Solid State Sciences 4 (2002) 197–203

www.elsevier.com/locate/ssscie

Investigations on the defect chemistry and the sintering of barium titanate

ceramics by oxygen coulometry
Hans Theo Langhammer a,∗ , Quan Ming Song a , Karl-Heinz Felgner a , Hans-Peter Abicht b
a Martin-Luther-Universität Halle-Wittenberg, Fachbereich Physik, Friedemann-Bach-Platz 6, D-06108 Halle, Germany
b Martin-Luther-Universität Halle-Wittenberg, Fachbereich Chemie, Kurt-Mothes-Straße 2, D-06120 Halle, Germany

Accepted 6 November 2001

Dedicated to Professor Dr. Dr. h.c. Hans-Georg von Schnering on the occasion of his 70th birthday

Abstract
The application of the oxygen coulometry method on the investigation of the defect chemistry and the sintering process of donor- and
acceptor-doped barium titanate ceramics is described. The measuring principle is based on two identical solid electrolyte circonia cells with
two electrode pairs both for measuring of the oxygen partial pressure and for oxygen pumping. Three different oxygen exchange processes of
the samples could be detected. (1) The oxygen exchange due to the change of the equilibrium temperature at a fixed oxygen partial pressure,
which is caused by the change of the concentration of oxygen vacancies. (2) The oxygen exchange which is related to the valence change
of MnTi during the change of the ambient atmosphere. The data are consistent with the assumption that manganese occurs as Mn3+ at an
oxygen partial pressure of 2.4 Pa and a temperature of about 1400 ◦ C. (3) During the sintering of donor-doped barium titanate ceramics,
oxygen expelling processes were detected which are related to the incorporation of the donor into the lattice. In the case of a doping level of
0.5 mol% La, the estimated amount of expelled oxygen is less than expected for exclusive electronic donor compensation.  2002 Éditions
scientifiques et médicales Elsevier SAS. All rights reserved.
Keywords: Barium titanate; BaTiO3 ; Defect chemistry; Sintering; Oxygen coulometry

