Ceramics International xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Microstructure evolution and reaction mechanism of Pb(Zr1/2Ti1/2)O3-Pb

(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics with plate-like
PbTiO3 template
Leilei Lia,1, Junting Liua,1, Shuyao Caoa, Jie Xua,d, Changying Wub, Emilia Pawlikowskac,
Mikołaj Szafranc, Feng Gaoa,∗
a
State Key Laboratory of Solidification Processing, MIIT Key Laboratory of Radiation Detection Materials and Devices, NPU-QMUL Joint Research Institute of Advanced
Materials and Structures (JRI-AMAS), School of Materials Science and Engineering, Northwestern Polytechnical University, Xi'an, Shaanxi, 710072, PR China
b
School of Electronics and Information, Northwestern Polytechnical University, Xi'an, Shaanxi, 710072, PR China
c
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland
d
Research & Development Institute of Northwestern Polytechnical University in Shenzhen, Shen zhen, 518057, PR China

ARTICLE INFO ABSTRACT

Keywords: 0.83 Pb(Zr1/2Ti1/2)O3-0.11Pb(Zn1/3Nb2/3)O3-0.06Pb(Ni1/3Nb2/3)O3 (PZNNT) samples with plate-like PbTiO3

PbTiO3 template (PT) template were prepared using tape casting technology. The microstructure evolution and reaction me­
PZNNT matrix Materials chanism between the matrix and PT template was investigated systematically. The quench heat treatment ex­
Microstructure evolution periment was designed and the microstructure was evaluated. The results showed that the plate-like PT template
Texture ceramics
has relatively low thermal stability which would decompose to form Pb-rich liquid phase and Ti-rich region at
the sintering temperature of 900 °C–1050 °C. Plate-like PT template reacted with the PZNNT matrix materials
during the sintering process, which did not contribute to the grain growth orientation for PZNNT matrix. Finally,
the mechanism of grain growth for the PZNNT ceramics with plate-like PT template is clarified. This work
demonstrated that the thermal stability of plate-like template is one of the key factors for fabricating textured
piezoelectric ceramics.

1. Introduction Textured ceramics are prepared by (reactive) template grain growth

Over the past two decades, piezoelectric properties of < 001 >
oriented ferroelectric single crystal materials, such as Pb(Mg1/3Nb2/3)
O3–PbTiO3, have attracted extensively attentions because of excellent
piezoelectric properties [1,2]. However, the high production cost, sized
barriers and compositional heterogeneity have limited the use appli­
cation of single crystal materials. Recently, oriented texture ceramics
are significant in enhancing the piezoelectric and ferroelectric proper­
ties of material, and the piezoelectric properties can be as high as
60%–80% of single crystal with the same component [1]. Thus, the <
001 > oriented Pb(Zr,Ti)O3 (PZT) based piezoelectric ceramics have
attracted much attention due to their high piezoelectric properties, as
well as their potential application in actuators and energy harvesting
field, such as PbTiO3–Pb(Mg1/3Nb2/3)O3 [2,3], Pb(Zr1/2Ti1/2)O3–Pb
(Zn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3 [4], (Pb0.8725Sm0.085)O3
(Ti0·98Mn0.02)O3 [5], etc.
((R)TGG) technology by controlling the grain orientation, using the
plate-like perovskite as template. The aligned templates are used to
guild oriented grain growth with a fine, dense grained ceramics matrix
[6]. Generally, the template should have a similar crystal structure with
the lattice constant below 15% to a good lattice matching degree with
the matrix materials [7]. The perovskite compounds with anisotropy
morphology, such as plate-like BaTiO3 [8], plate-like SrTiO3 [6], are
always fabricated by molten salt method and topochemical microcrystal
conversion, using the Aurivillius structure compounds as precursor.
Considering that PbTiO3 (PT) is a type of perovskite compound similar
to BaTiO3 and SrTiO3. And it is the primary element for PZT based
matrix material and has similar crystal structure and element compo­
sition with the matrix material, which avoids introducing new impurity
ions into PZT system. Besides, before fabricating the textured ceramics,
it is meaningful to explore the sintering process, reaction mechanism as
well as the microstructure evolution between template and matrix

