Journal of Solid State Chemistry 316 (2022) 123564

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Journal of Solid State Chemistry

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Effect of sintering additives on the densification and dielectric properties of

Sr0.5Ba0.5Nb2O6 ceramics synthesized by a soft-chemistry method
€ferstein *, Stefan G. Ebbinghaus
Roberto Ko
Institute of Chemistry, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Straße 2, 06120, Halle, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Nano-crystalline Sr0.5Ba0.5Nb2O6 powders with addition of LiNbO3 or LiF as sintering additives were prepared by
Sintering aid a soft-chemistry synthesis using polyethylene glycol. Calcination at 600
C results in nanocrystalline powders
Permittivity (dcryst.  30 nm) which were sintered between 1000 and 1300
C to ceramic bodies. By addition of 10 and 20 mol
Strontium barium niobate
% LiNbO3, the sintering temperature was reduced by about 200 K and the activation energy of the initial stage of
Band gap
Lithium niobate
sintering decreases from 386 to 271 kJ mol1. The sintering aid improves the grain growth and dense ceramic
Relaxor bodies were obtained after sintering at 1125
C for 1 h. A higher LiNbO3 content favors the formation of a pillar-
like microstructure. XRD patterns of ceramics sintered above 1000
C show only reflections of the Sr0.5Ba0.5Nb2O6
phase indicating an incorporation of LiNbO3 in the Sr0.5Ba0.5Nb2O6 structure. Dielectric measurements reveal a
diffuse phase transition and a relaxor-like behavior. The phase transition temperature (Tm) depends on the sin-
tering conditions and is between 117 and 127
C for 10 mol% LiNbO3, which is very close to pure
Sr0.5Ba0.5Nb2O6, while addition of 20 mol% shifts Tm to around 200
C and the transition becomes slightly more
diffuse. The optical band gap of the samples is  3.3 eV and depends slightly on the sintering conditions. We also
tried LiF as sintering aid, but this leads to the formation of considerable amounts of secondary phases in the
ceramics and relative densities of only 82%.

1. Introduction nano-sized powders [14,18–21]. Compacts of strontium barium niobate

reveal moderate densification behaviour. Thus, sintering to dense
As a lead-free and eco-friendly alternative to e.g. PZT (lead zirconate ceramic bodies requires high temperatures and long soaking times
titanate), strontium barium niobate, SrxBa1-xNb2O6 (SBN), is an inter- [14–22]. The densification behavior and the grain growth can generally
esting candidate because of its ferroelectric, pyroelectric, piezoelectric, be improved using sintering additives [23,24]. For example, Wang et al.
electro-optic, and photorefractive properties [1–4]. Due to its ferroelec- [25] used SiO2 as additive to decrease the sintering temperature. Due to
tric behavior, SBN is also used in magnetoelectric composites [5–7]. the addition of SiO2, Tm is shifted to lower temperatures. On the other
Furthermore, some authors report about photocatalytic activities [8,9]. hand, some authors utilized V2O5 as additive (liquid phase sintering) and
SrxBa1-xNb2O6 is ferroelectric in the x range from 0.25 to 0.75 and observed an increase of Tm [26–28]. Furthermore, addition of Bi2O3, PbO
crystallized in the tetragonal tungsten-bronze (TTB) structure. Its ferro- and Nb2O5 enhance the densification and influence the dielectric
electric properties are sensitive to the composition and preparation behavior marginally [27].
procedure [10,11]. With rising strontium content an increasing relaxor In this work, we investigated the influence of LiNbO3 and LiF on the
behavior can be observed [12]. For Sr0.5Ba0.5Nb2O6, the permittivity sintering and dielectric behavior of Sr0.5Ba0.5Nb2O6. The samples were
maximum (Tm), which reflects the ferroelectric ⇆ paraelectric phase synthesized by a one-pot soft-chemistry method leading to nano-scaled
transition, is between 110 and 130
C for single crystals [3,11], while for preceramic powders. Phase evolution and microstructure of ceramics
polycrystalline samples values between 40 and 177
C have been re- bodies were monitored by XRD and SEM. The sintering behavior was
ported [13–17]. investigated up to 1350
C. Additionally, the samples were characterized
Usually, Sr0.5Ba0.5Nb2O6 is synthesized by the conventional mixed- by diffuse reflectance and dielectric measurements.
oxide method which leads to coarse-grained powders. Additionally,
few soft-chemistry syntheses have been reported to produce sub-micro or

* Corresponding author.
E-mail address: [email protected] (R. K€
oferstein).

https://doi.org/10.1016/j.jssc.2022.123564
Received 27 June 2022; Received in revised form 2 September 2022; Accepted 4 September 2022
Available online 9 September 2022
0022-4596/© 2022 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