1. Introduction try [5–8], sometimes combined with mass spectroscopy to

For BaTiO3 as an oxide compound, its deviation from
the stoichiometric composition with respect to oxygen de-
termines the macroscopic properties of the material consid-
erably. As an example, oxygen vacancies act as donors and
can change the electric conductivity in a great extent. Hence,
the measurement of the high-temperature electrical conduc-
tivity in dependence on the oxygen partial pressure in a wide
pressure range is a common method for the development of
models for the majority defects of barium titanate, see, e.g.,
[1–4]. On the other hand, the determination of the amount
of oxygen exchange with the ambient atmosphere at ele-
vated temperatures is also an important task in the investi-
gation of the defect chemistry of BaTiO3 . In the past, the
mostly used method for this purpose is the thermogravime-
* Correspondence and reprints.
E-mail addresses: langhammer@physik.uni-halle.de
(H.T. Langhammer), felgner@physik.uni-halle.de (K.-H. Felgner),
abicht@chemie.uni-halle.de (H.-P. Abicht).
1293-2558/02/$ – see front matter  2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.
PII: S 1 2 9 3 - 2 5 5 8 ( 0 1 ) 0 1 2 4 9 - 3
identify oxygen as the mass changing element [9]. Other in-
teresting oxygen exchange processes occur during the incor-
poration of higher valency elements at Ba or Ti sites, if they
are introduced as oxides, or, during the reduction/oxydation
of 3d elements, e.g., MnTi, which can easily change their
valency state. Summarizing, the oxygen can be exchanged
with the ambient atmosphere both during the formation of
the final material, e.g., the sintering process, and/or during
the reaching of the equilibrium with the ambient atmosphere
with respect of temperature and oxygen partial pressure.
Although known for a long time [10,11], the method of
the oxygen coulometry was not applied to the investigation
of such processes in BaTiO3 until now, except for a short
note publication of our preliminary results [12]. Thus, the
aim of this paper is the investigation of different oxygen
exchange processes between the specimen and the ambient
atmosphere which occur both during the change of the
thermal equilibrium and during the sintering of barium
titanate as a structural forming process.
198 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203
Fig. 1. Scheme of the measuring equipment of the oxygen coulometry device. See Section 2.2 for details.
We report both on the development of a suitable measur-
ing system, on the measuring of the change of the oxygen
vacancy concentration due to the change of the thermal equi-
librium, on the change of the valency state of MnTi defects
in dependence on the oxygen partial pressure and on the sin-
tering of undoped and donor-doped barium titanate ceramics
with varying Ba/Ti stoichiometry.
2. Experimental procedure
2.1. Preparation of specimens and characterisation
Ceramic powders with a nominal composition of Ba1−x -
Lax TiO3 + y TiO2 (0
x
0.05, 0
y
0.05) and
BaTi1−x Mnx O3 (0
x
0.05) were prepared by the clas-
sical mixed-oxide powder technique. After mixing (agate
balls, water) and calcination (1100 ◦ C, 2 h in air) of
appropriate amounts of BaCO3 (Solvay, VL600), TiO2
