Journal of Alloys and Compounds 419 (2006) 271–280

A-site deficient perovskite-type compounds in the ternary

CaTiO3-LaCrO3-La2/3TiO3 system
V. Vashook a,∗ , L. Vasylechko b , N. Trofimenko c , M. Kuznecov c ,
P. Otchik c , J. Zosel d , U. Guth a,d
a Institute of Physical Chemistry and Electrochemistry, Dresden University of Technology, D-01062 Dresden, Germany
b Lviv Polytechnic National University, 12 Bandera St., Lviv 79013, Ukraine
c Fraunhofer Institute for Ceramic Technologies and Sintered Materials, D-01277 Dresden, Germany
d Kurt-Schwabe-Institute for Measuring and Sensor Technology Meinsberg, D-04720 Ziegra-Knobelsdorf, Germany

Received 29 June 2005; accepted 9 September 2005

Available online 28 November 2005

Abstract
Phase equilibriums in the CaTiO3 -LaCrO3 -La2/3 TiO3 quasi-ternary system have been studied by means of high-resolution powder diffraction
technique using X-ray and synchrotron radiation. Over 50 La(2+y−2x)/3 Cax Cry Ti1−y O3 compounds were synthesized by solid-state reactions in air
at 1350 ◦ C using La2 O3 , CaCO3 , Cr2 O3 and TiO2 . Based on the results of X-ray phase and structural analysis, the isothermal section of the
CaTiO3 -LaCrO3 -La2/3 TiO3 phase diagram at room temperature is constructed. The A-cation deficient La(2+y−2x)/3 Cax Cry Ti1−y O3 solid solution
with different perovskite-type structures (space groups Pbnm, Imma, I4/mcm and Cmmm or P2/m) is formed in the CaTiO3 -LaCrO3 -La2/3 TiO3
quasi-ternary system in air conditions. The compounds show high stability at high temperatures at reducing as well as at oxidizing conditions. The
substances with y = 0 and y = 0.2 show n-type conductivity at 900 ◦ C at pO2 = 10−15 to 105 Pa and with y = 0.5 show conductivity minima these shift
to the oxygen reach region with increasing A-site deficiency. The A-site deficient La(2+y−2x)/3 Cax Cry Ti1−y O3 samples have higher sintering ability
in comparison with the cation stoichiometric La1−x Cax Cr1−y Tiy O3 compositions and, in contrast to the latter, can be prepared as gas dense ceramics
in air at temperatures lower as 1300 ◦ C. Thermal expansion of the A-site deficient La(2+y−2x)/3 Cax Cry Ti1−y O3 ceramics is comparable with that
of yttrium stabilised zirconia (YSZ). No interaction between La(2+y−2x)/3 Cax Cry Ti1−y O3 and YSZ ceramics up to 1300 ◦ C was observed. Oxygen
mobility in these ceramics can be characterised with chemical diffusion coefficients (1–9) × 10−9 cm2 s−1 at 900 ◦ C and pO2 = 1000–21,000 Pa.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Perovskites; Chromites; Titanates; Crystal structure; A-site deficiency; Oxygen stoichiometry; Electrical conductivity; Oxygen mobility; Thermal
expansion; Chemical stability

1. Introduction cracking of hydrocarbon fuel (CH4 → C + 2H2 ) and for reform-

ing (CH4 + H2 O
CO + 3H2 ) in comparison with the elec-
The optimal variant of realization of SOFC consist is the trochemical reaction. Other disadvantages of the Ni/NiO + YSZ
application of light hydrocarbon fuel (CH4 ) with its direct elec- composites as SOFC-anode material are discrepancies between
trochemical oxidation at the anode to carbon dioxide and water the thermal expansion coefficients (TEC) of metallic nickel and
vapour [1]. Unfortunately, no optimal anode materials were yttrium stabilized zirconia [1,5], changes of the catalytic activity
found for the internal oxidation of dry fuel in the SOFC up during operation time in consequence of sintering of the nickel
to now. The basic imperfection of the most widespread SOFC particles [6], or nickel sulfide (NiS) formation [7], and mechan-
anode material (composition Ni/NiO + YSZ) is the restricted ical destruction of the anode by nickel oxidation.
possibility to use it in systems with internal reforming [2–4], Recently, a lot of new compounds have been offered as al-
because of the relative high catalytic activity for pyrolysis or ternative anode materials: La1−x (Sr,Ca)x CrO3 [5,8,9], La0.8
Sr0.2 Cr0.97 V0.03 O3 [10], ZrO2 (Y2 O3 + Nb2 O5 ) [11], (Sr1−x
Bax )0.6 Ti0.2 Nb0.8 O3 [12], La2 Sr4 Ti6 O19−δ [13], (Ti1−y Moy )2
∗ Corresponding author. Tel.: +49 351 463 34792; fax: +49 351 463 37752. O7 [14], La0.6 Sr0.4 Co0.2 Fe0.8 O3 [15,16], some individual com-
E-mail address: vladimir.vashook@chemie.tu-dresden.de (V. Vashook). positions in the system La1−a Caa Cr1−b Tib O3−δ [17] and others.