2. Experimental Sr0.5Ba0.5Nb2O6 leads to an enhanced densification at low sintering

temperatures with relative densities of 80(1) and 82(1) % after sintering
2.1. Material preparation at 1050
C and 1150
C, whereas at 1200
C a reduction to 77(1) % was
observed. XRD investigations (Fig. S1, supporting information) of
All samples were synthesized according to the one-pot soft-chemistry SBNþLF ceramics sintered at 1050
C and 1200
C leads to a mixture of
method as described earlier [14]. The amount of the added sintering Sr0.5Ba0.5Nb2O6, Li4Sr3.06Nb6O20 (JCPDS #01-089-7516), Li2O (JCPDS
additive is related to the amount of Sr0.5Ba0.5Nb2O6. For the addition of #01-012-0254), and Ba3Nb2O8 (JCPDS #01-072-0192). The fraction of
LiNbO3, the initial compositions of the samples were as follows: 1 mol secondary phases was calculated to be 25–30 wt%. For that reason, LiF is
Sr0.5Ba0.5Nb2O6 þ x mol LiNbO3 with x ¼ 0.1 and 0.2 (¼ 3.75 and 7.50 not suitable as sintering aid for Sr0.5Ba0.5Nb2O6.
wt%), abbreviated as SBNþLN-x.
In a typical reaction, 0.02 mol NbCl5 (Alfa Aesar, 99%) was dissolved
3.1. Sr0.5Ba0.5Nb2O6 þ LiNbO3
in 25 ml 2-methoxyethanol. 50 ml polyethylene glycol (PEG400) and 52
g citric acid were added under stirring on a heating plate at 150
C until a
3.1.1. Synthesis and powder characterization
clear solution resulted. Equimolar amounts of SrCl2⋅6H2O (Merck, 
In the following we used LiNbO3 as sintering aid. 1 mol
99%) and BaCl2⋅2H2O (Fluka,  99%) were solved together in 10 ml 1,2-
Sr0.5Ba0.5Nb2O6 þ x mol LiNbO3 (SBNþLN-x) with x ¼ 0.1 and 0.2 were
ethanediol and Li(CH3COO)⋅2H2O (Chemapol, purum) was solved in 5
synthesized by a one-pot synthesis. To obtain white nanoscaled powders,
ml 1,2-ethanediol. The amounts of the Sr-, Ba-, and Li-compounds are
the viscous (Sr,Ba,Nb,Li)-solutions were calcined at 600
C for 2 h. The
calculated as nSr ¼ nBa ¼ nNb/(2[2þx]) and nLi ¼ nNb⋅x/(2þx) (x ¼ 0.1
XRD patterns (Fig. 1) show only reflections of tetragonal Sr0.5Ba0.5Nb2O6
and 0.2; molar fraction of LiNbO3 related to the amount of
(JCPDS #01-074-6520) and rhombohedral LiNbO3 (JCPDS #01-078-
Sr0.5Ba0.5Nb2O6). Afterwards, both the (Sr,Ba)- and Li-solutions were
0250), however an increasing background level around 2θ ¼ 30
in-
added to the hot Nb-solution. The reaction mixture was continuously
dicates an amorphous fraction in the samples. The specific surface areas
stirred on the heating plate at 250
C for about 3–4 h until it turned to a
(BET method) were determined to be 32(3) m2 g1 for x ¼ 0.1 and 24(2)
white highly viscous solution. The resulting (Sr,Ba,Nb,Li)-solutions were
m2 g1 for x ¼ 0.2, which correspond to equivalent primary particle sizes
calcined at 600
C for 2 h (rate 10 K min1) in static air leading to white
of 35(3) and 47(3) nm. The volume-weighted average crystallite size of
nanoscaled powders. Ceramic bodies were fabricated from these powders
the Sr0.5Ba0.5Nb2O6 phase for SBNþLN-0.1 and SBNþLN-0.2 is 31(3) and
by mixing with 10 wt% of a saturated aqueous polyvinyl alcohol (PVA)
29(3) nm, respectively.
solution as pressing aid and uniaxially pressed at about 71 MPa into
pellets (green density: 2.2 g cm3). These pellets were sintered on a ZrO2
3.1.2. Sintering, microstructure, and phase composition of the ceramics
fibre mat between 1000 and 1300
C (heating-/cooling rate 5 K min1)
Non-isothermal dilatometric measurements of SBN and SBNþLN-x (x
with a soaking time of 1 h to the final ceramic bodies. These had a
¼ 0.1 and 0.2) powder compacts up to 1350
C in flowing air are shown
thickness of about 1–1.6 mm and diameters of 4–6 mm.
in Fig. 2. The SBN sample starts to shrink slightly at about 1100
C while
For comparative purposes, pure Sr0.5Ba0.5Nb2O6 (abbreviated as SBN)
at about 1220
C the shrinkage increases significantly. The shrinking rate
was also prepared according to the aforementioned synthesis.
achieves a maximum at 1325
C with 1.08% min1. The SBNþLN-x
The common sintering additive LiF was also tested. For this purpose,
compacts with the sintering additive show an improved shrinkage
Sr0.5Ba0.5Nb2O6, prepared as mentioned above, was calcined at 1100
C
behavior. A first slight shrinkage begins around 700
C, whereas a
for 2 h (rate 10 K min1) and mixed in a planetary mill with 76 mol% LiF
considerable densification process starts at 1150
C (SBNþLN-0.1) and
(¼ 5.0 wt%, Sigma-Aldrich, 98%) in a polyamide jar using propane-2-ol
1000
C (SBNþLN-0.2), respectively. The shrinkage maxima are shifted
and ZrO2-balls. After drying, the white powder was pressed and sintered
to lower temperatures of 1300
C and 1209
C with values in both cases
to ceramics as described above. The samples were abbreviated as
of 1.28% min1 as shown in the inset of Fig. 2. The shrinkage rates of
SBNþLF.
the three samples points to viscous flow (sliding process of whole grains)
as a dominant shrinkage mechanism, because diffusion processes cause
2.2. Characterization

X-ray powder diffraction patterns were recorded at room temperature

on a Bruker D8-Advance diffractometer, equipped with a one-
dimensional silicon strip detector (LynxEye™) using Cu-Kα radiation
and a counting time of 1 s per data point. Crystallite sizes and strain
parameters were calculated from XRD line broadening (integral peak
breadth) using the software suite WinXPOW [29] applying the Scherrer
and Wilson equations. Differential thermoanalytic (DSC) investigations
in flowing synthetic air (50 ml min1) were performed with a heating
rate of 10 K min1 using a Netzsch STA 449F5 system. Atom absorption
spectroscopy measurements were carried out with an Agilent AA 280FS.
Scanning electron microscope images were collected with a Phenom
ProX SEM in backscattered electron mode (BSE). For impedance in-
vestigations, the ceramic bodies with a thickness of 1.2–1.4 mm were
sputtered on both sides with 100 nm thick gold electrodes using a
Cressington Sputter Coater 108auto. An Impedance Analyzer 4192A
(Hewlett Packard) was used for frequency- and temperature dependent
impedance measurements.