(Merck, no. 808) and La2 (C2 O4 )3 ·9 H2 O (SKW Piesteritz)
or MnCO3 (Riedel de Haen, p.a.) the powder was milled
again and densified to disks with a diameter of 12 mm and a
height of nearly 3 mm. The samples were sintered both in a
special gas-tight furnace of the coulometry system (see be-
low) and in air at temperatures between 1300 and 1400 ◦ C
for the purpose of comparison. To avoid interfering contam-
ination during sintering they were contained in ZrO2 powder
covered Pt /Al2 O3 dishes.
The microstructure of the polished and chemically etched
specimens was examined by optical microscopy and by
scanning electron microscopy (SEM).
2.2. Oxygen coulometry
The measuring principle is described by means of the
schematic diagram in Fig. 1. The mean components of the
equipment are two identical, electronically controlled, oxy-
gen conducting ZrO2 Nernst cells (SensoTech, Magdeburg-
Barleben, Germany, model Oxylyt 10-21), which exhibit two
pairs of electrodes. One of them is used for the determining
of the oxygen partial pressure, pO2 , of the flowing gas stream
by measuring the voltage between the electrodes, U cell , ac-
cording to the Nernst equation (1)
RT pO2
U cell = ln ref , (1)
4F pO2
R molar gas constant, T absolute temperature, F Faraday
ref
constant, pO 2
oxygen partial pressure of air as the reference
gas.
The second pair of electrodes is used for the transport of
a well-defined amount of oxygen between the flowing gas
inside the cell and the ambient air by an applied electric
current, I , according to the following Eq. (2)
I
nO2 = t. (2)
4F
nO2 is the mole number of oxygen transported during the
time t. The sign of I determines the transport direction.
The maximum current amounts to 100 mA with a stability
better than 1 µA.
Both electrode pairs are connected by an electronic
control circuit with the set point U set and the control variable
I in that sense, that a constant output pO2 (U cell ) of the cell
is maintained by an oxygen transport into or out of the ZrO2
tube (see Fig. 1).
The measuring principle is described as follows. After
the preparation of the carrier gas (gas mixing and flow
control of total 200 ml min−1 by a device manufactured by
Horiba Ltd., Japan) cell 2 is used to produce a working
gas stream with well-defined pO2 for the furnace with the
sample to be investigated. After passing the furnace, the gas
streams through cell 1, which set point U set is chosen to
get a appropriate current I pump . As long as no change of
the oxygen partial pressure between the two cells occurs,
this current is constant and exhibites the base line of the
measurement I0 . If an oxygen exchange between the sample
and the ambient atmosphere occurs, e.g., during change
pump
of the furnace temperature, a changing current I1 will
compensate the changed oxygen partial pressure of the
output gas stream of the furnace. Thus, the total amount
 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203
Fig. 2. Oxygen pumping current I1 in dependence on temperature during
the heating without a specimen to determine the “empty effect” of the
coulometry device, pO2 = 2.4 Pa.
of exchanged oxygen during a time interval t2 − t1 can be
calculated by the following expression

