mill, then
dried and calcined at 850  C for 4h. The dried powders are mixed
with poly vinyl alcohol (PVA, 8%) and press into difform green
bodies by using different forming dies to meet the experimental
tests. After burning out the PVA, all samples are sintered at a certain
temperature for 2h in air. In order to obtain the best piezoelectric
properties for each composition, the samples with 0  x  0.4,
0.5  x  0.6, x ¼ 0.8 and x ¼ 1 are sintered at 1040  C, 1060  C,
1080  C and 1140  C, respectively.
2.2. Phase structure and microstructures
The fresh sintered discs (F10 mmh1 mm) are selected as the
testing samples. X-ray diffraction (XRD) (DX 2700, Dandong, China)
is used to measure the phase structure of all samples. The scanning
electron microscopy (SEM, S-3400 N, HIYACHI, Japan) is employed
to study the surface morphologies of sintered ceramics. Energy-
dispersive spectrometry (EDS) was used for elemental mapping of
the ceramics. The piezoresponse force microscopy (PFM) experi-
ments are carried out by using a commercial atomic force micro-
scopy (MFP-3D). The nanosensors PPP-EFM conductive probes with
a spring constant around 2.5 N/m and a resonance frequency in air
of around 70 kHz are used to obtain the vertical PFM images and
373
domain switching behaviors.
2.3. Electrical properties characterization
To evaluate the electrical properties of samples, silver paste
electrodes are coated on both sides of ceramics (F10 mmh1 mm)
and burned at 650  C for 10 min. The discs are poled under a DC
electric field of 2e4 kV/mm for 10e30 min at room temperature.
The capacitances of the sintered samples are measured by using an
LCR analyzer (HP 4980, Agilent, U.S.A. and TH2816A) with a varied
temperature between 150 and 500  C. Polarization verse electric
field (P-E) hysteresis loops of the ceramics are conducted at 10 Hz
using a Radiant Precision Work-station (USA). Their piezoelectric
constant d33, electromechanical coupling factor kp, mechanical
quality factor Qm, and relative dielectric constant εr etc. are char-
acterized by a Belincourt meter (ZJ-3A, Institute of Acoustics, Chi-
nese Academy of Sciences, China) and an impedance analyzer (HP
4294A, Agilent, U.S.A.) according to the IEEE standards.
2.4. Mechanical behaviours determination
Hardness Hv and fracture toughness KIC of the polished sintered
discs (F10 mmh0.8 mm) are measured by the indentation frac-
ture technique (IF) using a Vickers diamond indenter (AKASHI AVK-
A, Kanagawa, Japan). The compression strength sc of the sintered
cylinders (F10 mmh12 mm) and three point bending strength sb
of the sintered cuboid (L36 mmW4 mmh3 mm) are obtained
through the uniaxial compression loading on a universal testing
machine (INSTRON 8501, Grove City, PA), and their loading modes
are in the displacement control at a stroke rate of 0.5 mm/min.
3. Results and discussion
Fig. 1(a) displays the room temperature XRD patterns of bulk
KNNS-xLNNS-BNZ-CT ceramics in the range of 2q ¼ 20e60 , which
describes all ceramics with a typical perovskite structure. In addi-
tion, the principal crystalline phase of the ceramics is evolved from
KNN to LNN with increasing x from 0 to 1, which is identified by the
gradual appearance of discriminative peaks. The discriminative
peaks are some of the high-index facets in P21ma or R3c space
groups caused by the tilted oxygen octahedrons (these space
groups will be mentioned in Rietveld refinement part). Hence, the
discriminative peaks can be used to detect the presence of oxygen
octahedron tilting in the samples and further to identify the
changed crystalline phase. In Fig. 1(b), the enlarged XRD patterns in
Fig. 1. (a) XRD patterns of KNNS-xLNNS-BNZ-CT ceramics, the subscript of pc repre-
sents the pseudocubic plane, (b) enlarged XRD patterns in the 2q range of 21.5e23.5
and 45e47.5 .
374 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
the range of 21.5e23.5 and 45e47.5 clearly reflect the phase
structure evolutions of ceramics. The right-shift of diffraction peaks
with varied x could be attributed to the gradual distortion of lattice
caused by the substitution of Liþ at A-site. Moreover, the phase
transition behaviors in KNNS-xLNNS-BNZ-CT ceramics are further
expounded by the temperature-dependent dielectric constant
curves as shown in Fig. 2(a)e(g). The dielectric permittivity values
of KNNS-xLNNS-BNZ-CT ceramics exhibit a strong temperature
dependence on the existence of multiple phase transition in the
temperature range of 90e380  C. Two dielectric abnormal peaks
can be clearly observed in Fig. 2(a)-(e), which represent the ferro-
ferroelectric and ferro-paraelectric phase transition, respectively.