3. Results and discussion

Fig. 1. Room-temperature XRD patterns of SBNþLN-x (¼ Sr0.5Ba0.5Nb2O6þx-
LiF is used as a common sintering additive for various ceramic ma- LiNbO3) powders after calcining at 600
C for 2 h (heating rate 10 K min1): (a)
terials [30–34], therefore we tested LiF to reduce the sintering temper- x ¼ 0.1, (b) x ¼ 0.2. The inset shows a magnification of the XRD pattern for x ¼
ature of Sr0.5Ba0.5Nb2O6. Additions of 76 mol% (¼ 5 wt%) LiF to 0.1 recorded with a prolonged counting time of 10 s per data point.

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R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

mixed-oxide method [41]. By addition of LiNbO3 the activation energy

decreases to 300(18) and 271(15) kJ mol1 for SBNþLN-0.1 and
SBNþLN-0.2, respectively.
Based on these results, for further investigations the nanocrystalline
powders were pressed to pellets and sintered in static air at temperatures
between 1000 and 1300
C for 1 h (heating-/cooling rate: 5 K min1).
The bulk densities of the white-yellow ceramics bodies were calculated
from their weight and geometric dimensions. The obtained densities are
related to the single crystal density of Sr0.5Ba0.5Nb2O6 [42]. Dense ce-
ramics (relative density 90%) of pure Sr0.5Ba0.5Nb2O6 can be only ob-
tained after firing above 1300
C. In contrast, by the addition of LiNbO3
densities above 90% can be obtained already at 1175
C (x ¼ 0.1) and
1125
C (x ¼ 0.2) as shown in Fig. 4. Increasing temperatures raise the
relative bulk densities further up to 96(1) %. The SBNþLN-0.2 ceramics
show a very slight decrease in density after firing at 1300
C due to a
change in the microstructure as described below. In summary, the use of
the sintering additive LiNbO3 results in dense ceramics at significantly
lower temperature and shorter sintering time, compared to pure
Fig. 2. Non-isothermal dilatometric measurements up to 1350
C (heating rate Sr0.5Ba0.5Nb2O6.
5 K min1) in flowing air of (a) SBN, (b) SBNþLN-0.1, (c) SBNþLN-0.2 of Typical microstructures of SBNþLN-x ceramics are shown in Fig. 5.
compacted powders calcined at 600
C. The inset shows the shrinkage rates. The average grain size (Øli) was estimated by counting of at least 700
grains using the lineal intercept method [43]. Ceramics with x ¼ 0.1
typical shrinkage rates between 104 and 101 % min1 [35–38]. consist of globular and irregular shaped grains. Their sizes are between
Furthermore, DSC measurements of SBNþLN-0.2 up to 1350
C did not 0.5 and 3.7 μm (Øli ¼ 1.7(4) μm), 1–7 μm (Øli ¼ 3.0(5) μm), and 1–18 μm
show any indication of the formation of a liquid phase (Fig. S2, sup- (Øli ¼ 6(2) μm) after sintering at 1150, 1200, and 1300
C, respectively.
porting information) indicating that the densification process is caused SBNþLN-0.2 samples show globular/irregular grains after sintering at
by solid-state phase sintering. The activation energy of the initial state of 1100
C and 1150
C with grains sizes between 0.7 and 5.2 μm (Øli ¼
sintering can be calculated from the non-isothermal dilatometric mea- 2.3(2) μm) and 1–10 μm (Øli ¼ 4.8(4) μm). On the other hand, sintering
surements applying the equation for the constant heating rate (CHR) at 1200
C and 1300
C leads to a change of the microstructure. After
method (1) [39,40]. firing at 1200
C, we find a bimodal grain size distribution with irregular
grains from 1.2 to 6 μm and few grains of about 8 μm. In addition small
dðΔL Þ 2aEa ΔL pillars with lengths between 1.5 and 4 μm and widths ranging from 3 to
T 2ð 0 Þ ¼ 
L
(1)
dt nR L0 19 μm as well as large rectangular micro crystals up to 200 μm were
observed (Fig. S3, supporting information). After sintering at 1300
C the
where, T ¼ temperature, ΔL L1 0 ¼ relative shrinkage, t ¼ time, a ¼ ceramic bodies exclusively consist of pillars with dimensions similar to
heating rate, n ¼ constant depending on the mechanism of initial stage of the ones after firing at 1200
C and larger rectangular crystals with
sintering, Ea ¼ activation energy, R ¼ universal gas constant. As lengths up to 400 μm as shown in Fig. 5d.
mentioned above, the initial stage of sintering can be described by the The phase composition after sintering was examined by XRD. Fig. 6
viscous flow mechanism (n ¼ 2 [39]). Thus, Ea can be calculated from the shows the XRD patterns of SBNþLN-x sintered ceramics. After sintering
slope by plotting the left hand-side of equation (1) versus ΔL L1 0 (as at 900
C reflections of tetragonal Sr0.5Ba0.5Nb2O6, and traces of ortho-
depicted in Fig. 3). For Sr0.5Ba0.5Nb2O6 the activation energy for the rhombic SrNb2O6 (JCPDS #00-028-1243) are observed. Additionally, the
initial stage of sintering was calculated as 386(22) kJ mol1, which is sample with x ¼ 0.2 shows the presence of rhombohedral LiNbO3. The
significantly lower than the activation energy of 825 kJ mol1 found for LiNbO3 and SrNb2O6 reflections disappear after sintering at 1000
C for
coarse-grained Sr0.5Ba0.5Nb2O6 synthesized by the conventional both x ¼ 0.1 and 0.2, as visible in Fig. 6c and d. Up to the highest sin-
tering temperature of 1300
C the XRD patterns only show reflections of
the Sr0.5Ba0.5Nb2O6 phase (Fig. 6e,f). Even a prolonged counting time of

Fig. 3. Plot of T2[d(ΔL L1 1

0 )dt vs. ΔL L0 . For the sake of clarity, every 30th data Fig. 4. Bulk densities of ceramic bodies after sintering at various temperatures
point is marked by a symbol. Solid lines are the fit results. for 1 h (heating-/cooling rate 5 K min1).