0925-8388/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.09.063
272 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280

None of the proposed compounds fulfils the requirements of In accordance with results reported by Pudmich et al. [17],
SOFC anodes completely [18]. the most perovskite-type compounds in the system La-(Ca, Sr)-
Complex perovskite-type oxides (ABO3 ) based on rare earth Cr-Ti-O, have a low catalytic activity concerning hydrocarbon
and alkaline earth oxides with 3d-transition metal oxides are oxidation reactions. At the same time, catalytic activity varies
interesting candidates in search of materials with electrocatalytic notably with changing compositions within the cation stoichio-
properties. Subjects of investigation in this field are lanthanum metric series La1−x Cax Cr1−y Tiy O3 . The correlation between
chromites and titanates substituted with alkaline earth ions. total conductivity and catalytic activity was observed for some
Pudmich et al. [17] prepared and investigated a series of solid solutions, while such correlation was not found for some
lanthanum chromites partially substituted with alkaline-earth other solid solutions of these series [20].
elements in the A-position of the perovskite-type structure and Preliminary results demonstrate, that cation non-
with transition metals like Ti, Co, or Fe in the B-position with stoichiometric compounds with perovskite-type structure
regard to their application as anodes in solid oxide fuel cells. A exist in the system La(2.2−b)/3 Ca0.4 Cr1−b Tib O3 , and the cationic
broad range of variation of the physical properties such as elec- deficiency in the A-sub-lattice can reach up to 0.3 atomic
trical conductivity and thermal expansion was observed. van indexes [20].
Hassel et al. [19] published the first results on oxygen partial The A-site deficient lanthanide titanates Ln1−x TiO3 (Ln = La,
pressure dependence of the electrical conductivity and oxygen Nd, Sm) with x = 0.0–0.33, so-called partial vacancy doped
ionic transport in La1−a Caa CrO3−x . titanates, are known for a sufficiently long time. They can be
It is known, that both lanthanum chromite (LaCrO3 ) and prepared by solid-state reactions either at the presence of some
calcium titanate (CaTiO3 ) with perovskite structure are thermo- alkaline, alkaline-earth or transition metals, or under oxygen
dynamically stable compounds at high temperatures in a wide pressures lower than that of air. For the first time the existence
oxygen partial pressure range of (105 to 10−15 Pa). Thermal of La2/3 TiO3 was reported by Kestigian et al. in 1955 [26].
expansion coefficients of some of the investigated compounds Some of the compositions of the La1−x TiO3 solid solutions were
of this system are close to that of yttrium stabilized zirconia obtained and investigated by Leonov et al. [27,28] and Basuev et
[17]. The sizes of La–Ca and Cr–Ti cations are close to each al. [29]. According to literature data, the structure of La2/3 TiO3
other which raise hopes to achieve solubility in a wide range of is orhtorhombic [30,31], tetragonal or cubic [32]. MacEach-
cation concentrations. By changing ratios of cations with vari- ern et al. [33] studied the La1−x TiO3 system at 0.0 ≤ x ≤ 0.33
ous oxidation states in the separate sublattices of the perovskite and showed that three different orhtorhobmic structures are
structure, the concentrations both of cation and anion vacancies formed in this concentration range: Pban at 0.25 ≤ x ≤ 0.33,
in the compounds of this system can be adjusted at the desirable Ibmm at 0.20 ≤ x ≤ 0.25 and Pbnm at 0.0 ≤ x ≤ 0.20. The cation-
level. The expected stability of chromium cations with oxidation deficient La2/3 TiO3 compound is thermodynamically unstable in
states 3+ and 4+ in oxidizing environments and titanium cations air below 1400 ◦ C, but could be stabilized by low-level substi-
with oxidation states 4+ and 3+ in reducing environments can tution by PbTiO3 [34,35,30], Ti3+ [30], alkali metals [36,37],
provide the different types of electronic conductivity, depending Ca, Sr [38,39], Sc, Cr, Al [40,41], Nb [42] and Co [43]. The
on temperature and oxygen partial pressure, by varying cationic structure of La2/3 TiO3−δ could be stabilized also with the forma-
compositions. tion of oxygen vacancies [28,30]. The A-cation deficient com-
Recently, the reduction stability of the La1−x Cax Cr1−y pounds R1−x TiO3 with the perovskite-like structure are known
Tiy O3−␦ compositions in H2 /H2 O/Ar gas flows with in the systems of Ce, Pr and Nd [28,29,40,44–47]. Many other
pO2 = 10−15 Pa at temperatures 800–1000 ◦ C as well as investigations of physical and chemical properties of the A-site
the chemical compatibility with YSZ up to 1300 ◦ C in air were deficient titanates were performed in the last years [48–52].
demonstrated [20–25]. Depending on cationic composition and The correlations between the composition of the
oxygen partial pressure, the compounds exhibit high (up to La(2+y−2x)/3 Cax Cry Ti1−y O3 solid solution on the one hand
100 S/cm) p- or n-type conductivities in oxidizing or reduc- and crystal structure as well as electrical conductivity, oxygen
ing environments, respectively. Substances with alternating nonstoichiometry, oxygen mobility, thermal expansion on the
electronic conductivity types, depending on oxygen partial other hand are the objects of interest of this article.
pressure, were found as well as substances with high electrical
conductivities in both oxidizing and reducing atmospheres. 2. Experimental
It was found, that the La1−x Cax Cr1−y Tiy O3 mixed oxides
with cation stoichiometry have various degrees of oxygen allo- 2.1. Powder preparation and crystal structure
cation within the region of structure stability at temperatures
Calcium carbonate, lanthanum oxide, titanium dioxide and chromium(III)
of 700–1000 ◦ C and identical oxygen partial pressures [20–25]. oxide, all of Analytical Reagent grade having purity >99.5%, were used as ini-
The degree of dissociation is defined by the Ca/Ti ratio. The tial materials for preparation of the La(2+y−2x)/3 Cax Cry Ti1−y O3 (x, y = 0.0–1.0)
increase of this ratio is connected with an easier dissociation of powders and slightly modified compositions. The appropriate mixtures were
the oxides and with the approximation of their behaviour to the milled with ethanol in an agate ball mill for 24 h. The mixed powders were
properties of the La1−x Cax CrO3 solid solution. At decreasing dried and calcined in air at 1100 ◦ C for 20 h in alumina crucibles. After cool-
ing to room temperature the products were milled again and finally annealed
Ca/Ti ratios the dissociation of these oxides is reduced. In case in air at 1350 ◦ C for 20 h. The cooling and heating rates were about 5 ◦ C/min.
of Ca/Ti = 1, oxygen release was found only under very high The obtained substances were repeatedly milled and the obtained powders were
reducing conditions. used for further experiments. Before XRD and oxygen nonstoichiometry inves-
 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280 273