The ferro-ferroelectric phase transition temperature reaches the
smallest value around 20  C at the sample of x ¼ 0.2, and then
increases with increasing x. In contrast, in both Fig. 2(f) and (g), only
one dielectric peak can be observed, indicating no ferro-
ferroelectric phase transition or an independent-temperature
phase transition in these two samples. The variations of Curie
temperature (TC) and polymorphic phase boundary temperature
(TPPB) with x are shown in Fig. 2(h). It is generally believed that Li-
doping is a good way to increase TC values of KNN-based ceramics
[23,24]. In this work, KNNS-xLNNS-BNZ-CT ceramics exhibit the
similar results. When x  0.5, TC increases with increasing Li con-
tent. However, when x > 0.5, TC present an opposite tendency with
further increasing x, which may be attributed to the change of
principal crystalline phase. Additionally, from Fig. 2(f) and (g),
KNNS-xLNNS-BNZ-CT ceramics (especially at x ¼ 0.8 and 1) exhibit
diffuse phase transition around TC, which has been indicated as a
typical characteristic of relaxor ferroelectric based on their broad-
ening dielectric abnormal peaks. In addition, the frequency-
dependent dielectric peak can be found in Fig. 2(f) and (g).
Further detailed discussion has been provided as supplementary
information (Fig. s1 and Fig. s2).
In order to verify the detailed phase structure, Rietveld refine-
ment on the high precision XRD patterns (2q ¼ 10e120 ) of KNNS-
xLNNS-BNZ-CT ceramic powders is carried out by MAUD software.
The detailed experimental data and fitting curves of their Rietveld
results have been provided as supplementary information (Fig. s3).
The calculated crystal structure parameters and phase structure
information with reliability factors are listed in Table 1. Three
phases (rhombohedral-R3m, orthorhombic-Amm2, and tetragonal-
Fig. 2. (a)e(g) Temperature-dependent dielectric constant of the KNNS-xLNNS-BNZ-CT ceramics, measured at 1 kHz, 10 kHz and 100 kHz in the temperature range of 90e380  C,
insets in (f) and (g) are their enlarged Curie peak, (h) Curie temperature and polymorphic phase boundary temperature as a function of x.
P4mm co-existing) are found in KNNS-xLNNS-BNZ-CT ceramics
with x ¼ 0, which are reflected by the ferro-ferroelectric phase
transition peak observed in Fig. 2(a). The schematic diagrams of
these three ferroelectric phases have been shown in Fig. 3. All
ferroelectric phases exhibit lattice distortion caused by the
displacement of oxygen atoms and niobium atoms along different
directions. In R3m space group, the lattice distorts along [111] with
d1 ¼ d2 ¼ d3<d4 ¼ d5 ¼ d6 [Fig. 3(a)]. In Amm2 space group, the
perovskite-type (ABO3) orthorhombic structure includes mono-
clinic subcells with lattice parameters of am ¼ cm > bm, while bm is
perpendicular to (a-c)m plane with angle b of 89.57. The distortion
of subcell is along the [101]m as shown in Fig. 3(b). In P4mm space
group, the displacement of both oxygen and niobium atoms is
produced along [001] (c-axis), leading to the formation of tetrag-
onal phase as shown in Fig. 3(c). The three phases are typical
ferroelectric phases in KNN-based ceramics, and many high-
performance KNN-based piezoelectric ceramics are synthesized
by constructing the coexistence of two or three ferroelectric phases
near room temperature [4,6,9e12]. Subsequently, the sample with
x ¼ 0.2 shows the tetragonal structure as the predominant phase,
which is in good agreement with the low ferro-ferroelectric phase
transition temperature [about 20  C, as shown in Fig. 2(b)]. In
addition, some different space groups (rhombohedral-R3c and
orthorhombic-P21ma) have been introduced into the refinement
for the samples with x  0.5. The results show that the sample with
x ¼ 0.5 presents three-phase coexistence (R3c, P21ma and P4mm).
However, the two samples of x ¼ 0.8 and 1.0 only include two
phases (R3c and P21ma). The coexistence of two ferroelectric phases
is consistent with the formation of the vertical rhombohedral and
orthorhombic boundary in LNN ceramics (when Li content is
0.12e0.14), which has been reported by several previous works
[18,25]. It is worthy of note that R3c and R3m or P21ma and Amm2
belong to the same crystal system but different space groups. Fig. 4
shows the two kinds of crystal structures of sample with x ¼ 1.0.
The lattice parameters of R3c are characterized by a hexagonal unit
with a ¼ b ¼ 90 and g ¼ 120 . The tilting of oxygen octahedron
could be clearly observed in both Fig. 4(a) and (b), which is very
different with that in the R3m and Amm2 space groups. Actually, the
origin of the oxygen octahedron tilting is highly related to the
tolerance factor:
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384 375

Table 1
Crystal structure parameters of KNNS-xLNNS-BNZ-CT ceramics powders.