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R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

Fig. 5. SEM-BSE images of selected SBNþLN-x ceramic bodies sintered at different temperatures (Ts) for 1 h: (a) Ts ¼ 1150
C, (b) Ts ¼ 1150
C (c) Ts ¼ 1300
C, and
(d) Ts ¼ 1300
C.

10 s per step does not reveal any traces of secondary phases (Fig. S4, 1200 and 1300
C gave values of 3.26(3) eV. However, in x ¼ 0.2 ce-
supporting information) suggesting the formation of a solid solution ramics, sintered above 1100
C, an additional absorption feature appears
between Sr0.5Ba0.5Nb2O6 and LiNbO3 in the tetragonal tungsten–bronze at lower energies in the range between 2.4 and 3.1 eV, most likely caused
structure which will be the subject of further investigations. The pro- by defects due the incorporation of Liþ into the Sr0.5Ba0.5Nb2O6 structure
posed formation of a solid solution is additionally supported by the [54–56]. Because of the overlapping of these two absorption regions, we
absence of the melting peak of LiNbO3 around 1250
C [44,45] in the used a baseline approach according to Makuła et al. [47] to derive the
DSC measurement as mentioned above. The solid solution can be written band gap as seen in Fig. 7. The so obtained band gaps are 3.34(2) eV after
as Liy(Sr0.5Ba0.5)1-y/2Nb2O6, where y represents the molar fraction of sintering at 1100
C and 3.36(6) eV for x ¼ 0.2 samples sintered between
LiNbO3 which can be calculated from the x parameter as y ¼ x/(1þx). 1150 and 1300
C. As a conclusion, the use of the sintering additive
Solid solutions between SBN and (K,Na)NbO3 has been reported by LiNbO3 does not lead to a considerable change of the band gap compared
several authors [46–48]. Because of the volatility of lithium salts at high to pure Sr0.5Ba0.5Nb2O6 [14].
temperatures, sintering often leads to a partial sublimation of Li2O
[49–51]. For our samples, atom absorption spectroscopy indicates that 3.1.3. Impedance spectroscopy
the loss of lithium accounts to about 6–7% after sintering at 1300
C for 1 Fig. 8 shows the evolution of the relative permittivity (εr0 ) and
h. dissipation factor (tan δ) with temperature for ceramic bodies with x ¼
The optical band gap energies were obtained from diffuse reflectance 0.1 at 1 kHz. Samples fired at 1150, 1200, and 1300
C show diffuse
spectra using the KubelkaMunk theory. The optical band gap (Eg) can be ferroelectric ⇆ paraelectric phase transitions with broad maxima at
described by equation (2) [52]: 127(1), 117(1), and 118(1)
C, close to pure Sr0.5Ba0.5Nb2O6 [3,14]. The
εr0 values at these maxima increases with sintering temperature from
F(R)⋅hν ¼ k(hν  Eg)1/n (2) 1362(123) to 3135(282) most likely caused by increasing grain sizes and
(F(R) – Kubelka–Munk function, k – energy-independent constant, Eg densities. Fig. 9 shows the temperature (Tm) of the permittivity maxima
– optical band gap, n – exponent reflecting the type of transition with n ¼ depending on frequencies. Tm is shifted towards higher temperatures
2 for direct allowed transitions and n ¼ 0.5 for indirect allowed transi- with increasing frequencies due to the relaxor-like behavior of the sam-
tions). As described elsewhere, Sr0.5Ba0.5Nb2O6 has an indirect band gap ples [57,58]. The shift of Tm in the range from 1 kHz to 3 MHz is 6(2) K
of 3.40–3.29 eV, depending on the sintering temperature [14,53]. Thus, for the sample sintered at 1150
C and increases to 11(2) K after sintering
Eg can be calculated by plotting of (F(R) ⋅ hν)0.5 versus hν and extrapo- at 1300
C (inset in Fig. 9).
lating the slope to F(R) → 0 (Fig. 7). Using this method, the band gap The evolution of the permittivity depending on temperature for
energies of SBNþLN-x ceramics with x ¼ 0.1 were determined as 3.39(4) SBNþLN-0.2 ceramics can be seen in Fig. 10a. The samples with x ¼ 0.2
and 3.32(2) eV after sintering at 1100 and 1150
C, whereas sintering at show a shift of Tm towards higher temperatures. Sintering at 1100
C
does not lead to a clear phase transition at 1 kHz, whereas frequencies

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R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

Fig. 8. Temperature dependence of the real part of the relative permittivity (εr0 )
and tan δ at 1 kHz of SBNþLN-0.1 ceramic bodies sintered for 1 h at: (a) 1150


C, (b) 1200
C, and (c) 1300
C. The uncertainty of the data is smaller than the
symbol size and is lower than 5%.