∗
Corresponding author.
E-mail address: gaofeng@nwpu.edu.cn (F. Gao).
1
The authors contributed equally to this work.

https://doi.org/10.1016/j.ceramint.2020.08.154
Received 9 June 2020; Received in revised form 14 August 2020; Accepted 17 August 2020
0272-8842/ © 2020 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Leilei Li, et al., Ceramics International, https://doi.org/10.1016/j.ceramint.2020.08.154
L. Li, et al.
materials.
In this paper, we choose the plate-like PT particles as template and
0.83 Pb(Zr1/2Ti1/2)O3-0.11 Pb(Zn1/3Nb2/3)O3-0.06 Pb(Ni1/3Nb2/3)O3
(PZNNT) ceramics as matrix to prepare the PZNNT-PT ceramics by tape
casting technology. The influence of sintering temperatures on the
microstructure of PZNNT-PT ceramics was investigated, and the reac­
tion mechanism between PT template and PZNNT matrix material
during the sintering stage was discussed.
2. Experiment
The PZNNT matrix materials were fabricated by solid state process.
Analytical pure mixtures of PbO, ZrO2, TiO2, Nb2O5, Ni(CH3COO)·4H2O
and ZnO were milled in the ethanol for 12 h and calcined at 780 °C for
2 h. Then calcined PZNNT powders were milled in the ethanol for 6 h
by Nano grinding machine (Vgreen Nano-tech, China) to obtain the
nano-powders with powder size lower than 200 nm.
Plate-like PT template was synthetized by two step molten salt
method, using plate-like PbBi4Ti4O15 (PBIT) as precursor. Firstly, mix­
ture of analytical PbO, TiO2 (rutile), Bi2O3 with an equal weight KCl
salt was ball milling in the ethanol, then calcined at 900 °C for 5 h. The
plate-like PBIT precursor was washed with deionized water several
times to remove the residual Cl−. Subsequently, the obtained PBIT
microcrystals was added into mixtures of Pb(CH3COO) 2•3H2O and
equal weight KCl salt to prepare the plate-like PT template, with mix­
tures calcined at 900 °C for 5 h. Finally, the PT product was washed
with deionized water to remove Cl− and the 30% HNO3 was used to
eliminate the Bi2O3 byproduct. The AgNO3 solution was used to detect
the residual Cl−.
The PZNNT-PT ceramics prepared by tape casting method with the
addition of 10 wt% plate-like PT as template. The PZNNT matrix ma­
terials with the organic binder and ethanol/toluene solvents were ball
milling for 12 h to prepare the slurries, then added the plate-like PT
template. Later, the mixed slurry was casted by tape casting methods.
The dried green tapes were stacked, dealt with hot pressing. Samples
were sintered at 920 °C, 1050 °C and 1150 °C for 2 h in a lead-rich
atmosphere. And the samples were sintered at 920 °C, 1050 °C and
1150 °C for 5 min in a lead-rich atmosphere and then immediately
water quenched to observe the microstructure and composition evolu­
tion in PZNNT-PT ceramics. Phase structure and microstructure were
determined by XRD (Bruker, Germany) and FESEM (JSM-6701F,
Japan), with the element percentage carried out by energy dispersive
spectroscopy (EDS). High resolution transmission electron microscopy
(HRTEM, FEI Talos F200X, USA) was performed to analysis the mi­
crostructure and domain structure in PZNNT-PTceramics, and the TEM
sample was fabricated using the conventional ion-cutting method using
the precision ion polishing system (PIPS, Gatan 691, USA).
3. Results and disccution
XRD and SEM images of PBIT precursor and PT template by molten
salt method are shown in Fig. 1. By Fig. 1 (a,b), pure plate-like PBIT
microcrystals phase (JCPDF No. 43–0972) was obtained using one step
molten salt method, with an average diameter of ~7.74 μm and a
thickness of ~0.29 μm. The result then showed that the plate-like PT
microcrystals (Fig. 1 (c,d)) with a diameter of 5 μm–20 μm and a
thickness less than 0.5 μm were obtained by topochemical microcrystals
conversion with PBIT as precursor, coexisted some of intermediate
phase Pb4Bi4Ti7O27 due to its stable Aurivillius structure [9]. Since,
bismuth lies next to lead in the periodic table, and its atomic weight is
as large as lead. So the electronic configuration of Bi3+ is identical to
that of Pb2+, which can contribute to the similar chemical behavior of
two elements [10].
XRD patterns of PZNNT and PZNNT-PT ceramics sintered at dif­
ferent temperatures is shown in Fig. 2. All samples showed the pure
perovskite phases, and (110) diffraction peak was also the strongest
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while {00l} peaks were weak. The result indicated that there was no