tigations were carried out, the powders were treated at 1000 ◦ C during 10 h and 3. Results and discussion
cooled to room temperature with a rate 2 ◦ C/min.
The crystal structures were investigated at room temperatures by means
3.1. Powder preparation and investigation of the crystal
of the powder diffraction technique using a Siemens D5000 powder X-Ray
diffractometer (Cu K␣-radiation; θ/2θ: scanning mode; step width of 0.02◦ ; structure
counting time per step: 7 s). High temperature behaviour of the crystal struc-
tures was studied by means of high-resolution powder diffraction technique and All prepared compositions as well as their crystal structures
synchrotron radiation in the temperature range of 20–1000 ◦ C in air. In situ at room temperatures are shown in Fig. 1 and Table 1. Fig. 2
diffraction experiments were carried out at the Hamburg Synchrotron Radia-
represents an example of profile fitting for La0.13 Ca0.8 TiO3 .
tion Laboratory (HASYLAB) by using powder diffractometer at beam line B2,
equipped with STOE furnace. The continuous solid solution with orthorhombic Pbnm struc-
The crystal structures were refined by the full-profile Rietveld analysis ture is formed in the (1 − x)LaCrO3 -xCaTiO3 pseudo-binary
method, including refinement of lattice parameters, positional and displace- system (Fig. 3). As the distorted cubic lattices of LaCrO3 and
ment parameters, site occupancy, scaling factor, sample shift, background and CaTiO3 have different ratios of cell parameters within the same
Bragg-peak profile parameters. The atomic displacement parameters are refined
GdFeO3 -type structure (a > b and a < b, respectively), some of
anisotropically for La(Ca) cations and isotropically for all other atoms. All cal-
culations were performed using the WinCSD (Crystal Structure Determination) the samples from this system display the tetragonal or cubic
program package [53]. lattices. The diffraction data from the in situ high-temperature
synchrotron experiments indicate that the orthorhombic
2.2. Oxygen nonstoichiometry (pseudo-cubic) Pbnm structure of La0.5 Ca0.5 Cr0.5 Ti0.5 O3
transforms into the Imma one above 1070 K.
The initial oxygen content in compounds was determined by iodome- In the (1 − x)LaCrO3 -xLa2/3 TiO3 pseudo-binary system, two
try method after digestion of powders in KJ/HCl solution at elevated tem- kinds of the perovskite-like structures are found. LaCrO3 -rich
peratures in sealed glass ampoules [25]. Oxygen nonstoichiometry changes
compositions have the GdFeO3 -type Pbnm structure, whereas in
were measured by solid-electrolyte technique using a PC-controlled device
OXYLYT (SensoTech Magdeburg, Germany) [25]. The concept of combined the La2/3 TiO3 rich region of the system the solid solution with
coulometric–potentiometric arrangement for the investigation of solid–gas inter- the ordered A-cation vacancies and P2/m structure is formed.
actions in the carrier gas mode was described earlier in [54,55]. Both La(3−x)/3 Cr1−x Tix O3 perovskite-type phases co-exist in a
The investigation of oxygen nonstoichiometry was performed on some wide concentration range of x = 0.2–0.8 (Fig. 4).
powders, the preparation of which is described in Section 2.1, in the tem-
A-cation deficient perovskite-type solid solutions La2(1−x)/3
perature range of 20–1000 ◦ C and at oxygen partial pressures from 10−15 to
21,000 Pa. The ceramic samples were used for simultaneous measurements of Cax TiO3 with four different crystal structures are formed in the
oxygen nonstoichiometry and the electrical conductivity. Air, Ar/O2 with 1 Pa pseudo-binary system (1 − x)La2/3 TiO3 -xCaTiO3 depending
O2 , and Ar/H2 /H2 O with pH2 O/pH2 = 0.01 gas mixtures were utilised as initial on composition. Similar to CaTiO3 , the samples with molar
reagents. fraction of La2/3 TiO3 0/0.4 display the GdFeO3 -type structure.
A-cation vacancies in these structures are statistically distributed
2.3. Electrical conductivity in Ca(La) cation positions. At intermediate concentration of
La2/3 TiO3 (0.4/0.7) the solid solution with body-centered
The electrical conductivity of ceramic samples was measured in gas
atmospheres with controlled oxygen partial pressures by a dc four-point
orthorhombic (pseudo-tetragonal) Imma structure is formed.
method described elsewhere [56]. The powders were pressed into bars The continuing increase of La2/3 TiO3 content and the following
1 mm × 3 mm × 10 mm together with four Pt wires (0.1 mm thickness) and sin- A-cation deficiency lead to the formation of the tetragonal
tered for 20 h in air at temperatures of 1250–1400 ◦ C depending on composition.
Heating and cooling rates during sintering were 5 ◦ C/min. The conductivity
was measured at 20–1000 ◦ C in air and in the flowing gas mixtures of Ar/O2
(1–100 Pa O2 ) and Ar/H2 /H2 O with pH2 O/pH2 = 0.01–50. The equilibrium val-
ues of the conductivity at 900 ◦ C and different oxygen partial pressures can be
achieved after 1–100 h exposition depending on composition and ceramic struc-
tures of the samples and the oxygen partial pressure range. The temperature
dependencies of the electrical conductivity in air and in gas flow of Ar/H2 O/H2
with pH2 O/pH2 = 0.01 were recorded during cooling at a rate of 5 ◦ C/min.