t2
1  pump 
nO2 = I1 (t) − I0 dt.
4F
t1
pump
Minimum peaks of I1 indicate an oxygen release or a
reduction of the sample, while maximum peaks point to an
oxygen consumption or oxidation process.
A quantitative check of the procedure was performed by
the decomposition reaction
+Q
BaO2 −→ BaO + 1
O2 ↑,
2 1347 → 1245
and resulted in errors
5% within a mass range of BaO2
of between 0.4 and 4.0 mg which corresponds to about 10−6
and 10−5 mol O2 ↑. The interesting oxygen exchange effects
of the BaTiO3 samples investigated (mass ≈ 1 g) amount
to between 10−7 and 10−5 mol. The sensitivity limit of
the apparatus can be estimated by Eq. (2) to
10−9 mol
or 0.032 µg O2 if we assume a pumping current of 10 µA
during a measuring time of 60 s. Hence, the sensitivity is at
least one order better than the sensitivity of a commercial
thermobalance (≈ 1 µg at 1400 ◦ C).
To separate the influence of alumina (furnace tube and
sample holder) and zirconia (sample pad, ≈ 300 mg) on the
oxygen exchange, empty tests were performed. As shown
in Fig. 2, only at temperatures higher than about 1300 ◦ C a
noticeable release of oxygen is observed. The total expelled
oxygen amounts to maximum 1.0 × 10−7 mol during the
heating at 10 K min−1 up to 1400 ◦ C. Probably, the oxygen
loss is caused by the formation of Schottky-type oxygen
vacancies in ZrO2 and Al2 O3 . All further quantitative results
were corrected by subtracting of that apparatus effect.
3. Results and discussion
3.1. Equilibrium measurements in “undoped” BaTiO3
To investigate the response of BaTiO3 ceramics to a
change of the thermal equilibrium, nominally undoped ma-
terial was chosen, having an accidental acceptor impurity of
199
Fig. 3. Oxygen pumping current I1 and temperature T in dependence on
the measuring time during a two-step temperature change between 1140
and 1350 ◦ C of “undoped” BaTiO3 , pO2 = 2.4 Pa.
(3)
Table 1
Change of the total concentration of oxygen vacancies [VOtot ] (cm−3 ) after
the change of the equilibrium temperature from T1 to T2 at an oxygen
partial pressure of 2.4 Pa, both determined by oxygen coulometry and
calculated by means of the defect model of Daniels et al. [1]
T1 → T2 (◦ C) Experimental data Model calculation
1245 → 1140 9.3 × 1017 5.0 × 1017
1140 → 1245 8.8 × 1017 5.0 × 1017
1245 → 1347 26.2 × 1017 14.4 × 1017
(4)
26.7 × 1017 14.4 × 1017
about 100 ppm (see [2], e.g.) caused by the raw materials.
The oxygen exchange of a specimen during the temperature
change between 1140 and 1350 ◦ C in two intervals at an oxy-
gen partial pressure of 2.4 Pa is shown in Fig. 3. Assuming
that all exchanged oxygen is caused by the formation (oxy-
gen release) or by the annihilation (oxygen consumption) of
oxygen vacancies after changing the equilibrium tempera-
ture, the change of their total concentration, [VOtot], can be
determined by the measured oxygen exchange nO2 accord-
ing to
  NA ρBaTiO3
 VOtot = 2nO2 , (5)
msample
where NA is the Avogadro constant, ρBaTiO3 is the sample
density and m is the sample mass. The good correspondence
of the data between the heating and cooling steps (see Fig. 3
or Table 1) proves the reversibility of that processes and
supports the assumption above.
To compare the experimental data with existing de-
fect models of BaTiO3 , we used the data of Daniels and
Härdtl [1], who published a complete set of constants of the
mass action laws of their defect model, enabling the calcu-
lation of the total oxygen vacancy concentration in depen-
dence on temperature and oxygen partial pressure. Table 1
shows the comparison between the experimental and the cal-
culated data of [VOtot ]. Although the model does not in-
clude all defect types which are established by now (e.g.,
200 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203