oriented grain growth appeared in PZNNT-PT ceramics by the addition
plate-like PT [2,3]. For PZNNT ceramics without PT template, the dif­
fraction peak around 45° means the coexisting rhombohedral and tet­
ragonal phases at the morphotropic phase boundary (MPB) [2]. The
splitting of (002) and (200) peaks of PZNNT-PT ceramics can be ob­
served obviously with the increase of sintering temperatures. In order to
better understand the phase evolution of PZNNT-PT ceramics, the
content of rhombohedral phase (R.P.) is quantified by the fitting curves
in the 2θ range from 44° to 46° by equation (1) [11].
I(200) R
R. P. % = × 100%
I(200) T + I(002) T + I(200) R (1)
where I(200)T, I(002)T and I(200)R are integral intensity of tetragonal and
rhombohedral peaks, respectively. The fitting curves represented the
tetragonal (002) and (200) peaks, and the rhombohedral (200) peaks.
With the increase of sintering temperature, the splitting intensity of
(200) peak became obviously, indicating the increase of tetragonal
phase in PZNNT-PT ceramics. When the sintering temperature was
1150 °C, the R.P.% of 10.9% can be obtained and obviously deviated
from the MPB content. Since the PT material is a type of typical fer­
roelectrics with tetragonal symmetry, adding plate-like PT to the
PZNNT would improve the phase transition from the rhombohedral to
the tetragonal phase at the MPB [12].
Fig. 3 shows the TEM images of PZNNT-PT ceramics sintered at
1050 °C. In Fig. 3, the nano-domain of herringbones and watermarks
can be observed in the PZNNT-PT ceramics, which corresponded to 60°
and 180° domains, respectively [13]. The width of nano-domain was
around 30–70 nm, moreover, insides the nano-domain, there were
many miniaturized domains with domain widths of 10 nm, as shown by
yellow solid lines in Fig. 3 (Ⅰ,Ⅱ). As we known, for PZT based piezo­
electric ceramics, it coexisted the tetragonal and rhombohedral phase at
the MPB. The tetragonal phase takes the six [001] polarization direc­
tion, consisted of 180° and 90° domain, the rhombohedral phase takes
eight [111] polarization orientations, consisted of 60°, 120°, 71° and
109° domain [14]. Thus, we can deduced that the coexistence of 60°
and 180° domains in PZNNT-PT ceramics indicates the coexistence of
tetragonal and rhombohedral phase in the PZNNT-PT ceramics. Thus,
combined with XRD and TEM analysis, with the rising the temperature,
the content of rhombohedral in the PZNNT-PT ceramics was decreasing.
Fig. 4 and Fig. 5 shows the SEM fracture images and corresponding
grain size distribution of PZNNT and PZNNT-PT ceramics. The grain
size of PZNNT-PT ceramics was increased with the increase of sintering
temperature, which was 2.72 ± 0.07 μm, 3.07 ± 0.07 μm,
4.76 ± 0.11 μm, respectively. And the density was 7.27–7.58 g/cm3
range. Compared with PZNNT ceramics without PT, however, the
PZNNT-PT ceramics clearly display equiaxed grain and no orientation
grains. The compactness between PZNNT-PT ceramics grains is poor
when sintered at 920 °C, with a low relative density of 90.9%. In
PZNNT-PT ceramics the sintering hysteresis appeared because the size
of matrix material was much smaller than template grains. The tem­
plate was therefore regarded as a rigid grain nucleation core in the
matrix material and generated the tensile stress around the template
[15]. Thus, the part of sintering drive force would be released with the
interface development between the template and matrix materials.
With the sintering temperature further increased, the sintering activity
between PT template and PZNNT matrix enhanced, resulting in the
grain growth. Since some of the most persistent intermediate Aurivillius
phases coexisted in the plate-like PT microcrystal, the PT template
showed relative low stability and high chemical activity at the high
sintering temperature [16,17]. Consequently, the chemical reaction
between the PT template and the PZNNT matrix was easy to occur. So,
the plate-like PT template failed to act as the oriented growth template
and no PZNNT-PT texture ceramics were finally obtained.
To further analyze the existing forms of PT template and PZNNT
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Fig. 1. (a) XRD, (b) SEM images of PBIT precursor by one step molten salt methods, (c) XRD and (d) SEM images of PT template by two step molten salt methods.