2.4. Thermal expansion

Along with the high-resolution powder diffraction technique on synchrotron

radiation (Section 2.1), the thermal expansion some of ceramic samples was
also investigated in a LINSEIS dilatometer in air in the temperature range of
293–1123 K.

2.5. Chemical diffusion coefficients

As presented elsewhere [57], chemical diffusion coefficients were deter-

mined at 900 ◦ C by measurements of the electrical conductivity relaxation of
the gas dense ceramic samples after an abrupt change of the oxygen partial
pressures around the samples. Relaxation data were presented in the form of Fig. 1. Phase diagram of the perovskite-type system La(2+y−2x)/3 Cax Cry
fractional conductivity changes versus elapsed time after pO2 jumps [58]. Ti1−y O3 .
274 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280

Table 1
La(2+y−2x)/3 Cax Cry Ti1−y O3 compositions prepared in the system xCaTiO3 − yLaCrO3 − (1 − x − y)La2/3 TiO3

System Formula x Compositions Structure

1 (1 − x)LaCrO3 − xCaTiO3 La1−x Cax Cr1−x Tix O3 or x=0 LaCrO3 Pbnm

La(2+y−2x)/3 Cax Cry Ti1−y O3 at y = 1 − x x = 0.2 La0.8 Ca0.2 Cr0.8 Ti0.2 O3 Pbnm
x = 0.4 La0.6 Ca0.4 Cr0.6 Ti0.4 O3 Pbnm
x = 0.5 La0.5 Ca0.5 Cr0.5 Ti0.5 O3 Pbnm
x = 0.6 La0.4 Ca0.6 Cr0.4 Ti0.6 O3 Pbnm
x = 0.8 La0.2 Ca0.8 Cr0.2 Ti0.8 O3 Pbnm
x=1 CaTiO3 Pbnm
2 (1 − x)LaCrO3 − xLa2/3 TiO3 La(3−x)/3 Cr1−x Tix O3 or x=0 LaCrO3 Pbnm
La(2+y−2x)/3 Cax Cry Ti1−y O3 , x = 0; y = 1 − x x = 0.1 La0.967 Cr0.9 Ti0.1 O3 Pbnm
x = 0.2–0.8 Multiphase region
x = 0.82 La0.727 Cr0.18 Ti0.82 O3 P2/m
x = 0.84 La0.72 Cr0.16 Ti0.84 O3 P2/m
x = 0.86 La0.714 Cr0.14 Ti0.86 O3 P2/m
x = 0.88 La0.707 Cr0.12 Ti0.88 O3 P2/m
x = 0.9 La0.7 Cr0.1 Ti0.9 O3 P2/m
x = 0.92 La0.693 Cr0.08 Ti0.92 O3 P2/m
x = 0.94 La0.687 Cr0.06 Ti0.94 O3 P2/m
x = 0.96 La0.68 Cr0.04 Ti0.96 O3 ?
x = 0.98 La0.673 Cr0.02 Ti0.98 O3 ?
x=1 La0.667 TiO3 ?
3 (1 − x)La2/3 TiO3 − xCaTiO3 La2(1−x)/3 Cax TiO3 or x=0 La0.667 TiO3 ?
La(2+y−2x)/3 Cax Cry Ti1−y O3 , y = 0 x = 0.02 La0.653 Ca0.02 TiO3 Cmmm
x = 0.04 La0.64 Ca0.04 TiO3 Cmmm
x = 0.06 La0.63 Ca0.06 TiO3 Cmmm
x = 0.08 La0.613 Ca0.08 TiO3 Cmmm
x = 0.1 La0.6 Ca0.1 TiO3 Cmmm
x = 0.12 La0.587 Ca0.12 TiO3 Cmmm
x = 0.16 La0.56 Ca0.16 TiO3 Cmmm
x = 0.18 La0.556 Ca0.18 TiO3 Cmmm
x = 0.2 La0.553 Ca0.2 TiO3 Cmmm
x = 0.25 La0.5 Ca0.25 TiO3 14/mem
x = 0.3 La0.467 Ca0.3 TiO3 14/mem
x = 0.4 La0.4 Ca0.4 TiO3 Imma
x = 0.5 La0.333 Ca0.5 TiO3 Imma
x = 0.6 La0.267 Ca0.6 TiO3 Imma
x = 0.7 La0.2 Ca0.7 TiO3 Pbnm
x = 0.8 La0.133 Ca0.8 TiO3 Pbnm
x = 0.9 La0.067 Ca0.9 TiO3 Pbnm
x=l CaTiO3 Pbnm
4 xCaTiO3 − yLaCrO3 − (1 − x − y)La2/3 TiO3 La(2+y−2x)/3 Cax Cry Ti1−y O3 x = 0.2; y = 0.6 La0.333 Ca0.6 Cr0.2 Ti0.8 O3 Pbnm
x = 0.5; y = 0.3 La0.433 Ca0.5 Cr0.3 Ti0.7 O3 Pbnm
x = 0.4; y = 0.4 La0.533 Ca0.4 Cr0.4 Ti0.6 O3 Pbnm