Parameters x¼0 x ¼ 0.2 x ¼ 0.5 x ¼ 0.8 x¼1

Sig 1.553 1.553 1.649 1.574 1.713

Rw (%) 7.528 7.714 8.088 7.709 8.035
Space group R3m Amm2 P4mm Amm2 P4mm R3c P21ma P4mm R3c P21ma R3c P21ma
Symmetry R phase O phase T phase O phase T phase R phase O phase T phase R phase O phase R phase O phase
Proportion 12.7% 22.2% 65.1% 2.8% 97.2% 7.62% 59.39% 32.98% 58.67% 41.33% 64.08% 35.92%
a (Å) 3.9739 3.9517 3.9606 3.9665 3.9460 5.6768 5.5975 3.9243 5.5123 5.5706 5.4972 5.5509
b (Å) 3.9739 5.6161 3.9606 5.4724 3.9460 5.6768 7.8314 3.9243 5.5123 7.7816 5.4975 7.7504
c (Å) 3.9739 5.6584 4.0019 5.7673 3.9922 13.6549 5.5579 3.9644 13.6731 5.5084 13.4646 5.4800
a ¼ b ( ) 90.0679 90 90 90 90 90 90 90 90 90 90 90
g ( ) 90.0679 90 90 90 90 120 90 90 120 90 120 90
u ( ) 0 0 0 0 0 11.03 7.9065 0 9.65 6.25 5.94 9.59
V (Å3) 62.755 125.578 62.775 125.187 62.162 356.003 243.638 61.052 359.802 238.779 352.3767 235.759
Z 1 2 1 2 1 6 4 1 6 4 6 4
Ps (mC/cm2) 42.41 14.80 18.23 25.63 12.76 51.14 36.43 6.56 41.31 33.00 28.54 14.17
Ps (mC/cm2) 20.54 13.12 29.70 37.88 23.38

Fig. 3. Crystal structures of the KNNS-xLNNS-BNZ-CT ceramics with x ¼ 0, (a) rhombohedral - R3m, (b) orthorhombic - Amm2, (c) tetragonal - P4mm.
376 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384

Fig. 4. Crystal structures of the KNNS-xLNNS-BNZ-CT ceramics with x ¼ 1, (a) rhombohedral (characterized by hexagonal unit) - R3c, (b) orthorhombic e P21ma.

r þ rO
t ¼ pffiffiffi A ; (1)
2ðrB þ rO Þ
where rA, rB and rO denote radii of A, B cations and O anions,
respectively [26]. Generally, for a centrosymmetric perovskite, the
tilting of oxygen octahedron will not occur when t is around 1 [21].
However, if t is smaller than 1 and the deviation is relatively large,
A-O bonds are tensed while B-O bonds are compressed, resulting in
the tilting of oxygen octahedron and the bending of B-O-B bonds
[17]. Such distortion will give rise to stacking along rotate direction
[27]. It was reported that the tilting usually happens when
t  0.9825 in some perovskite compounds [21]. In this work, the
calculated values of t are 1.010, 1.000, 0.984, 0.969, 0.959 for x ¼ 0.0,
0.2, 0.5, 0.8, 1.0, respectively. The continuously decreased values of t
are attributed to the smaller radii of Liþ and Naþ than that of Kþ.
Fig. 5 can help us to understand why oxygen octahedron tilts in
the perovskite structure. It is well known that potential energy is a
function of the distance in two atoms system, whose relationship is
shown in Fig. 5(b) (r0 is the equilibrium distance corresponding the
lowest value of potential energy). There is a similar situation be-
tween cation and anion. When the distance is large, the ions will be
attracted each other electronically. Conversely, the ions will be
repulsive when the ions are too close due to the restriction of ion
size. Fig. 5(a) illustrates the crystal structure of KNN, where the O2
is located at the center of four A-site atoms, and d is the distance
from A1 to A2. Obviously, the potential energy u(r) is symmetric
along d direction from A1 to A2. Therefore, there are two cases for
the curves of u(r) vs. r. The u(r) gets local minimum in the middle
point (d/2) when d  2r0 as shown in Fig. 5(c), which refers to the

Fig. 5. Illustration for the oxygen octahedral tilting, (a) crystal structure of KNN, d is the distance between A1 and A2; (b) potential energy u(r) as a function of interatomic separation
r in the two atoms system, r0 is the equilibrium internuclear distance; (c) the potential energy distribution for O2 from A1 to A2 in the case of d  2r0; (d) the potential energy
distribution for O2 from A1 to A2 in the case of d > 2r0.
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
case that A-site atoms have a larger size (a larger A-site cation will
give rise to a larger r0). However, once d > 2r0, u(r) has two local
minimums which are symmetrically distributed around the middle
line. This result shows the middle state is a non-equilibrium posi-
tion for the O2. The O2 tends to shift left or right to meet the
condition and then get the lowest local potential. For the
perovskite-type compounds, a smaller A-site ion results in a
smaller tolerance factor t, and the tilting of oxygen octahedron can
be confirmed experimentally at t  0.9825 in the perovskite
structure [19]. Therefore, as expected, the space symmetry of
KNNS-xLNNS-BNZ-CT changes at x ¼ 0.5 because t is close to
0.9825. The oxygen octahedron of R3c shows an antiphase tilting
described by Glazer notation a-a-a- tilt system [28]. On the contrary,
the space group of P21ma shows the antiphase tilting at the a-c
plane, but an inphase tilting pattern can be found along the b-axis
(described as a-a-cþ) [29e31]. All the large tilting angle of oxygen
octahedron can be seen clearly in Fig. 4.
In Fig. 3, the relative ionic displacements of R3m, Amm2 and
P4mm are easily observed, showing some different directions of
spontaneous polarization (Ps) for the three kinds of phase struc-
tures, which have been indicated in their structure diagrams.