matrix materials in the sintering process, Fig. 6 gives the back-scat­
tering SEM images, EDS images of Ti-rich regions and equiaxed grains
of PZNNT-PT ceramics. The obviously equiaxed grain distribution in
PZNNT-PT ceramics can be observed at different sintering tempera­
tures. Additionally, it is interested that some Ti-rich regions can be
observed in the samples sintered at 920 °C and 1050 °C. In PZNNT-PT
ceramics, the grain morphology of the Ti-rich regions gradually
changed from plate-like to equiaxed shape. With the sintering tem­
perature increasing to 1150 °C, the Ti-rich regions were missing. From
spot 1 in Fig. 6 (d), the main elements in Ti-rich regions with plate-like

Fig. 2. XRD patterns of PZNNT-PT samples sintered at different temperature, (a) PZNNT 920 °C, (b) PZNNT-PT 920 °C, (c) PZNNT-PT 1050 °C, (d) PZNNT-PT
1150 °C.

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Fig. 3. TEM images of PZNNT-PT ceramics sintered at 1150 °C.

morphology were Pb, Ni, Ti, Zn, and O. The result indicated that the
element diffusion occurred between PT template and PZNNT matrix
materials, and the Ti-rich regions formed at 920 °C. From spot 3 and
line-scanning SEM in Fig. 6 (g,f), the obvious distribution of rich zinc
and titanium elements can be observed, indicating the key elements
changed to Zn, Ti, and O in Ti-rich regions. However, the elements in
equiaxed grains (spot 2, 4) were Pb, Zr, Ti, Nb, Ni, Zn and O. The atom
ratio of Pb2+/(Zr4++Ti4+) was close to 1:1, thus it can be concluded
that the equiaxed grains mainly consisted of PZNNT matrix. The above
result indicated that the chemical reaction between PT template and
PZNNT matrix materials has occurred at 920 °C, so that the PT was
failed to template orientation under the higher sintering temperatures.
It is known that Pb(Zn1/3Nb2/3)O3 and Pb(Ni1/3Nb2/3)O3 com­
pounds have a low stability with a partially disordered perovskite
structure, which are easy to decompose and form the new phase, e.g.
ZnO [18,19]. In this work, PT template can decompose the PbO at the
high temperature (equation (2)), which can act as the liquid phase and
promote the ionic diffusion between PT template and PZNNT matrix
material [20–22]. Besides, some Ti4+ in PT template may substitute the
Zn2+, Ni2+ and Nb5+ elements in B-site of Pb(Ni1/3Nb2/3)O3 and Pb

Fig. 4. SEM fracture images of PZNNT-PT samples containing 10 wt% PT template, (a) PZNNT 920 °C, (b) PZNNT-PT 920 °C, (c) PZNNT-PT 1050 °C, (d) PZNNT-PT
1150 °C.

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Fig. 5. Grain size distribution of PZNNT-PT samples containing 10 wt% PT template, (a) PZNNT 920 °C, (b) PZNNT-PT 920 °C, (c) PZNNT-PT 1050 °C, (d) PZNNT-PT
1150 °C.

Fig. 6. Back-scattering SEM frature images of PZNNT-PT samples sintered at different temperature, (a) 920 °C, (b) 1050 °C, (c) 1150 °C, the EDS images and
corresponding values (d,e,g,h,i) of rich phase and equiaxed grain, and line scanning results (f) along the yellow arrow in Fig. 6(b). (For interpretation of the
references to colour in this figure legend, the reader is referred to the Web version of this article.)