x = 0.3; y = 0.5 La0.633 Ca0.3 Cr0.5 Ti0.5 O3 Pbnm
x = 0.4; y = 0.5 La0.567 Ca0.4 Cr0.5 Ti0.5 O3 Pbnm
x = 0.2; y = 0.6 La0.733 Ca0.2 Cr0.6 Ti0.4 O5 Pbnm
x = 0.2; y = 0.6 La0.733 Ca0.2 Cr0.6 Ti0.4 O3 Imma
x = 0.5; y = 0.2 La0.4 Ca0.5 Cr0.2 Ti0.8 O3 Pbnm
x = 0.5; y = 0.2 La0.4 Ca0.5 Cr0.2 Ti0.8 O3 Imma
x = 0.4; y = 0.2 La0.467 Ca0.4 Cr0.2 Ti0.8 O3 Imma
x = 0.3; y = 0.3 La0.567 Ca0.3 Cr0.32 Ti0.7 O3 Imma
x = 0.3; y = 0.2 La0.533 Ca0.3 Cr0.2 Ti0.8 O3 Imma
x = 0.2; y = 0.2 La0.6 Ca0.2 Cr0.2 Ti0.8 O3 Imma
x = 0.1; y = 0.2 La0.667 Ca0.1 Cr0.2 Ti0.8 O3 Imma
x = 0.05; y = 0.2 La0.7 Ca0.05 Cr0.2 Ti0.8 O3 Imma

structure (space group I4/mcm). In the La2/3 TiO3 -rich range of ters of the perovskite phases, formed in the CaTiO3 -La2/3 TiO3
the system (molar fraction of La2/3 TiO3 0.8/0.96) the ordered system, in dependence on the La2/3 TiO3 content.
perovskite-like structure is formed. The alternation of fully and Increasing Cr- and La-contents in the
partially (∼40%) occupied layers of A-cations is observed in La(2+y−2x)/3 Cax Cry Ti1−y O3 series, that is characterised with the
these structures. Fig. 5 illustrates the changes of lattice parame- orthorhombic perovskite-type structure (Pbnm) and constant
 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280 275

Fig. 2. Calculated (line) and observed (dots) patterns of the difference spectrum for La0.13 Ca0.8 TiO3 .

A-site deficiency 0.07 (solid solution La0.13 Ca0.8 Ti1.0 O3 -

La0.93 Cr0.8 Ti0.2 O3 ), are accompanied with increasing lattice
parameters and cell volumes. Fig. 6 indicates that the separate
lattice parameters change with different slopes. The highest
increase shows the a- and the lowest the b-parameter.
Fig. 7 presents crystal structures and lattice parame-
ters changing with decreasing A-site deficiency (growing
La0.5 Ca0.5 Cr0.5 Ti0.5 O3 content) in the system “La2/3 TiO3 ”-
La0.5 Ca0.5 Cr0.5 Ti0.5 O3 . The compositions with large A-site defi-
ciency have tetragonal Cmmm or P2/m structures and the same
lattice parameters at increasing La0.5 Ca0.5 Cr0.5 Ti0.5 O3 content.
The sample with 0.24 mol fraction of La0.5 Ca0.5 Cr0.5 Ti0.5 O3 in
this system can be refined in both tetragonal and cubic struc-
tures. Nevertheless, there are traces of peaks at the pattern, which
could not be indexed in body-centered lattices. These may indi-
cate a beginning of ordering of A-cation vacancies. The change
Fig. 3. Concentration dependence of the lattice parameters in the
of slope of the cell volume occurs at ∼0.3 and ∼0.7 mole frac-
La1−x Cax Cr1−x Tix O3 (LaCrO3 -CaTiO3 ) system. Lattice parameters and cell tions of La0.5 Ca0.5 Cr0.5 Ti0.5 O3 and may be associated with the
volume are transformed to perovskite-type cell. existence areas of different perovskite structures and ordering
of A-cation vacancies.