Fig. 9. Temperature dependence of the relative permittivity (εr0 ) and the

dissipation factor (tan δ) at various frequencies for SBNþLN-0.1 sintered at
Fig. 6. Room-temperature XRD patterns of SBNþLN-x ceramics after sintering 1200
C for 1 h. The inset shows the temperature of the permittivity maximum
at different temperatures (Ts) for 1 h (heating-/cooling rate 5 K min1). (Tm) depending on frequency and sintering temperature for samples sintered at:
(a) 1150
C, (b) 1200
C, and (c) 1300
C. The uncertainty of the data is smaller
than the symbol size and is lower than 5%.

above 1 kHz reveal a maximum at 213(2)
C (Fig. 10b and Fig. S5,
supporting information). The permittivity maximum of the dense
ceramic, sintered at 1150
C (x ¼ 0.2), appears at 196(2)
C with εr0 ¼
3071(277) at 1 kHz and shifts to 200(2)
C at 3 MHz with εr0 ¼ 2580(232)
(Fig. S6, supporting information). The development of εr0 for samples (x
¼ 0.2) sintered at 1200 and 1300
C shows only at frequencies 100 kHz
a clear permittivity maximum at 223(2) and 221(2)
C corresponding to
the diffuse ferroelectric ⇆ paraelectric phase transition (Figs. S7 and S8,
supporting information). Moreover, both the considerable shift of Tm to
higher temperatures and the reduction of the permittivity maxima after
sintering from 1150 to 1300
C correlates with the appearance of a pillar-
like microstructure as also observed in pure Sr0.5Ba0.5Nb2O6 [14].
Frequency-dependent dielectric measurements at room temperature (23


C) in the range from 0.5 kHz to 10 MHz are shown in Fig. 11. The
samples show decreasing permittivity values with rising frequency, while
the dissipation factor (tan δ) slightly increases. The εr0 values of the x ¼
0.1 ceramics (Fig. 11a) rise with sintering temperature caused by an
increase in density and grain sizes. However, a different behavior can be
Fig. 7. (F(R) ⋅ hν)0.5 versus hν of SBNþLN-x ceramics sintered at 1200
C for 1
observed for x ¼ 0.2 ceramics (Fig. 11b). Sintering from 1100 to 1150
C
h. (a) x ¼ 0.1, (b) x ¼ 0.2. The inset shows the diffuse reflectance spectra.
results in larger permittivities, while firing at 1200 and 1300
C leads to
significant lower εr0 values, due to the change in microstructure after

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R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

Fig. 10. Temperature dependence of the real part of εr0 and tan δ at 1 kHz (a)
Fig. 11. Frequency dependence of the real part of εr0 and the dissipation factor
and 100 kHz (b) of SBNþLN-0.2 ceramic bodies sintered for 1 h at: (a) 1100
C,
at 23
C for SBNþLN-x ceramic bodies sintered at the indicated temperatures.
(b) 1150
C, (c) 1200
C and (d) 1300
C. The uncertainty of the data is smaller
(a) x ¼ 0.1, (b) x ¼ 0.2. The uncertainty of the data is smaller than the symbol
than the symbol size and is lower than 5%.
size and is lower than 5%.

sintering at these temperatures as mentioned above. The ceramics sin- ρdc

tered at 1200
C (x ¼ 0.2) consist of globular/irregular grains along with ρ* ¼ (4)
1 þ ðiωτÞβ
pillar-like grains which effects higher εr0 values compared to those sin-
tered at 1300
C, which only show pillar-like grains. Decreasing (β  constant phase shift (CPE) coefficient, τ ¼ ρdcεε0). The high-
permittivity values by changing from a globular/irregular to a pillar-like temperature impedance data were modelled using equivalent circuits
microstructure were also observed in Sr0.5Ba0.5Nb2O6 ceramics [14]. consisting of one or two parallel resistance-capacitor (RC) elements. For
The dielectric behavior of a relaxor ferroelectric can be expressed by x ¼ 0.2 ceramics sintered at 1200 and 1300
C, the impedance data
the following Curie-Weiss type law (3) [59]: reveal two semicircle arcs, which can be described by two parallel con-
nected RC-elements suggesting two different relaxation processes
1 1 ðT  Tm Þγ (Fig. 12). The two obtained relative permittivities for each of these ce-
 ¼ (3)
ε εm C0 ramics are 13⋅103 and 27⋅104 sintered at 1200
C, whereas values of and
9⋅103 and 17⋅104 were found after sintering at 1300
C. The smaller
where, εm is the permittivity maximum, Tm is the temperature at εm, C0 is values can be related to bulk contributions, while the larger values most
a constant, and the exponent γ is the diffuseness coefficient. Thus, γ can likely corresponds to grain boundary effects, as, according to Irvine et al.
be obtained from a plot of ln(ε1ε1m ) versus ln(TTm). x ¼ 0.1 ceramics [63], the bulk permittivity is at least one order of magnitude lower than
reveal diffuseness coefficients between 1.7 and 1.8, which is comparable grain boundary permittivity. Cole-Cole plots for the other ceramic sam-
with pure Sr0.5Ba0.5Nb2O6 [14], whereas x ¼ 0.2 samples show a slightly ples (Fig. S9 and Fig. S10, supporting information) show single semicircle
larger γ value of 1.8–1.9. Larger γ values indicate an increasing degree of arcs indicating a single relaxation process. Because of the calculated
lattice disorder most likely due to formation of a solid solution between permittivities between 1.6⋅103 and 3.5⋅103 these values can be assigned
LiNbO3 and Sr0.5Ba0.5Nb2O6 [60,61]. to the bulk effect, showing that grain boundary contributions play a
The discussion above is based on the model of a lossy capacitor and negligible role in these samples.
does not consider a possible dc-conductivity. At elevated temperatures Due to the addition of LiNbO3, we observed an increase of the
the ceramics show considerable dc-conductivities suggesting a semi- permittivity maximum up to 50% and a considerable shift of Tm for x ¼
conducting nature. As reported elsewhere [62] for a single 0.2, compared to pure Sr0.5Ba0.5Nb2O6 [14].
resistance-capacitor (RC) element, the specific impedance (ρ*) is
described by equation (4):
4. Conclusion

Sr0.5Ba0.5Nb2O6 ceramics with the addition of 10 and 20 mol%

6
R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

Data availability

Data will be made available on request.

Acknowledgments

We are grateful to Dr. F. Oehler for AAS investigations.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://do

i.org/10.1016/j.jssc.2022.123564.