background acceptor impurity), the corresponding order of

the data in Table 1 indicate that, nevertheless, parts of the
model can be used to estimate the defect concentrations in
the considered temperature and pO2 region.
The systematic investigation of the oxygen exchange
between specimen and the ambient atmosphere after change
of the thermal equilibrium in a wide range of temperature
and oxygen partial pressure is the subject of our future work.
These data shall be used for the check of existing defect
models, or, to refine the model parameters by additional
coulometry data.

3.2. Sintering of Mn-doped BaTiO3

For Mn-doped BaTiO3 it is known that Mn substitutes Fig. 4. Oxygen pumping current I1 and temperature T in dependence
for titanium and can adopt the valency states 4+, 3+ and on the measuring time during the sintering of BaTi1−x Mnx O3 ceramics
2+ [13–17]. While in air-sintered and otherwise undoped (0.005
x
0.04), pO2 = 2.4 Pa.
samples the isovalent defect Mn4+Ti dominates, the sintering
or annealing in reducing atmosphere reduces manganese to Table 2
Mn3+ 2+
Ti and MnTi , respectively [13,16,17]. In the valence Amount of the expelled oxygen (mole fraction xO ) due to the change
states 3+ and 2+, respectively, Ti-site occupying manganese of the valency of Mn from 4+ to 3+ or 2+, respectively, during the
is negatively charged (Mn Ti and Mn Ti, respectively) and sintering of BaTi1−x Mnx O3 in reducing atmosphere (pO2 = 2.4 Pa). The
data were determined both coulometrically (roughly estimated maximum
must be compensated either electronically by holes or
values) and calculated, assuming exclusive oxygen vacancy compensation
by positively charged oxygen vacancies VO•• according to of either Mn3+ or Mn2+ as the dominating valence state of manganese
following equations:1 x Roughly estimated Compensation Compensation
experimental data of Mn3+ of Mn2+
MnxTi ↔ Mn Ti + h• ↔ Mn Ti + 2h• , (6)
0.005 0.0024 0.0025 0.005
2 MnxTi + OxO ↔ 2 Mn Ti + VO•• + 12 O2 ↑, (7) 0.02 0.011 0.010 0.020
0.03 0.016 0.015 0.030
MnxTi + OxO ↔ Mn Ti + VO•• + 12 O2 ↑. (8) 0.04 0.019 0.020 0.040

While hole compensation produces no oxygen vacancies, in

the case of vacancy compensation, depending on the valency relative inaccuracy of the experimental data, the comparison
state of Mn, different amounts of VO•• are created and, clearly indicates Mn3+ as the dominating valency state
consequently, different amounts of oxygen are expelled and at a pO2 of 2.4 Pa. This is in partial accordance with
can be measured by coulometry. Hence, these data are useful the defect model of Kim et al. [19]. But, of course, a
for the determination of the percentage of the valency states simultaneous occurence of Mn4+ , Mn3+ and Mn2+ , which
of MnTi in dependence on temperature and oxygen partial could be compensated partially by oxygen vacancies and
pressure which data are known only very vague. Fig. 4 holes, cannot be excluded.
shows the results for the sintering of a series of Mn-doped
samples in reducing atmosphere at pO2 = 2.4 Pa which 3.3. Sintering of “undoped” and donor-doped BaTiO3
were calcined in air before. To be seen distinctly in Fig. 4,
at least two different oxygen expelling processes overlap
Fig. 5 shows the coulometry measurement during the
during the sintering. Except of the creation of oxygen
sintering of undoped BaTiO3 as the pumping current versus
vacancies due to the valency change of Mn mentioned
temperature for the complete heating and cooling cycle.
above, inter alia, Schottky-type equilibrium vacancies are
During the heating cycle, a distinct oxygen release peak is
formed at high temperatures. Therefore, the amount of
observed, which occurs more or less pronounced with all
expelled oxygen which can be assigned to the valency
BaTiO3 samples, doped or undoped, at an onset temperature
change of Mn could be estimated only approximately.
between 950 and 1150 ◦ C and has no counterpart during
Table 2 shows the comparison of the mole fraction of that
cooling contrary to the oxygen release due to the formation
expelled oxygen xO = 2nO2 /nsample with data calculated
of Schottky-type oxygen vacancies VO . The reoxidation
under the assumption of an exclusive occurrence of Mn
Ti
process during cooling related to the annihilation of VO is
(Eq. (7)) and Mn