Fig. 4. Concentration dependence of the lattice parameters in the Fig. 5. Concentration dependencies of the lattice parameters in the
La(3−x)/3 Cr1−x Tix O3 (LaCrO3 -La2/3 TiO3 ) system. Lattice parameters and cell La2(1−x)/3 Cax TiO3 (CaTiO3 -La2/3 TiO3 ) system. Lattice parameters and cell vol-
volume are transformed to perovskite-type cell. umes are reduced to perovskite-like cell.
276 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280

Fig. 8. Titration current of the cell 2 and oxygen content of the La0.6 Ca0.1 TiO3−␦
powder during heating–exposition–cooling in Ar/O2 gas flow with oxygen par-
Fig. 6. Lattice parameters in the La(2+y−2x)/3 Cax Cry Ti1−y O3 (La0.13 tial pressure 1 Pa.
Ca0.8 Ti1.0 O3 -La0.93 Cr0.8 Ti0.2 O3 ) quasi-binary system with constant A-cation
deficiency (0.07 of A atomic index).

3.2. Oxygen nonstoichiometry and electrical conductivity

No oxygen release was observed during heating of the com-

pounds of the system LaCrO3 -CaTiO3 -La2/3 TiO3 from room
temperature up to 1000 ◦ C in Ar/O2 gas flow with pO2 ≥ 1 Pa.
For example, Fig. 8 illustrates no changes of the both titra-
tion current and calculated oxygen atomic index (3 − δ) for
La0.6 Ca0.1 TiO3 . Only small oxygen release (δ = 0.002–0.015)
was observed in H2 /H2 O/Ar gas flow, as it is shown in Fig. 9
for La0.6 Ca0.1 TiO3 and two other compounds of this series
La0.33 Ca0.6 Cr0.2 Ti0.8 O3 and La0.5 Ca0.5 Cr0.5 Ti0.5 O3 . The initial
oxygen content in compounds was estimated as 2.99 ± 0.01 by Fig. 9. Change of oxygen content some of the La(2+y−2x)/3 Cax Cry Ti1−y O3 pow-
iodometry method. High reduction stability of the investigated der compounds during heating–exposition–cooling in H2 /H2 O/Ar gas flow
compositions indicates absence or presence of indefinable small pH2 O/pH2 = 0.53.
amounts of chromium cations in oxidation states higher as 3+,
as for example in LaCrO3 [25]. and presented in Fig. 10 is relatively low and increases with tem-
The electrical conductivity some of the La(2+y−2x)/3 Cax perature like by typical semiconductors. Chromites–titanates
Cry Ti1−y O3 compounds with different x and y measured in air show much lower activation energy (0.35–0.37 eV) in compar-
ison with pure titanates (1.55–1.65 eV). The conductivity level

Fig. 7. Concentration dependencies of the lattice parameters in the

La(2+y−2x)/3 Cax Cry Ti1−y O3 (“La2/3 TiO3 ”-La0.5 Ca0.5 Cr0.5 Ti0.5 O3 ) system. Lat- Fig. 10. Temperature dependence of the electrical conductivity some of the
tice parameters and cell volumes are transformed to perovskite-like cell. La(2+y−2x)/3 Cax Cry Ti1−y O3 ceramic samples measured in air.
 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280 277