References

[1] A.M. Glass, Investigation of the electrical properties of Sr1-xBaxNb2O6 with special
reference to pyroelectric detection, J. Appl. Phys. 40 (1969) 4699–4713.
[2] D. Rytz, B.A. Wechsler, R.N. Schwartz, C.C. Nelson, C.D. Brandle, A.J. Valentino,
G.W. Berkstresser, Temperature dependence of photorefractive properties of
Fig. 12. Cole-Cole plots measured at the indicated temperatures of SBNþLN-0.2 strontium-barium niobate (Sr0.6Ba0.4Nb2O6), J. Appl. Phys. 66 (1989) 1920–1924.
[3] T. Lukasiewicz, M.A. Swirkowicz, J. Dec, W. Hofman, W. Szyrski, Strontium–barium
ceramic bodies sintered for 1 h at (a) 1200
C and (b) 1300
C. Fits were carried
niobate single crystals, growth and ferroelectric properties, J. Cryst. Growth 310
out using two parallel connected RC-elements. Lines are the respective fit re- (2008) 1464–1469.
sults, while symbols correspond to experimental data. The uncertainty of the [4] R.R. Neurgaonkar, L.E. Cross, Piezoelectric tungsten bronze crystals for SAW device
data is smaller than the symbol size and is lower than 5%. applications, Mater. Res. Bull. 21 (1989) 893–899.
[5] S. Tiwari, S. Vitta, Magnetoelectric and magnetodielectric coupling and microwave
resonator characteristics of Ba0.5Sr0.5Nb2O6/CoCr0.4Fe1.6O4 multiferroic composite,
LiNbO3 as sintering aid were synthesized by a one-pot method using Sci. Rep. 8 (2018), 11619.
PEG400. Calcining at 600
C results in white nanocrystalline powders [6] X.M. Chen, Y.H. Tang, I.-W. Chen, Z.C. Xu, S.Y. Wu, Dielectric and magnetoelectric
characterization of CoFe2O4/Sr0.5Ba0.5Nb2O6 composites, J. Appl. Phys. 96 (2004)
with crystallite sizes of 31(3) and 29(3) nm and specific surface areas of 6520–6522.
32(3) and 24(2) m2 g1. Dilatometric measurements on powder com- [7] R. K€ oferstein, F. Oehler, S.G. Ebbinghaus, Fine-grained magnetoelectric
pacts show that the sintering starts at significant lower temperatures with Sr0.5Ba0.5Nb2O6CoFe2O4 composites synthesized by a straightforward one-pot
method, Mater. Chem. Phys. 278 (2022), 125616.
addition of LiNbO3. The activation energies for the initial stage of sin-
[8] G. Han, S. Cao, B. Lin, UV photocatalytic activity for water decomposition of
tering were calculated as 300(18) and 271(15) kJ mol1 for 10 and 20 SrxBa1xNb2O6 nanocrystals with different components and morphologies, J. Chem.
mol% LiNbO3, respectively, while Sr0.5Ba0.5Nb2O6 without any sintering (2017), 2163608.
additive reveals an activation energy of 386(22) kJ mol1. Dense ceramic [9] K. Yoshida, H. Masai, Y. Takahashi, R. Ihara, T. Fujiwara, Fabrication of
Sr0.5Ba0.5Nb2O6-precipitated microstructured ceramics for photocatalytic
bodies were obtained after sintering at 1125
C, which is about 200 K application, J. Ceram. Soc. Jpn. 119 (2011) 731–735.
lower than for Sr0.5Ba0.5Nb2O6 ceramics without any sintering aid. XRD [10] S.-I. Kang, J.-H. Lee, J.-J. Kim, H.Y. Lee, S.-H. Cho, Effect of sintering atmosphere on
and DSC measurements indicate the incorporation of LiNbO3 into the densification and dielectric characteristics in Sr0.5Ba0.5Nb2O6 ceramics, J. Eur.
Ceram. Soc. 24 (2004) 1031–1035.
Sr0.5Ba0.5Nb2O6 structure by forming a solid solution during sintering. [11] A.A. Ballmann, H. Brown, The growth and properties of strontium barium
Temperature and frequency-dependent dielectric investigations show a metaniobate SrxBa1–xNb2O6, A tungsten bronze ferroelectric, J. Cryst. Growth 1
diffuse ferroelectric ⇆ paraelectric phase transition and a relaxor (1967) 311–314.
[12] W.H. Huang, Dwight Viehland, R.R. Neurgaonkar, Anisotropic glasslike
behavior. The dielectric maximum (Tm) slightly depends on the sintering characteristics of strontium barium niobate relaxors, J. Appl. Phys. 76 (1994)
temperature. Tm is around 120–130
C for the addition of 10 mol% 490–496.
LiNbO3 and shifts to about 200
C for 20 mol%. [13] S.H. Kshirsagar, A.N. Tarale, S.R. Jigajeni, D.J. Salunkhe, P.B. Joshi, Effect of Ni
doping on ferroelectric, dielectric and magneto dielectric properties of strontium
LiNbO3 as sintering additive considerably reduced the sintering barium niobate ceramics, Indian J. Pure Appl. Phys. 53 (2015) 119–124.
temperatures of SrxBa1-xNb2O6 ceramics without the formation of a [14] R. K€ oferstein, F. Oehler, S.G. Ebbinghaus, Investigations of nano-crystalline
liquid phase. Due to the additive, the phase transition temperature (Tm) Sr0.5Ba0.5Nb2O6 and bulk ceramics synthesized by a polymerization method using
PEG400, J. Eur. Ceram. Soc. 39 (2019) 1156–1163.
and the grain sizes can be easily tuned. LiNbO3 is also a potential
[15] M. Said, T.S. Velayutham, W.C. Gan, W.H. Abd Majid, The structural and electrical
candidate as sintering aid in SrxBa1-xNb2O6 based magnetoelectric properties of SrxBa(1-x)Nb2O6 (SBN) ceramic with varied composition, Ceram. Int.
composites. 41 (2015) 7119–7124.
[16] P.K. Patro, A.R. Kulkarni, C.S. Harendranath, Microstructure and dielectric
properties of strontium barium niobate ceramics synthesized by partial
CRediT authorship contribution statement coprecipitation, J. Eur. Ceram. Soc. 23 (2003) 1329–1335.
[17] T. Chen, S.Y. Wu, X.Q. Liu, X.M. Chen, A novel sol–gel route to synthesize
Roberto Ko € ferstein: Conceptualization, Data curation, Formal (Sr0.5Ba0.5)Nb2O6 ceramics with enhanced electrocaloric effect, J. Adv. Dielectr. 7
(2017), 1750012.
analysis, Investigation, Project administration, Resources, Validation, [18] A.B. Panda, A. Pathak, P. Pramanik, Low temperature preparation of
Visualization, Writing – original draft, Writing – review & editing. Stefan nanocrystalline solid solution of strontium–barium–niobate by chemical process,
G. Ebbinghaus: Conceptualization, Project administration, Resources, Mater. Lett. 52 (2002) 180–186.
[19] S.R. Dhage, R. Pasricha, V. Ravi, Synthesis of Sr0.5Ba0.5Nb2O6 by urea method,
Supervision, Validation, Writing – original draft. Mater. Lett. 59 (2005) 1053–1055.
[20] R. Pasricha, V. Ravi, Synthesis of Sr0.5Ba0.5Nb2O6 by citrate gel method, mater,
Declaration of competing interest Chem. Phys. 94 (2005) 34–36.
[21] C.M. Dudhe, S.B. Nagdeot, C.P. Chaudhari, Ferroelectric domains in
Sr0.5Ba0.5Nb2O6 (SBN50) at nanolevel, Ferroelectrics 482 (2015) 104–112.
The authors declare that they have no known competing financial [22] S.B. Deshpande, H.S. Potdar, P.D. Godbole, S.K. Date, Preparation and ferroelectric
interests or personal relationships that could have appeared to influence properties of SBN:50 ceramics, J. Am. Ceram. Soc. 75 (1992) 2581–2585.
[23] R. K€ oferstein, L. J€ager, M. Zenkner, H.-P. Abicht, Preparation and sintering
the work reported in this paper.
behaviour of a fine grain BaTiO3 powder containing 10 mol% BaGeO3, J. Mater. Sci.
43 (2008) 832–838.
[24] A. Talimian, H.F. El-Maghraby, M. Michalkova, D. Galusek, Sintering and grain
growth behaviour of magnesium aluminate spinel: effect of lithium hydroxide
addition, J. Eur. Ceram. Soc. 41 (2021) 5634–5643.