However, the structures of R3c and P21ma are relatively complex
and it is difficult to directly define the direction of spontaneous
polarization. Considering that the spontaneous polarization (Ps) is
mainly attributed to the ion pair of Nb5þ/O2, the distances be-
tween Nb5þ and O2 in some oxygen octahedron can be measured
to determine the directions of Ps. In R3c, Fig. 4(a) shows that Ps is
along [001] direction due to d1 ¼ d2 ¼ d3>d4 ¼ d5 ¼ d6. On the one
hand, in P21ma, the adjacent oxygen octahedral with respect to
(020) plane is mirror-symmetric. Therefore, there is no component
of Ps along b-axis even though d1sd2. On the other hand, the O
atoms occupy the internal coordinates of z, -z, 1-z and 1 þ z, while
the Nb atoms occupy the internal coordinates of z and 1-z in c di-
rection. The above facts show the direction of Ps along a-axis [100].
According to the refinement results, the obtained atomic positions
and lattice parameters are taken to calculate the octahedron tilting
angle u and the spontaneous polarization Ps (Table 1) for the KNNS-
xLNNS-BNZ-CT ceramics with x ¼ 0 to 1. The spontaneous polari-
zation is estimated by
e X 00
Ps ¼ z Di; (2)
V i i
where V is the unit cell volume; e is the electron charge; Di is the
00
shifts of ith atom along the ferroelectric axis; zi is the nominal ionic
valence [32].
In Fig. 6(a), the frequency dependence of dielectric properties of
KNNS-xLNNS-BNZ-CT ceramics are investigated at room tempera-
ture. It is found that the dielectric permittivity of KNNS-xLNNS-
BNZ-CT ceramics depends on not only composition but also fre-
quency. The ceramics with lower LNN content exhibit higher
dielectric permittivity but poorer frequency stability. In contrary,
relatively low but almost frequency-independent permittivity
curves (ε0 ) are observed in the ceramics with higher LNNS content
(x ¼ 0.8 and 1). The decrease of dielectric permittivity with
increasing x can be attributed to several reasons. Generally, for
ferroelectric ceramics, the static dielectric permittivity derives from
electronic displacement polarization, ionic displacement polariza-
tion, and dipole orientation polarization (temperature-indepen-
dence) [33]. At the constant temperature, the replacement of
(Li0.15Na0.85)þ for (K0.5Na0.5)þ tends to decrease the electron
displacement polarizability (ae) because of their small electron
orbital radius. And for isovalent ions, the ionic displacement
377
polarizability (ai) is proportional to the cube of the sum of the
radius concerning positive ions and negative ions [33]. Since the
radius of (Li0.15Na0.85)þ is smaller than that of (K0.5Na0.5)þ, the
dielectric permittivity of KNN-based ceramics decreases with
increasing doping content of LNN (x). In addition, the ionic
displacement polarizability of solid dielectric is also related to the
ionic polarizability of constituent ions. (Li0.15Na0.85)þ has a lower
polarizability than (K0.5Na0.5)þ
þ 3 þ 3
(a(Li ) ¼ 0.029 Å <a(K ) ¼ 0.839 Å ), which contributes to the
decrease of dielectric permittivity based on the analysis of the
Clausius-Mossotti Equation [34]. Additionally, the microstructure,
particularly to the grain size, have a huge influence on dielectric
permittivity [35]. It is well known that dielectric permittivity of
ceramics with the Schottky barrier of the grain boundary can be
affected by the grain size and the barrier width as [36].
0 d
ε ¼ εB ; (3)
tB
where the d is the grain size and the tB is the internal permittivity of
barrier boundary. Therefore, the decrease of grain size will result in
the decline of the dielectric constant, which is consist with the
change of the average grain size in Fig. s5.
Further, the frequency-dependent ac conductivity could be
given by
0
sac ¼ ε0 ε utand; (4)
here, sac is the real part of ac conductivity and u is angular fre-
quency [37]. Fig. 6(b) displays the frequency dependence of sac of
KNNS-xLNNS-BNZ-CT ceramics with different x at room tempera-
ture. It can be seen that sac decreases with varied x at a certain
frequency, especially a decrease of two orders of magnitude in the
ceramics with x ¼ 0.8 and 1, which may be attributed to the
increasing oxygen octahedral tilting. The tilting can reduce the
overlap between the Nb d and O 2p orbitals, therefore, leading to a
higher bandgap for the perovskite oxides [19]. Consequently, the
ceramics with x ¼ 0.8 and 1 present a lower intrinsic conductivity.
Fig. 7(a)-(g) show the hysteresis loops of KNNS-xLNNS-BNZ-CT
ceramics. These ceramics are measured under different electric
fields according to their different dielectric breakdown strength
(DBS) and coercive electric field (EC). Generally, the DBS of dielectric
bulk ceramic materials is related to their microstructure features,
including grain size, porosity, grain boundary and so on [38].
Among these factors, the grain size plays a major role in the DBS of
dielectric ceramics. The smaller grain size usually presents a higher
DBS. In this work, the details about grain sizes and their distribu-
tion of KNNS-xLNNS-BNZ-CT ceramics have been provided in sup-
plementary information (Fig. s4 and Fig. s5). The grain size
decreases gradually with increasing x, so that the hysteresis loops of
KNNS-xLNNS-BNZ-CT ceramics could be measured under a higher
electric field when the value of x becomes larger. To further
investigate the ferroelectric properties of KNNS-xLNNS-BNZ-CT
ceramics, the plotting of remanent polarization (Pr) and coercive
electric field (EC) vs. x are depicted in Fig. 7(h). As can be seen, Pr
firstly decreases from x ¼ 0 to 0.4, and then increases from x ¼ 0.4
to 0.8, finally drops down at x ¼ 1. The Pr is given to a minimum
value of 15.1mC/cm2 at x ¼ 0.4, which mainly be attributed to its
unique crystal structure. As shown in Table 1, the tetragonal phase
of P4mm usually has a lower polarization value than orthorhombic
and rhombohedral ones. The internal physical mechanism is that
the displacement of Nb5þ is just along z-axis and only two oxygen
atoms contribute to the polarization in an oxygen octahedron. The
ceramics with x ¼ 0.2 and 0.4 contain the most of tetragonal
378 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384

Fig. 6. Frequency dependences of (a) real part ε0 of dielectric permittivity and (b) real part of ac conductivity of KNNS-xLNNS-BNZ-CT ceramics at room temperature.