Due to reduction of Ti4+ -cations to Ti3+ at elevated temper-

atures in reducing conditions, the yellow coloured compounds
change their colour to black. The observed n-type conductivity
of the prepared samples in terms of the Kröger–Vink notation
[59] can be explained with oxygen release:
•• /
O× ×
O + 2TiTi
VO + 2TiTi + 0.5O2 (1)
assuming that conduction electrons are located on Ti3+ -cations.
The observed log(σ)/log(pO2 ) slope was near −1/4.
Most likely, appearing oxygen vacancies cannot annihilate
with La,Ca-vacancies, because all the B-site positions in the
perovskite-type structure stay occupied with Cr3+ , Ti4+ and Ti3+
cations and no other compounds enriched with Cr or Ti were
Fig. 11. pO2 -dependence of the electrical conductivity some of the
detected by XRD method after reduction processes.
La0.567±␥ Ca4 Cr0.5 Ti0.5 O3 ceramic samples at 900 ◦ C. The p-type conductivity of the La(2+y−2x)/3 Cax Cr0.5 Ti0.5 O3
compounds in the relatively high oxygen partial pressure region
below 1000 ◦ C increases with increasing Cr-content on the B- (Fig. 11) can be explained with existence of Cr4+ cations:
sites of the perovskite-type structures. Changing La/Ca-ratio and •• •
2Cr× ×
Cr + VO + 0.5O2
2CrCr + OO (2)
corresponding A-site deficiency of titanates influence only a lit-
tle the conductivity level and activation energy. assuming that conduction holes are located on Cr4+ -cations.
The pO2 dependencies of the conductivity of the The experimental slope log(σ)/log(pO2 ) = +1/6 was observed.
La(2−2x)/3 Cax TiO3 compounds at 900 ◦ C presented in [57] The formation of Cr4+ states may be understood as result of
demonstrate very good linearity in logarithmic coordinates with the partial disproportionation of Cr3+ cations into Cr2+ –Cr4+
a slope around −1/4. Only small slope increase was observed pairs. This possibility for perovskite and perovskite-related
at changed structures from Cmmm at x = 0.1 to Imma at x = 0.4 structures was shown theoretical by Goodenough [60] and then
and to Pbnm at x = 0.8. The La(2+y−2x)/3 Cax Cry Ti1−y O3 com- suggested for stabilization of Mn3+ ions into Mn2+ –Mn4+ pairs
pounds with y = 0 and 0.2 show linear dependences, but the in La1−x Srx MnO3 [61] and Bi4+ cations into Bi3+ –Bi5+ pairs in
samples of this series with y = 0.5 demonstrate conductivity min- BaBiO3 [62,63], for example.
ima in the pO2 region 10−4 to 102 Pa. Fig. 11 presents the The observed shift of the conductivity minima to oxygen
pO2 -dependences for three La0.567±␥ Ca4 Cr0.5 Ti0.5 O3 samples reach site with increasing A-site deficiency may be related with
with different A-site deficiency near La(2+y−2x)/3 Cax Cry Ti1−y O3 changing Cr4+ and Ti3+ cation concentrations at these experi-
nominal composition. Decreasing A-site deficiency shifts mental conditions.
conductivity minima to higher pO2 from 10−3.5 to 10−3
and 10−1.5 Pa, respectively. Due to this strong composi- 3.3. Thermal expansion
tional influence, the solid-state synthesis of the compounds
with comparable Cr and Ti contents can result in the Thermal expansions of La0.4 Ca0.4 TiO3 in the a-, b- and c-
formation of materials with noticeable different electrical directions determined by synchrotron radiation are practically
properties. similar up to ∼550 ◦ C (Fig. 12). A slope change of the a-
Increasing from 0.547 to 0.597 La-content in La0.567±␥
Ca4 Cr0.5 Ti0.5 O3 changes colour of the powders from deep-green
to chlorine. The corresponding ceramic samples sintered in air
at 1250 ◦ C and cooled to room temperature at 7 ◦ C/min showed
changing surface colour from light-grey to deep-yellow. The
grey colour was probably caused by the presence of the Cr4+ -
cations. Increasing La-content apparently reduces the content of
Cr4+ -cations in these compositions.
As majority of the single phase La(2+y−2x)/3 Cax Cry Ti1−y O3
compositions prepared in the quasi-ternary system CaTiO3 -
LaCrO3 -La2/3 TiO3 in air had yellow colour, the oxidation
states of chromium and titanium cations in these com-
positions can be assumed near 3+ and 4+, respectively.
The general formula for the A-site deficient compounds of
the series La(2+y−2x)/3 Cax Cry Ti1−y O3 synthesized in air can
be written as La3+ 2+ 3+ 4+ 2−
(2+y−2x)/3 Cax Cry Ti1−y O3 . Probable, the
A-site vacancies in the cationic sub-lattice are distributed Fig. 12. Temperature dependence of the lattice parameters and the cell volume
statistically. of La0.4 Ca0.4 TiO3 powder determined by diffraction of synchrotron radiation.
278 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280

Fig. 13. Temperature dependence of the relative expansion (L/L0 ), thermal

Fig. 14. Relative thermal expansion of La0.47 Ca0.4 Cr0.2 Ti0.8 O3 determined by
expansion coefficient (TEC) and the first derivative of the relative expansion of
dilatometry and diffraction of synchrotron radiation.
the La(1.2+y)/3) Ca0.4 Cry Ti1−y O3 ceramics.

parameter is observed at temperatures above 550 ◦ C. The dif-

ference between a- and c-parameters at temperatures higher
than 550 ◦ C decreases and disappears at 900 ◦ C indicating a
transition to the cubic structure. The slope changes of the
a-parameter and the cell volume of the La0.4 Ca0.4 TiO3 sam-
ple correspond with the observed anomalies of the thermal
expansion, obtained by dilatometric method (Fig. 13). The
derivative of the relative expansion with respect to tempera-
ture was used for more visibility of the anomalies registered by
dilatometry.
Fig. 13 represents the linear thermal expansion of the
La(1.2+y)/3 Ca0.4 Cry Ti1−y O3 ceramic samples with x = 0.4 and
y = 0, 0.2 and 0.5 measured in air by dilatometry in comparison
with the YSZ ceramics. The thermal expansion coefficients of
the La0.4 Ca0.4 TiO3−␦ (x = 0.4, y = 0) and YSZ samples measured
by dilatometric method are almost equal. Increasing Cr-content
(y) is accompanied by decreasing thermal coefficients of the Fig. 15. Time dependence of the conductivity of the gas dense La0.47
Ca0.4 Cr0.2 Ti0.8 O3−δ ceramic sample after the corresponding gas flow switches.
corresponding ceramics.
The agreement of the thermal expansions of La0.4 Ca0.4
TiO3−␦ and YSZ in air within the temperature range 20–
950 ◦ C is typical for all others compounds of the series
La2(1−x)/3 Cax TiO3 . Thermal expansion of La0.47 Ca0.4
Cr0.2 Ti0.8 O3 and YSZ in the temperature range 20–900 ◦ C in
air has only small difference. Properly, no thermo-mechanical
compatibility problems should appear at stable contact between
lanthanum–calcium titanates and solid electrolyte membranes
based on YSZ.
The differences of the thermal expansion of the
La0.47 Ca0.4 Cr0.2 Ti0.8 O3 samples observed by using dilatometry
and diffraction of synchrotron radiation are negligible small
(Fig. 14).