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L. Li, et al.
Fig. 7. Map scanning SEM surface images of PZNNT-PT ceramics sintered at 1050 °C.
(Zn1/3Nb2/3)O3 because their unstable perovskite structure and similar
ionic diameter, it would result in the generation of Ti-rich regions in­
cluding Zn, Ni, etc [23]. When the sintering temperature was 1150 °C,
PT template saluted into PZNNT matrix materials and established the
stable solid state of PZNNT-PT ceramics due to the high sintering
driving force.
PbTiO3(s) = PbO(l) + TiO2(s) (2)
Fig. 7 displays a map scanning SEM images to verify the composi­
tion fluctuation of PZNNT-PT ceramics. From Fig. 7, the main elements
were Pb, Zr, Zn, Ti, Ni, Nb and O, etc in the PZNNT-PT ceramics. The
key elements of Ti-rich regions from the back scattering SEM were Zn,
Ti and O, with a slight amount of Ni. The result further confirmed that
the PT template decomposed at the high sintering temperature when
the PZNNT matrixs grew along the plate-like PT template. The Pb ele­
ment was diffusion into matrix materials, which can act as the sintering
aids to promote chemical reaction and grain growth.
When preparing the texture ceramics, the template should have
anisotropy morphology with particle size larger than 5 μm, in order to
avoid the engulfing by the surround matrix materials during the sin­
tering process. At the same time, it should also have identical crystal
structure with matrix materials, i.e., the PT template and PZNNT matrix
materials all belong to perovskite structure. In addition, according to
the Gibbs-Thomson equation, the growth dynamics of textured grains
are governed by the solubility of template and matrix materials in the
liquid phase [24]. The solubility of template (ST ) and matrix materials
(Sm ) is related with the grain size of materials (equations (3) and (4))
[7].
2 TM
ST = S0 exp
rT RT (3)
Sm = S0 exp
2 mM
rm RT (4)
where S0 is the equilibrium solubility, m is the average matrix surface
energy, rT and rm are the average template and matrix grain size, R is the
gas constant, is the density of the matrix material, T is the tempera­
ture, M is the molecular weight of the material.
Suppose Sm ≫ ST, then Sm/ST≫1, thus [7].
2 mM TM
exp 1 liquid phase, and the grain size of PZNNT matrix material increased
RT rm rT (5)
Consequently, the TGG process is related with the difference in
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particle size between the template and matrix materials. That is, the
smaller particle size of the matrix material was easier to dissolve into
the surrounding liquid phase, and then grew on the large particle with
low saturation. Therefore, the matrix materials should have enough
small particle size to provide the larger driving force for orientation
grain nucleation [24]. Take into account the above result, the grain size
of the PT template (rT ) and PZNNT matrix materials (rM ) we used here
were larger than 5 μm and smaller than 200 nm, respectively, with rT / rM
of 25, and the high driving force could be given during the texture
process. Considering that the driving force for the TGG process is the
reduction of surface free energy, and the template growth is pre­
dominantly a result of radial growth. Suvaci et al. [25] suggested that
the requirement for the growth of template in matrix materials is shown
in equation (4).
GST > kGSm (6)
In TGG system k is ~1.5. So the ratio of template thickness (rD ) and
matrix grain size (rM ) is used to measure the driving force for grain
growth. That means that for template orientation and matrix coar­
sening, the size ratio for rD/ rM must ≥1.5 [25]. In the PZNNT-PT
system, rD/ rM is around 2.5, we can conclude that the initial grain size of
PT template and PZNNT matrix material satisfied the requirement to
fabricate the texture ceramics. Finally, however, the PZNNT-PT cera­
mics with grain orientation are not obtained. In order to further analyze
the variation in chemical reaction between PT template and PZNNT
matrix materials, a quench heat treatment experiment has been de­
signed and the fracture SEM images of PZNNT-PT ceramic are shown in
Fig. 8. The corresponding EDS results are shown in Fig. 9 and Table 1.
From Fig. 8(a and b), with the sintering temperature between 600
and 800 °C, the PT template distribution was clearly arranged and be­
came thinner, and the PZNNT matrix grain size gradually increased.
The ceramic densification gradually resulted in the increase of contact
area between PT template and PZNNT matrix. As the high surface en­
ergy difference between the template and matrix materials existed due
to the high curvature radius difference, the PZNNT matrix material
would carry out template grain growth along the lowest energy surface
{100} of PT template, and the template interface gradually grown into
the PZNNT matrix material, e.g., the PT template became thinner [26].
Simultaneously, the grain size of PZNNT matrix material far away from
the PT template enhanced because of its relatively small size and high
surface energy. Later, the PT template gradually decomposed with some
obviously at 900 °C. Then the PT template decomposition finished at
1000 °C, with the existence of some unreacted liquid phase and Ti-rich
L. Li, et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 8. SEM fracture images of PZNNT-PT ceramics sintered at different temperature and immediately water quenched.