Fig. 7. (a)e(g) Hysteresis loops of KNNS-xLNNS-BNZ-CT ceramics, measured at room temperature and 10Hz, (h) is the Pr and EC values vs. x.

structure (showing low PBB in Fig. 2), resulting in the lower po-
larization. This change of polarization is also in good agreement
with the variation of calculated spontaneous polarization (Ps,
shown in Table 1). The EC increases monotonically with increasing
x, which may be probably due to the following factors: (Ⅰ) Grain size
effect. The mobility of domain wall will be restricted by the grain
boundary, so that the decreased grain size gives rise to an
increasing EC [39,40]. (Ⅱ) Crystal symmetry. High symmetry of
crystal structure can reduce the anisotropy of crystal, and decrease
the energy barrier between two polarization directions. In this
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384 379

work, all space groups of R3m, Amm2, and P4mm have a higher
symmetry than P21ma and R3c. (Ⅲ) The more distorted and com-
pacted crystal lattice make ions become tighter and difficult to
move. As a result, the higher external electric field is required to
rearrange the polarization.
The piezoelectric properties of KNNS-xLNNS-BNZ-CT ceramics,
with 5 samples for each composition, have been investigated using
the quasi-static method (d33) and piezoelectric resonance method
(kp and Qm) as shown in Fig. 8. Both d33 and kp values decrease with
the increase of x, exhibiting the maximum value at x ¼ 0
(d33 ¼ 350 pC/N and kp ¼ 0.412) and the minimum value at x ¼ 1
(d33 ¼ 45 pC/N and kp ¼ 0.148). The high d33 and kp of x ¼ 0 can be
attributed to the large grain size and the formation of PBB at room
temperature in KNN-based piezoceramics. The low piezoelectric
properties of x ¼ 1 can be attributed to the intrinsic characteristic of
LNN-based ceramics, as the some reports [16e18]. However, a
contrary change tendency could be observed for Qm, exhibiting the
minimum value at x ¼ 0 (Qm ¼ 49) and the maximum value at x ¼ 1
(Qm ¼ 473). The vertical PFM is carried out to investigate the
microstructural evolution mechanism. The contact mode is used
firstly to obtain a better topography image (20  20 mm), and then
this area is scanned with an AC voltage (1V) to get the piezoelectric
response images as shown in Fig. 8(b). Obviously, the two typical
ceramics with x ¼ 0 (KNN) and x ¼ 1 (LNN) present the totally
different PFM results. To further characterize the domain structures
of the two ceramics, the PFM images marked with rectangle and
circle in Fig. 8(b) are amplified as shown in Fig. 8 (c). For the KNN
ceramics, one can see that a large number of lamellar domains with
lengths of several micrometers and widths of hundreds of nano-
meters dominate the domain structures. Besides, some nano-
domains can also be observed in the sample. This kind of sub-
micron domain and nanodomain structures have widely been
found in several piezoelectric materials, especially for some ma-
terials at the MPB composition [41e43]. The lamellar domain
structure is considered to present lower domain wall energy and
favorable polarization rotation under an external field [44], which
contributes to a high piezoelectric performance of ceramics. To
illustrate the domain switching behaviors of ceramics, the
switching spectroscopy PFM (SSPFM) with a DC voltage (20V) is
performed as shown in Fig. 8(d). Expectedly, the typical and satu-
rated PFM hysteresis and butterfly loops are observed, which in-
dicates that the ferroelectric domain has been switched under an
external field and present a better piezoelectric properties. As for
the LNN ceramics, the domains with size of around 3 mm are
distributed into the grains. Generally, such irregular domains are
disadvantaged of the polarization switching of ferroelectric mate-
rials, which can be manifested by the unsaturated PFM hysteresis
and butterfly loops obtained from the SSPFM results of LNN ce-
ramics in Fig. 8(d). The ferroic domains of LNN ceramics are hard to
be switched under an external field, which is also agreement with

Fig. 8. Piezoelectric properties and PFM mappings of the KNNS-xLNNS-BNZ-CT ceramics, (a) Piezoelectric constant d33, electromechanical coupling factors kp, and mechanical
quality factor Qm with error bars as a function of x, (b) the PFM images of ceramics with x ¼ 0 (KNN) and x ¼ 1 (LNN), (c) the local amplified PFM images marked with rectangle and
circle in Fig. 8(b), (d) the SSPFM images.