3.4. Oxygen mobility

The gas dense ceramic samples could not be prepared on the

basis of A-site stoichiometric compounds La1−x Cax Cr1−y Tiy O3 Fig. 16. X-ray diffractograms of La0.47 Ca0.4 Cr0.2 Ti0.8 O3−δ before and after
[25] by sintering in air up to 1350 ◦ C. Even small A-site defi- annealing at 900 ◦ C for 100 h in H2 /H2 O/Ar gas flow with pH2 O/pH2 = 0.01.
 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280 279

ciency gives this opportunity. The oxygen mobility in selected

gas dense ceramic samples was estimated by using the con-
ductivity relaxation method [64]. Fig 15 demonstrates the
conductivity relaxation of the La0.3 Ca0.4 Cr0.2 Ti0.8 O3 speci-
men with density 4.10 g/cm3 (93% of the theoretical den-
sity) at 900 ◦ C after abrupt change of the oxygen partial
pressure around the ceramic sample between air and Ar/O2
gas mixture with pO2 = 916 Pa. The chemical diffusion coef-
ficient of this ceramic sample at the mentioned conditions
was estimated as (5–9) × 10−9 cm2 s−1 . Similar values between
(1–10) × 10−9 cm2 s−1 were found for the samples of the
series La0.6−γ Ca0.4 Cr0.2 Ti0.8 O3 with y = 0.05–0.3. No essential
changes of the chemical diffusion coefficients for samples with
different A-site deficiency were observed.
Fig. 17. X-ray diffractograms of La0.47 Ca0.4 Cr0.2 Ti0.8 O3−δ and (La0.47
Ca0.4 Cr0.2 Ti0.8 O3−δ + YSZ) powder mixture after annealing at 1300 ◦ C for 200 h
3.5. Chemical stability
in air.
All prepared single-phase La(2+y−2x)/3 Cax Cry Ti1−y O3 com-
positions were phase stable at 20–1000 ◦ C and pO2 = 10−15
to 105 Pa. For example, Fig. 16 demonstrates identity of the
X-ray difractogramms of the La0.47 Ca0.4 Cr0.2 Ti0.8 O3 powder
before and after annealing at 900 ◦ C in H2 /H2 O/Ar gas flow
with pH2 O/pH2 = 0.01 and Fig. 17 shows no reactivity between
La0.47 Ca0.4 Cr0.2 Ti0.8 O3 and YSZ after annealing up to 1300 ◦ C
in air. No interaction was detected by scanning and raster elec-
tron microscopy, too (Fig. 18). The corresponding smooth con-
centration profiles of the separate elements were observed in the
range of 1–2 ␮m.

4. Conclusions

A-site deficient La(2+y−2x)/3 Cax Cry Ti1−y O3 solid solution

with different perovskite-type structures (space groups Pbnm,
Imma, I4/mcm and Cmmm or P2/m) is formed in the CaTiO3 -
LaCrO3 -La2/3 TiO3 quasi-ternary system in air conditions. Sta-
bilization of the La2/3 TiO3 structure by low-level substitution
of the both A- and B-cation sites is observed. Continuous phase
transitions from orthorhombic (Cmmm) or monoclinic (P2/m),
to tetragonal (I4/mcm), orthorhombic (Imma) and orthorhombic
(Pbnm) are registered for the Ca- and Cr-stabilized La2/3 TiO3
structures. The compounds show high stability at high tem-
peratures and reducing as well as oxidizing conditions. No
reactivity between A-site deficient chromites–titanates and YSZ
was observed in air up to 1300 ◦ C. At 900 ◦ C, the compositions
with y = 0, 0.2 are n-type semiconductors, and with y = 0.5 show
conductivity minima versus oxygen partial pressure these shift
to oxygen reach region with the increasing, A-site deficiency.
The A-site deficient samples have higher sintering ability in
comparison with the cation stoichiometric La1−x Cax Cr1−y Tiy O3
compositions and in contrast to the latter can be prepared in
gas dense state in air at temperatures 1200–1300 ◦ C. Ther-
mal expansion of the A-site deficient ceramics is comparable
with YSZ. The oxygen mobility can be characterised with
chemical diffusion coefficients (1–9) × 10−9 cm2 s−1 at 900 ◦ C
and pO2 = 1000–21,000 Pa. It seems that the relatively low
Fig. 18. Raster electron microscopy and EDX-analysis of the
La0.47 Ca0.4 Ti0.8 Cr0.2 O3 /YSZ boundary after annealing at 1300 ◦ C dur- oxygen mobility of the A-site deficient chromites–titanates
ing 5 h in air. serves as the only disadvantage of these compositions with
280 V. Vashook et al. / Journal of Alloys and Compounds 419 (2006) 271–280

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