7
R. K€
oferstein, S.G. Ebbinghaus Journal of Solid State Chemistry 316 (2022) 123564

[25] L. Wang, S. Wanmei, M. Kunchang, L. Shijun, Effect of silica sintering additive on [45] B.A. Scott, G. Burns, Determination of stoichiometry variations in LiNbO3, and
the sintering behavior and dielectric properties of strontium barium niobate LiTaO3, by Raman powder spectroscopy, J. Am. Ceram. Soc. 55 (1972) 225–230.
ceramics, J. Eur. Ceram. Soc. 29 (2009) 1427–1432. [46] Y.B. Yao, C.L. Mak, B. Ploss, Phase transitions and electrical characterizations of
[26] Q.W. Huang, L.H. Zhu, J. Xu, P.L. Wang, H. Gu, Y.B. Cheng, Effect of V2O5 on (K0.5Na0.5)2x(Sr0.6Ba0.4)5xNb10O30 (KNSBN) ceramics with ‘unfilled’ and ‘filled’
sintering behaviour, microstructure and dielectric properties of textured tetragonal tungsten–bronze (TTB) crystal structure, J. Eur. Ceram. Soc. 320 (2012)
Sr0.4Ba0.6Nb2O6 ceramics, J. Eur. Ceram. Soc. 25 (2005) 957–962. 4353–4361.
[27] S. Nishiwaki, J. Takahashi, K. Kodaira, Effect of additives on microstructure [47] Y. Jiang, R. Guo, A.S. Bhalla, Single crystal growth and ferroelectric properties of
development and ferroelectric properties of Sr0.3Ba0.7Nb2O6 ceramics, Jpn. J. Appl. α(Ba1-xSrx)Nb2O6:β(Na1-yKy)NbO3 solid solutions, J. Appl. Phys. 84 (1998)
Phys. 33 (1994) 5477–5481. 5140–5146.
[28] A.Y. Oral, M.L. Mecartney, Properties of sol-gel derived strontium barium niobate [48] R.R. Neurgaonkar, W.K. Cory, J.R. Oliver, W.W. Clark III, G.L. Wood, M.J. Miller,
ceramics and the effect of V2O5 additive, J. Mater. Sci. 36 (2001) 5519–5527. E.J. Sharp, Growth and ferroelectric properties of tungsten bronze Ba2-xSrxK1-
[29] Program WinXPOW v2.11, Stoe & Cie GmbH, Darmstadt, 2004. yNayNb5O15 (BSKNN) single crystals, J. Cryst. Growth 84 (1987) 629–637.
[30] U. Intatha, S. Eitssayeam, K. Pengpat, K.J.D. MacKenzie, T. Tunkasiri, Dielectric [49] A.Z. Sim~ oes, A.H.M. Gonzalez, A.A. Cavalheiro, M.A. Zaghete, B.D. Stojanovic,
properties of low temperature sintered LiF doped BaFe0.5Nb0.5O3, Mater. Lett. 61 J.A. Varela, Effect of magnesium on structure and properties of LiNbO3 prepared
(2007) 196–200. from polymeric precursors, Ceram. Int. 28 (2002) 265–270.
[31] S. Balabanov, D. Permin, T. Evstropov, P. Andreev, L. Basyrova, P. Camy, [50] R. K€oferstein, Thermoanalytical, optical, and magnetic investigations on
M. Baranov, X. Mateos, P. Loiko, Hot pressing of Yb:Y2O3 laser ceramics with LiF nanocrystalline Li0.5Fe2.5O4 and resulting ceramics prepared by a starch-based soft-
sintering aid, Opt. Mater. 119 (2021), 111349. chemistry synthesis, J. Solid State Chem. 287 (2020), 121380.
[32] Y. Lai, H. Su, G. Wang, X. Tang, X. Huang, X. Liang, H. Zhang, Y. Li, K. Huang, [51] E. Antolini, Lithium loss from lithium cobalt oxide: hexagonal Li0.5Co0.5O to cubic
X.R. Wang, Low-temperature sintering of microwave ceramics with high Qf values Li0.065Co0.935O phase transition, Int. J. Inorg. Mater. 3 (2001) 721–726.
through LiF addition, J. Am. Ceram. Soc. 102 (2019) 1983, 1903. [52] R. K€oferstein, T. Buttlar, S.G. Ebbinghaus, Investigationson Bi25FeO40 powders
[33] J.P. Guha, H.U. Anderson, Reaction during sintering of barium titanate with lithium synthesized by hydrothermal and combustion-like processes, J. Solid State Chem.