380 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
the result of its largest coercive electric field obtained from P-E
loops in Fig. 7. Besides, in terms of the inner physical mechanism,
the ions are bound by deeper potential well because of compact
crystal lattice (per pseudo-cubic unit cell) and larger tortuosity of
oxygen octahedron of LNN ceramics, and then the domains are
pinned at macroscopic level, which extremely weakens the con-
sumption of domain motion at the AC field and depresses the
piezoelectric properties [45]. As a result, the piezoelectric proper-
ties are deteriorated compared with the more KNN content
ceramics.
Additionally, an abnormal value at x ¼ 0.5 can be found in Fig. 8
(a), which might result from the formation of new ferro-
ferroelectric phase boundary at room temperature. The ferro-
ferroelectric phase boundary makes lower potential barrier be-
tween different polarization directions, the easier orientation can
not only improve d33 value but also increase the consumption of
domain motion (corresponding to the relatively low Qm). The more
detailed piezoelectric and elastic parameters are listed in supple-
mentary information (Table s1 and s2), which provide a reference
for the future theoretical analysis and practical applications.
Fig. 9 shows the mechanical properties of KNNS-xLNNS-BNZ-CT
ceramics. The typical pattern of the indentation and cracks pro-
duced beneath the Vickers diamond indenter are displayed in
Fig. 9(a). It can be seen that the symmetric rhombic indentation is
formed on the surface of ceramics and four cracks extend straightly
along the diagonal direction of rhombic indentation simulta-
neously. Generally, the area within the rhombic indentation is
Fig. 9. The mechanical properties of KNNS-xLNNS-BNZ-CT ceramics as a function of x, (a) indentation pattern (x ¼ 1), (b) the hardness and fracture toughness, (c) Stress-strain
curves and ferroelastic deformation, (d) bending strengths and compression strengths.
considered as the plastic deformation zone, while the crack growth
outside is related to the elastic deformation according to the me-
chanical model of sharp indenter of brittle materials [46]. This kind
of reversible (elastic deformation) and residual (plastic deforma-
tion) part play a significant role to the hardness (H) and fracture
toughness (KIC) of materials, which can be determined by following
formulas [47],
P
H ¼ 0:4636 ; (5)
a2
 1=2  
Y P
KIC ¼ 0:016 ; (6)
H C 3=2
where, P is applied load (here it is 19.6 N), a is the average radius of
rhombic indentation, Y is the Young's modulus shown in Table. s1
(Y E11 ), and C is the length of crack measured form center of the
indentation. The detailed geometry pattern of cracks are depicted
in Fig. 9(a). According to Eqs. (5) and (6), the hardness and fracture
toughness of KNNS-xLNNS-BNZ-CT ceramics as a function of x are
shown in Fig. 9(b). Obviously, the ceramic with x ¼ 1 obtains the
highest hardness of 4.88 GPa, while the lower hardness is given to
those ceramics with coarse grains, which can be explained by the
Hall-Petch equation (H ¼ H0 þ kd1=2 , where H0 and k are material
constants, d is the grain size of materials) [48], indicating that the
fine-grained materials are supposed to have a high hardness
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
corresponding to the weak plastic deformation of rhombic inden-
tation. On the other hand, the fracture toughness presents a sig-
nificant variation trend with the content of x. The highest fracture
toughness of 3.04 MPa m1/2 is obtained for ceramics with x ¼ 0.8.
The fracture toughness, as a characterization of the ability to
impede cracks growth of materials, is related to both of elastic
deformation (Young's modulus) and plastic deformation (Hard-
ness). The higher Young's modulus and Hardness of ceramics with
x ¼ 0.8 contribute to its highest fracture toughness. Besides, the
coarse grains in the ceramics with x ¼ 0.8 [Fig. s4(d)] are also
related to another toughen mechanism of materials. Coarse grains
existing in the matrix tend to resist the crack propagation and
toughen the materials based on the mechanism of crack deflection
[49], which is illustrated by the model of inserted figure in Fig. 9 (b).
The crack will change the previous route of approximately straight
extending when runs into the coarse grains, which could absorb
much energy of crack propagation leading to the crack thinner and
decrease the length of crack propagation (L) as well as improve the
fracture toughness. However, the ceramic with x ¼ 1 with the
highest Young's modulus and Hardness obtains a lower fracture
toughness of 1.99 MPa m1/2, which may be attributed to lacking
toughening mechanism of coarse grains due to its small and uni-
form grains or unfavorable and unstable local microstructure
leading to the local failure shown in Fig. 9 (a) when subjected to the
crack propagation of indentation cracks.
Fig. 9(c) describes the stress-strain curves of KNNS-xLNNS-BNZ-
CT ceramics under a uniaxial compression loading. For each stress-
strain curve, nonlinear region and linear region are formed during
subjected to the compressive load, corresponding to the ferroelastic
deformation and elastic deformation of materials, respectively [50].