Ti (Eq. (8)), respectively. Despite of the
observed in all measurements. During the repetition of the
measurement under the same oxygen partial pressure, the
1 Here and in the following the Kröger–Vink notation of defects [18] is oxygen release peak is completely vanished. Obviously, it is
used. caused by the lower oxygen partial pressure of 2.4 Pa during
 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203
Fig. 5. Oxygen pumping current I1 in dependence on temperature both
during the sintering of undoped BaTiO3 + 2.0 mol% TiO2 and during the
re-heating of the same sample, which was annealed before in air for two
hours at 1200 ◦ C, pO2 = 2.4 Pa.
the coulometry measurement, compared to air (pO2 = 2.1 ×
104 Pa) as the ambient atmosphere during the calcination
of the powder. Hence, the sample releases oxygen for as
long as the new equilibrium oxygen activity is reached.
To check this, the sample was annealed at 1200 ◦ C for
two hours in air to reoxidize and then measured again
at a pO2 of 2.4 Pa. The results, also shown in Fig. 5,
exhibit the expected behaviour. Due to the circumstance
that the restoration of the thermodynamic equilibrium in the
sintered, coarse-grained sample needs much more time than
in the fine-grained power compact, the onset temperature of
the peak is shifted for about 70 K to higher temperatures
as well as the expelled oxygen amounts to approximately
50% of the corresponding value of the former sintering step.
Whereas the oxygen exchange between sample and ambient
atmosphere is determined mainly by bulk diffusion in or
out of the large grains of the sintered specimen, the much
faster grain barrier diffusion is the rate-controlling process
for the oxygen release of the sintering green compact. This
oxygen release effect strongly varies with different powder
qualities and with different chemical compositions, and it is
significantly influenced by the Ba/Ti stoichiometry.
The oxygen exchange during the sintering of donor-
doped BaTiO3 is shown in Figs. 6 and 7a with NbTi and
Ti + 6 O×
LaBa as the dopant elements, respectively. In both cases, four
oxygen release peaks can be observed during the heating
cycle, denoted with increasing temperature by numbers I–
IV. Peak (I), which is strongly developed only in the case of
La-doping, results from the different oxygen partial pressure
of the ambient atmospheres during calcination and sintering
which was described above. Only peak (IV), for La-doped
BaTiO3 strongly overlapping with peak (III), corresponds
to a reversible process since it has a counterpart during
the cooling cycle as in the case of undoped BaTiO3 (see
Fig. 5) and obviously originates from the formation of
201
Fig. 6. Oxygen pumping current I1 in dependence on tempera-
ture during the sintering of a sample (supplied by Miha Drofenik,
Jožef Stefan Institute Ljubljana, Slovenia) with a composition of
BaTi0.9974 Nb0.0026 O3 + 4.0 mol% TiO2 + 0.6 mol% SiO2 (heating and
cooling cycle), pO2 = 2.4 Pa. Marks (I)–(IV) are explained in the text.
Schottky-type equilibrium oxygen vacancies. To attribute
peaks (II) and (III) to particular processes during the
sintering, additional measurements at soaking temperatures
of 1200 and 1300 ◦ C were performed in the case of La-doped
material. The results together with the related microstructure
data are shown in Fig. 7b,c. While a sintering temperature
of 1200 ◦ C is too low to initiate the anormal grain growth
of BaTiO3 , the microstructure of the specimens sintered at
1300 and 1430 ◦ C exhibits the typical bimodal intermediate
and final stage, respectively. The onset temperatures of
the peaks (II) and (III) correspond very well with the
starting temperatures of the exaggerated grain growth in
the presence of a SiO2 and TiO2 containing liquid phase,
respectively [20–22]. In the case of La-doped material, the
SiO2 impurities result from the abrasion of the agate balls
during milling. Their small amount causes an incomplete
grain growth. The Nb-doped samples exhibit an analogous
behaviour with respect to the microstructure development at
different sintering temperatures.
Hence, the oxygen release related to the peaks (II) and
(III) originates from the incorporation reaction of La at Ba
sites
La2 O3 + 2 TiO2 → 2 La•Ba + 2 Ti
O + 2 O2 ↑,
1
(9)
which is in accordance to the findings of Drofenik [23], who
stated that in BaTiO3 the endothermic donor incorporation
according to Eq. (9) is only possible as long as a constant,
sufficient high energy is provided by the stored free surface
energy during the exaggerated grain growth. It should be
noted that this finding is in contradiction to numerous
publications where the authors assumed that the donor
dopant is already incorporated after the calcination of
the ceramic powder at about 1150 ◦ C. To confirm the
coincidence of the beginning of the liquid phase promoted
anomalous grain growth with a distinct oxygen release
202 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203