regions. The result showed that the grain growth between PT template Table 1
and its surrounding PZNNT matrix materials was mainly based on the EDS values (atom%) of PZNNT-PT ceramics sintered at different temperature
liquid phase sintering mechanism at 900–1000 °C. The liquid phase and immediately water quenched.
may gradually promote the template corrosion and chemical reaction Positions Elements
between the PT template and surrounding PZNNT matrix material.
Migration driving force from PT template to surrounding PZNNT matrix PbL ZnK NiK TiK NbL ZrL OK
material enhanced due to the solubility difference of liquid phase
Spot 1 42.61 15.91 1.52 8.75 0.72 3.43 27.07
boundary layer between PT template and PZZNT matrix material [26]. Spot 2 61.23 3.53 1.41 9.78 0.39 4.27 19.39
Meanwhile, the surrounding fine grain size of PZNNT matrix materials Spot 3 25.78 53.83 1.88 4.04 1.17 4.33 8.96
dissolved into the liquid phase, and precipitated on the surface of the Spot 4 14.71 0.29 0.34 8.68 1.77 10.13 64.07
Spot 5 13.24 22.19 1.37 10.58 1.77 4.96 35.89
large grains with low saturated solubility. Therefore, the large grains
Spot 6 25.02 0.88 1.02 12.08 2.53 12.78 45.70
gradually engulfed the surrounding small PZNNT grains and grown Spot 7 16.31 0.42 0.54 8.75 2.02 11.28 60.67
rapidly. Spot 8 15.89 0.39 0.42 9.88 2.15 9.77 61.50
However, the growth driving force of PZNNT matrix materials far
away from the PT template was mainly based on reducing their surface
energy. With the sintering temperature increased, the viscosity of liquid was gradually approaching the theoretical stoichiometric ratio of Pb2+/
phase decreased and grains growth accelerated in PZNNT-PT system. (Zr4++Ti4+) in PZNNT matrix materials. With the sintering tempera­
From Fig. 9, the rich Pb element distribution (spot 1) and equiaxed ture at 1050 °C, the grain size of PZNNT-PT ceramics obviously in­
grain (spot 2) in PZNNT-PT ceramics existed at 900 °C. Because liquid creased. Later, more stable solid solution of PZNNT-PT ceramics with
phase formation would promote ionic diffusion and transmission, the no Ti-rich regions can be obtained. Consequently, with the liquid phase
chemical reaction between PT template and PZNNT matrix materials disappearing around 1050–1150 °C, the grain growth in PZNNT-PT
was starting. When the sintering temperature was 1000 °C, some re­ system primarily related with the PZNNT matrix materials. At 1050 °C,
gions were consisted of rich Zn and Pb phase (spot 3) and the ratio of the rich Zn and Ti elements existed in Ti-rich regions (spot 5) with the
Pb2+/(Zr4++Ti4+) in equiaxed grain (spot 4) was around 1:1.2, which ratio of Pb2+/(Zr4++Ti4+) ~1:1 (spot 6) in PZNNT-PT ceramics. With

Fig. 9. EDS images of PZNNT-PT ceramics sintered at different temperature of Fig. 8.