The nonlinear ferroelastic deformation could be induced by the
ferroelastic domains switching when the compression loads
exerting on the samples surpass the coercive stress of domains. In
order to further expound these, a dramatic model is shown by the
inserted picture (Ⅰ) in Fig. 9 (c), which based on the fact that the
spontaneous polarization direction of ferroelastic domains would
be forced to be lying on the plane normal to the compression di-
rection due to certain ions rescheduling the new equilibrium po-
sitions as the ferroelastic deformation happened [51]. Therefore, a
small stress increment in this process could give rise to the large
strain because of the domain switching and reorientation, which is
also the reason why domain switching is regarded as another
toughen mechanism for piezoceramics materials. It can be seen
that the ceramics with x ¼ 0.8 seems to have the largest macro-
scopic remnant strain induced by domain switching, which may
result from an easy switching process of its unique domain struc-
tures, and the preeminent domain toughen behaviors also
contribute to its best fracture toughness shown in Fig. 9 (b). In
addition, several microcracks could be formed due to the inner
stress mismatch (such as discordant twinning shear) induced
during the process of domain switching [52]. On the other hand,
more or less curve discontinuity (load drop) behaviors are shown in
certain stress-strain curves, which may be attributed to the local
failure when subjected to a larger external stress. After the
nonlinear ferroelastic deformation is completed, the material starts
to express more stiffness and presents a linear elastic deformation
with the increase of stress. In this section, the intrinsic microcracks
(formed during sintering process), the extrinsic microcracks (pro-
duced by domain reorientation), and other defects (such as impu-
rities or pores) as the potential crack initiation origins play
important roles to the failure of materials. Then, the crack initiates
and propagates rapidly to form the main crack, and sequentially the
sample occurs to the axial flurry due to the mechanical strength
381
degeneration and unable to bear further crack propagation and
eventually fractures as shown by inserted picture (Ⅱ) in Fig. 9 (c).
The compression strengths of KNNS-xLNNS-BNZ-CT ceramics
obtained from stress-stain curves are shown in Fig. 9(d). The lowest
value of compression strength of 318 MPa is obtained for the typical
KNN ceramics, while the typical LNN ceramics have the highest
compression strength of 788 MPa, which is over twice times than
the former. As we know, the micro defects including microcracks
and pores have vital effects on the compression strength, and less
defects lead to higher compression strength. Besides, the
compression strength also depends on the grain size of brittle
materials. Fine grain size expects to exhibit large compression
strength [53]. Therefore, the ceramic with x ¼ 1 presents the best
compression strength benefited from its least defects (low dielec-
tric loss) and smallest grain size. On the other hand, the bending
strengths of KNNS-xLNNS-BNZ-CT ceramics are also displayed in
Fig. 9(d). It can be seen that the bending strength presents an up-
trend with the increasing content of x. Similarly, the typical LNN
ceramic gains the highest bending strength of 125 MPa, while the
typical KNN ceramic obtains the lowest bending strength of
36 MPa. In fact, the bending strength of ceramics can be described
by the following equation [54],
K
sb ¼ p
IC
ffiffiffi ; (7)
j c
where, j is the parameter dependent on the crack or sample ge-
ometries; c is the critical crack length, which generally is propor-
tional to the grain size in ferroelectric ceramics [50]. The equation
manifests that the reduction in grain size can improve bending
strength, and fracture toughness also has a great influence on
bending strength. Therefore, the typical LNN ceramic with x ¼ 1.0
with the smallest grain size are supposed to obtain higher bending
strength. However, the ceramic with x ¼ 0.8 with the highest
fracture toughness and relative smaller grain size could not obtain
the highest bending strength, which may mainly be attributed to
the effect of coarse grain in the matrix and a sort of competition
mechanisms between fracture toughness and inhomogenous grain
sizes for dominating the bending strength of ceramics.
The KNN ceramic can obtain excellent electrical properties but a
feeble mechanical strength, while the LNN ceramic presents con-
trary properties. The huge differences between electrical and me-
chanical properties of KNNS-xLNNS-BNZ-CT ceramics can be
explained through the constitutive relationship of stress-stain in
piezoelectric physical mechanism. Generally, the polarization of
alkali niobate-based piezoelectric materials is mainly contributed
by the pairs of Nb5þ/O2 because of their larger ionic charge than
that of A-site ion. However, this work shows that even isovalent A-
site replacement can also affect the piezoelectric and mechanical
properties significantly. The substitution of (Li0.15Na0.85)þ with
lower ionic radius decreases the lattice volume per pseudocubic
unit cell (Table 1) and gives rise to the oxygen octahedron tilting.
These changes make the crystal become more compact, and the
inner ions will be restricted by shorter and stronger bonds, which
are supposed to lead to a better intrinsic mechanical strength.
Hence, in this kind of compact structure, a constant stress s will
yield a smaller strain h, and their relationship can be expressed by
Hook's law,
X
6
si ¼ Cij hj ; (8)
j¼1
where Cij is the elastic stiffness tensor. The equation shows that Cij
382 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
Fig. 10. Illustration for the influence of A-site replacement and the results that applying constant stress for different structures. DP3 is the change value of polarization along z
direction.
will be increased and ceramics become harder with increasing LNN
content, which is consistent with our results in Table s1 of
supplementary information and Fig. 9(b). We also use first-
principle method to check the relationship of Cij and lattice pa-
rameters. The results of calculation support our inference (the
related computational method and results are shown in
supplementary Table s3 and s4). On the other hand, although the
ceramics with high LNN content show higher spontaneous polari-
zation shown in Table 1, the piezoelectric constant d33 gradually
decreases with increasing x. The piezoelectric stress constant d33 is
described by differentiating equation as
vP3
d33 ¼ ; (9)
vs 3
where P3 is polarization along z direction; s3 is the stress along z
direction and applied on the plane normal to the z direction. For the
ceramics with higher LNN content, a constant stress s3 just yield
smaller strain in z direction because of higher elastic stiffness
constant. Subsequently, the smaller strain leads to smaller change
in the P3, so that the smaller d33 can be found. The related illus-
trations have been shown in Fig. 10, which can help us to better
understand the relationship of structural, mechanical and piezo-
electric properties in the alkali niobate-based piezoelectric ce-
ramics. This research demonstrates that the small A-site cation can
compress the lattice volume and improve the intrinsic mechanical
strength in niobate-based piezoelectric materials. Meanwhile, the
improved intrinsic mechanical properties also suppress the piezo-
electricity. This result also shows the high piezoelectric properties
and good mechanical properties are hard to obtain simultaneously
in the same materials, and it may be found that their balance is
more reasonable for practical piezoelectric applications.