Fig. 7. Oxygen pumping current I1 in dependence on time during the sintering of specimens with a composition of Ba0.995 La0.005 TiO3 + 1 mol% TiO2 at three
different maximum temperatures 1430 ◦ C (a), 1200 ◦ C (b) and 1300 ◦ C (c). Ambient atmosphere: pO2 = 2.4 Pa. Optical micrographs of the corresponding
microstructure are also presented (bar = 500 µm). Marks (I)–(IV) are explained in the text.

in the range of between 1300 and 1350 ◦ C (not shown here)

Fig. 8. Oxygen pumping current I1 in dependence on temperature during
the sintering of samples (supplied by Silvio Gablenz, FB Chemie, Univer-
sity Halle, Germany) with a composition of Ba0.998 La0.002 TiO3 + x mol%
TiO2 (3.0
x
5.0), pO2 = 2.4 Pa. The grain growth related oxygen re-
lease peaks are marked by an arrow.
+ 3 Ti× ×
peak, a series of 0.2 mol% La-doped specimens with
varying excess of TiO2 (0–5 mol%) were investigated. The
coulometric data (Fig. 8) show a systematic shift of the
onset temperature of the grain growth related oxygen release
peak towards higher temperatures with increasing excess
of TiO2 . Investigations of the microstructure and of the
room temperature electrical conductivity of the samples in
dependence on the sintering temperature with steps of 10 K
reflect that tendency very well.
In the case of 0.5 mol% La-doped BaTiO3 , a quantitative
analysis of the oxygen release was performed. By means of
the three coulometry measurements at different maximum
sintering temperatures (see Fig. 7) and the subtraction of the
contributions of the Schottky-type oxygen vacancies both
from the specimen and from the apparatus, the mole fraction
of expelled oxygen of the sample sintered at 1430 ◦ C caused
by the La incorporation was estimated to xO = 0.0012.
If the total amount of 0.5 mol% La would be incorporated
during the sintering according to Eq. (9), an oxygen release
of xO = 0.0025 is expected. Since no La segregation
at grain boundaries or triple points was detected, this
discrepancy may be explained by two different assumptions.
First, about the half of the donors are incorporated really
already during the calcination. Second, not all La•Ba ions
are electronically compensated, but, e.g., by Ti vacancies
according to following equation
2 La2 O3 + 3 TiO2 → 4 La•Ba + VTi
Ti + 12 OO . (10)
Meanwhile, the titanium vacancies are commonly accepted
as the dominating charge compensating defect in highly
donor-doped BaTiO3 [24]. But, in the case of low doping
concentrations up to about 1 mol%, the question for the act-
ing compensating mechanism(s) is still open. Recently, Mor-
rison et al. [25] published the hypothesis that even for low
concentrations of the donor dopant, where the air-sintered
samples are semiconducting and electrical conductivities of
 H.T. Langhammer et al. / Solid State Sciences 4 (2002) 197–203
0.1 ( cm)−1 or more are reached, all donors are compen-
sated by titanium vacancies. They explain the observed elec-
trical conductivity and its well-known anomaly in BaTiO3
by the exclusive influence of oxygen vacancies as intrinsic
donors which should be inhomogeneously distributed be-
tween the core and the outer regions of the grains of the ce-
ramic samples. This hypothesis is a quite new variant in the
long-standing discussion of the doping anomaly of BaTiO3 ,
but, nevertheless, it seems to be a somewhat doubtful one. In
our opinion, the observed coincidence between the oxygen
release and the start of the rapid exaggerated grain growth
during sintering is a good argument for the occurence of the
electronic donor compensation, if Drofenik’s model of the
grain growth anomaly is accepted.
4. Summary
The qualitative and quantitative determination of the
oxygen exchange between the barium titanate ceramic and
its ambient atmosphere both during the restoration of the
thermodynamic equilibrium and during non-equilibrium
processes like sintering as well as the determination of the
onset temperatures of the corresponding defect reactions
by means of the oxygen coulometry method were shown.
Nominally undoped, acceptor- and donor-doped material
was investigated.
(1) In the case of “undoped” BaTiO3 , the change of the
equilibrium oxygen vacancy concentration due to a
changed equilibrium temperature between 1140 and
1350 ◦ C at pO2 = 2.4 Pa was determined. Correspond-
ing data calculated by a defect model [1] are in the
same order. Systematic investigations of the oxygen ex-
change after the change of equilibrium parameters like
temperature and oxygen partial pressure of the ambient
atmosphere shall be done in the future to check existing
defect models with respect of their validity as a whole or
for the correction of the values of the model parameters.
(2) The oxygen exchange of Mn-doped BaTiO3 due to the
formation of oxygen vacancies caused by the change of
the valence state of MnTi was detected. The amount of
the expelled oxygen during the sintering of air-calcined
specimens in a reducing atmosphere of pO2 = 2.4 Pa can
be explained by the complete transition from Mn4+ to
Mn3+ in the doping range of 0.5
[MnTi ]
4.0 mol%.
(3) The oxygen release caused by the incorporation of the
donor into the BaTiO3 lattice related to the anomalous
grain growth during sintering was proved for La and
Nb which substitute for Ba and Ti, respectively. In the
case of 0.5 mol% La-doped material about the half of
the expected amount of oxygen release was detected
if total donor incorporation and exclusive electronic
203
charge compensation is assumed. Hence, a portion of
lanthanum is already incorporated during calcination
and/or the donors are, at least partially, compensated by
cation vacancies. To disentangle this question and other
problems related to the donor incorporation in BaTiO3 ,
a systematic, quantitative analysis of the grain growth
related oxygen release in a wide range of the doping
level and with different donor dopants is the subject of
our further work.
Acknowledgements
The authors would like to thank Dr. Helfried Näfe from
the Max Planck Institute für Metallforschung Stuttgart for
valuable discussion. Financial support from the Kultusmin-
isterium des Landes Sachsen-Anhalt and from the Fonds der
Chemischen Industrie is gratefully acknowledged.
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