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L. Li, et al.
Fig. 10. TG-DSC curves of PZNNT-PT ceramics prepared by tape casting methods.
further increase the sintering temperature, the chemical reaction be­
tween PT template and PZNNT matrix materials became completely.
The ratio of Pb2+/(Zr4++Ti4+) was slightly deviated the stoichio­
metric ratio in PZNNT-PT ceramics, because of PbO volatilization at the
higher sintering temperatures.
TG-DSC curves of PZNNT-PT ceramics using tape casting methods is
shown in Fig. 10. From TG curves, there was no obviously weightless
peak until 1100 °C, and the corresponding DSC curve showed en­
dothermic peaks at 905 °C and 1120 °C. Because the melting point of
PbO is 889 °C, the endothermic peaks at 905 °C can be attributed to the
PbO liquid phase from the PT template. When the temperature was
higher than 1100 °C, the TG curve showed obvious weight loss, corre­
sponding to the endothermic peak of 1120 °C, which was due to the
volatilization of PbO in PZNNT-PT ceramics.
From above analysis, the chemical reaction between PT template and
PZNNT matrix was mainly divided into two processes: one is the gradual
decomposition and disappearance of the PT template, accompanying
with the grain boundary motion between PT template and surrounding
PZNNT matrix. The other is the gradual grains growth of PZNNT far
away from PT template, which is dominated by Ostwald ripening me­
chanism. Finally, the more stable solid state of PZNNT-PT materials can
be obtained at 1150 °C. Fig. 11 shows the sketch map of reaction
Fig. 11. Reaction mechanism of PZNNT-PT ceramics prepared by plate-like PT as template.
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mechanism for PZNNT-PT ceramics. From Fig. 10, the plate-like PT
template was distributed parallel to tape casting direction in PZNNT
matrix materials at initial stage. With the sintering temperature in­
creased, firstly the situ chemical reaction based on element diffusion
occurred between the interface of PT template and PZNNT matrix ma­
terials, then PT template decomposed to form Pb-rich liquid phase,
which enhanced the dissolution of the PT template, the PZNNT/PT in­
terface movement, the PZNNT grain growth surrounding the PT tem­
plate, and leaving the Ti-rich regions. Finally, the equiaxed grains of
PZNNT-PT ceramics were obtained with the disappearance of PT tem­
plate. Consequently, it was failed to fabricate the PZNNT-PT texture
ceramics. So, choosing an optimal anisotropy perovskite template to
fabricate the texture ceramics, the stability of template in matrix mate­
rials at the high sintering temperature is one of the most important
factors.
4. Conclusion
The plate-like PbTiO3 (PT) particles were added to the PZNNT
matrix materials by tape casting technology. The PZNNT-PT textured
ceramics was not fabricated successfully. Through the analysis of mi­
crostructure evolution, firstly the situ chemical reaction based on the
L. Li, et al.
element diffusion occurred between the interface of PT template and
PZNNT matrix materials, then the PT template decomposed to form the
Pb-rich liquid phase, which enhanced the dissolution of PT template.
Later, the PZNNT grains grow surrounding the PT template, leaving the
Ti rich regions. Finally, the equiaxed grains of PZNNT-PT ceramics were
obtained with the disappearance of PT template. Since PT template
with low thermal stability would react with PZNNT matrix materials
and did not contribute to grain orientation, in order to successfully
fabricate the textured ceramics, plate-like PT template with high
thermal stability is needed.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ­
ence the work reported in this paper.
Acknowledgements
This work was supported by the China-Poland International
Collaboration Fund of National Natural Science Foundation of China
[Grant no. 51961135301], the Fundamental Research Funds for the
Central Universities [Grant no. 3102019GHJD001, 3102019MS0406],
the National Natural Science Foundation of China [Grant no.
51702259, 51672219], the International Cooperation Foundation of
Shaanxi Province China [Grant no. 2019 KW-054, 2020 KW-032], the
“111” Project [Grant no. B08040] and the Basic Research Program of
Shenzhen [Grant no. JCYJ20170306155944271]. Sponsored by the
seed foundation of Innovation and Creation for Graduate Students in
Northwestern Polytechnical University [CX2020079]. The XRD, SEM
and TG-DSC were characterized in Analytical and Testing Center of
Northwestern Polytechnical University.
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