4. Conclusion
A series of KNNS-xLNNS-BNZ-CT ceramics have been prepared
by conventional solid-state reaction method. Their phase struc-
tures, microstructures, dielectricity, ferroelectricity, piezoelectricity
and mechanical properties have been comprehensively studied.
Rietveld refinement results on XRD patterns suggest the ceramics
undergo several ferro-ferroelectric phase transitions with
increasing LNN content. Moreover, the oxygen octahedron tilting
occurs when x > 0.5 and the tilting angle increases with further
increasing LNN content, which can be attributed to the potential
energy field changing caused by the gradually decreased grain size
of A-site atom. Although multi-phase coexistence can be found in
certain composition, the compressed crystal lattice still gives rise to
the decreased dielectric constant at high level of LNN content. The
change of piezoelectric constant is similar to dielectric constant
except for the one with x ¼ 0.5, the abnormal piezoelectric constant
owes to the formation of ferro-ferroelectric phase boundary.
Moreover, the strongly restricted ions make the pinned domains, so
that the Qm increases rapidly when x > 0.5. As for mechanical be-
haviors, ferroelastic deformation is observed in these samples, and
the mechanical properties such as hardness, fracture toughness,
bending strength, and compression strength show a significant
change tendency with increasing content of x, while KNN ceramic
presents a feeble mechanical strength in all. The decreased lattice
parameters and titled oxygen octahedron result in a compact
structure at high LNN level because of the small radius of
(Li0.15Na0.85)þ. Then the shorter and stronger bands could greatly
prevent the deformation when the sample is under the pressure, so
that the large intrinsic hardness could be found when x increases.
This increased hardness, in turn, yields the small change of polar-
ization when sample is under a constant stress. In other words, the
increased intrinsic hardness gives rise to the suppressed piezo-
electric constant d33.
In short, our work reveals there are strongly relationship be-
tween crystal structure, piezoelectric properties and mechanical
properties in niobate system piezoelectric ceramics. The evolutions
of phase structure, dielectricity, piezoelectricity and mechanical
properties from KNN to LNN-based ceramics have been
 Z. Tan et al. / Journal of Materiomics 5 (2019) 372e384
demonstrated in this paper, and the inner physical mechanism also
has been discussed. We hope it can help us to further understand
the relationship between structure and piezoelectricity as well as
mechanical strength for promoting the application of alkali
niobate-based piezoelectric materials.
Conflicts of interest
There are no conflicts to declare.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (Grant No. 51332003, No. 11572057 and No.
11702037), and Program for Changjiang Scholars and Innovative
Research Team (IRT14R37). Authors thank to Ms. Hui Wang
(Analytical & Testing Center, Sichuan University, China) for the help
in the test and analysis of SEM and EDS.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jmat.2019.02.001.
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Prof Jianguo Zhu Jianguo Zhu received his MS degree in
1987 and PhD degree in 1988 in physics from Sichuan
University. In 1987e1988, he worked at the Department of
Physics, Sichuan University as an assistant professor. Since
1988, he has worked at the Department of Materials Sci-
ence, Sichuan University as an assistant professor, associ-
ated professor and professor, respectively. His research
interests mainly focus on the controllable-synthesis, char-
acterization and properties of ferroelectric, piezoelectric
and dielectric functional materials. Zhu is the author of
over 300 peer-reviewed articles, 9 books and over 20 Chi-
nese patents and has given about 50 invited lectures in
various meetings and conferences.
Prof Qingyuan Wang Solid mechanics and structural
engineering PhD tutor. Deputy-director of the National
experimental mechanics committees. Vise-chairman of
Sichuan province architectural institute. His research ac-
tivity is focused on Very High Cycle Fatigue, Accelerated
Fatigue Testing Method, Mechanical Behavior of Structural
Materials and Structures under Fire/Cyclic Loading, Me-
chanical Behavior and Durability of Recycled Aggregate
Concrete, Composite Repairs of damaged Structures. He
received his PhD from Ecole Centrale Paris, France, fol-
lowed by postdoctoral experience in Faculty of Engineer-
ing of Purdue University, USA, and JSPS fellow at
Kagoshima University, Japan. Prof. Wang has published
over 120 technical papers in refereed journals and confer-
ence proceedings. Dr. Wang was Enlisted Scientist for “100
Talents Program” of Chinese Academy of Sciences in 2003.
He received the Excellent Young Teachers Program Award
in 2003, New Century Excellent Talents Program Award in
2005, First class Natural Science Award of Research in
2006 from National Ministry of Education, and the special
award of Chinese Central Government in 2008.