fluoride, J. Am. Ceram. Soc. 69 (1986) C193–C194. 217 (2014) 50–56.
[34] J.M. Huassonne, G. Desgardin, Ph Bajolet, B. Raveau, Barium titanate perovskite [53] J. Hormadaly, S.N. Subbarao, R. Kershaw, K. Dwight, A. Wold, Preparation and
sintered with lithium fluoride, J. Am. Ceran. Soc. 66 (1983) 801–807. comparison of the photoelectronic properties of Sr2Nb2O7 and Ba0.5Sr0.5Nb2O6,
[35] R. K€oferstein, L. J€
ager, M. Zenkner, T. Müller, H.-P. Abicht, Shrinkage mechanism J. Solid State Chem. 33 (1980) 27–32.
and phase evolution of fine-grain BaTiO3 powder compacts containing 10 mol% [54] V. Sa-Yakanit, H.R. Glyde, Urbach tails and disorder, comments cond, Mat. Phys. 13
BaGeO3 prepared via a precursor route, Mater. Chem. Phys. 112 (2008) 531–535. (1987) 35–48.
[36] W. Schatt, Sintervorg€ ange, VDI-Verlag, Düsseldorf, 1992, pp. 78–100. [55] P. Makuła, M. Pacia, W. Macyk, How to correctly determine the band gap energy of
[37] W. Schatt, E. Friedrich, Dislocation activated sintering processes, Powder Metall. 28 modified semiconductor photocatalysts based on UVVis spectra, J. Phys. Chem.
(1985) 140–144. Lett. 9 (2018) 6814–6817.
[38] W. Schatt, B. Vetter, E. Friedrich, Non-isothermal shrinkage of compacts, Powder [56] F.P. Koffyberg, K. Dwight, A. Wold, Interband transition of semiconducting oxides
Metall. 34 (1991) 179–182. determined from photoelectrolysis spectra, Solid State Commun. 30 (1979)
[39] L.A. Perez-Maqueda, J.M. Criado, C. Real, Kinetics of the initial stage of sintering 433–437.
from shrinkage data: simultaneous determination of activation energy and kinetic [57] L.E. Cross, Relaxor ferroelectrics: an overview, Ferroelectrics 151 (1994) 305–320.
model from a single nonisothermal experiment, J. Am. Ceram. Soc. 85 (2002) [58] T. Tsurumi, K. Soejima, T. Kamiya, M. Daimon, Mechanism of diffuse phase
763–768. transition in relaxor ferroelectrics, Jpn. J. Appl. Phys. 33 (1994) 1959–1964.
[40] J.L. Woolfrey, M.J. Bannister, Nonisothermal techniques for studying initial-stage [59] K. Uchino, S. Nomura, Critical exponents of the dielectric constants in diffused
sintering, J. Am. Soc. 55 (1972) 390–394. phase-transition crystals, Ferroelectrics 44 (1982) 55–61.
[41] J.-T. Sgiue, T.-T. Fang, The sintering behavior of CeO2-doped strontium barium [60] X. Qin, D. Shihu, S. Tianxiu, W. Homgni, Diffuse phase transition of
niobate ceramics, J. Eur. Ceram. Soc. 22 (2002) 1705–1709. Ba0.92Ca0.08(Ti0.82Zr0.18)O3 based ceramics, Ferroelectrics 426 (2012) 282–289.
[42] G.W. Marks, L.A. Monson, Effect of certain group IV oxides on dielectric constant [61] L.E. Cross, Relaxor Ferroelectrics, Ferroelectrics 76 (1987) 242–267.
and dissipation factor of barium titanate, Ind. Eng. Chem. 47 (1955) 1611–1620. [62] F. Oehler, H.-T. Langhammer, S.G. Ebbinghaus, Preparation and dielectric
[43] M.I. Mendelson, J. Am. Ceram. Soc. 52 (1969) 443–446. properties of CaTaO2N and SrNbO2N ceramics, J. Eur. Ceram. Soc. 37 (2017)
[44] R.L. Byer, J.F. Young, R.S. Feigelson, Growth of high-Quality LiNbO3 crystals from 2129–2136.
the congruent melt, J. Appl. Phys. 41 (1970) 2320–2325. [63] J.T.S. Irvine, D.C. Sinclair, A.R. West, Electroceramics: characterization by
impedance spectroscopy, Adv. Mater. 2 (1990) 132–138.