346

lonics 6 (2000)

Structural and Electrical Investigations of

(Y,Gd)l.xCro.sGao.zO3
D. Westphal 1'*, A. Laske ~, S. Jakobs 2 and U. Guth 3
1Sensor Research Center Greifswald, Germany
2Institute for Chemistry and Biochemistry, University of Greifswald, Germany
3Kurt-Schwabe-Institut Meinsberg, Technical University of Dresden, Germany

Abstract. Pure and gallium doped YCrO 3 and GdCrO 3 with the formula (Y,Gd)l_xCro.sGa~).203 (x =
0 ..... 0.2), prepared by a conventional oxide method, were investigated regarding the influence of Acation-deficiency on structure, conductivity and electrode behaviour in a special modified galvanic
cell for the determination of gaseous hydrocarbons (HC). All samples form the GdFeO 3type orthorhombic perovskite structure but with A-site-substoichiometry a second phase,
(Y,Gd)3GasO~2, with garnet structure occurs. All investigated chromites are semiconductors. The
total conductivity in air is influenced by the second phase. The use of these samples as electrode
materials does not show a HC sensitive behaviour.

1. Introduction
The properties of perovskite type oxides (ABO3), e.g. the

ciency. These samples have been investigated regarding

structure, conductivity and electrode behaviour on special

electrochemical and catalytic behaviour, can be modified

by partial substitution of A- and B-site-cations without
changing the structure [1]. The perovskite structure also

galvanic cells using YSZ as electrolyte for potentiometric

HC determination.

seems to permit a small A-cation-deficiency without for-

2.
Experimental Description
The mixed oxides was prepared from the appropriate

mation of a second phase [2].

Lanthanum chromites show a low catalytic activity
for the combustion of hydrocarbons, which can be further
diminished by partial replacement of chromium by
gallium [3]. Therefore gallium doped chromites could be

amounts of Y203, Gd203, Ga203 and Cr203. Various reaction mixtures with the following composition (Y,Gd)j_x
Cro.sGa0.203 (x = 0 ..... 0.2) were prepared and sintered at
1673 K for 10 h in air.

used as electrode materials for high temperature HC sensors based on yttrium stabilized zirconia solid electrolyte.
Due to the HC sensitivity of the gallium doped lan-

The structure determination was carried out by XRD.

The XRD patterns were registered using CuK~ radiation.

thanum chromites, the following question arose: is

ployed.
Electrical conductivity was investigated on pressed

lanthanum necessary or do similar ions cause comparable

properties? To try to answer this question gallium doped

A 20-step of 0.02 ~ and a counting time of 1 s were em-

pellets, sintered at 1273 K for 10 h. Electrodes were

yttrium and gadolinium chromites were investigated.

deposited on both sides of the pellets by platinum paint.

After calculation of the GOLDSCHMIDT tolerance factor

The conductivity was obtained by impedance spectroscopy

it should he possible to get the perovskite phase in the

case of the stoichiometric and also of the substoichiometric chromites with a small A-cation-defi-

with a frequency response analyser over a frequency range

of I00 Hz - 100 kHz.
For testing as electrode materials the samples were

*corresp. author: D. Westphal, phone: +49-3834-864395

fax +49-3834-864427, e-mail: westphal@mail.uni-greifswald.de

Ionics 6 (2000)

347

poroussteatitebody
to fix the YSZ pellet referenoeelectrode
themlcx:x~ple

n suring

gas

air

)
.

mites. For a better differentiation between the stoichiometric and the substoichiometric sample (GdCro.~Ga~203
and Gdo.9Cro.sGao.203)a diagram with higher resolution is
shown (Fig. 3). In the substoichiometric samples a
second phase with garnet structure (Y3GasOI2, Gd3GasO~2)
occurs besides the orthorhombic perovskite phase as the
major one. Therefore we assume that the stoichiometric

~"~////////////////////////////////////////d'

," I \ \
I
YSZ r~let ~th

The same results were found for the gadolinium chro-

said eeetraytetube 0'SZ)

perovskite type orthorhombic phase is formed in any case

while the biggest part of the rest of the starting oxides

Fig. 1. Cell arrangement (schematic).

form garnet type cubic phases like Y3GasO~ or

Gd3Ga50~2. It is known that at normal pressure the garnet
type (Y,Gd)3GasO~2-structure [4] is formed. Formation of

deposited as thick-films onto YSZ substrates by screenprinting. The HC sensitivity of the chromite electrodes

YGaO 3 and GdGaO 3 [5] needs additionally high pressure

and high temperature. Of course there must be at least one
phase more to fit the nominal chemical composition. A

test electrode

was determined using propylene (C3H6) in a special galvanic cell (Fig. 1) by measuring the cell voltage. The

C3H6 concentration varied from 0 to 0.8 Vol.-% in a gas

mixture with N2 and 1.5 Vol.-% 02. The gas flow was
200 ml/min and the measuring temperature ~ 700 ~
3.

Results and D i s c u s s i o n

3.1.

small amount of the starting oxides Y203 and Gd203

should remain unreacted, but these phases could not be
identified because of the limits of the XRD technique.
After these results we assume that the gallium doped
yttrium- and gadolinium chromites do not permit an Acation-deficiency in the lattice if prepared by the conventional oxide method.

Structural Characterization.

3.2. Conductivity. All investigated oxides are semi-

The stoichiometric
compounds YCrO3, YCr~.sGar~.203, GdCrO3 and GdCr~.~

conductors, their conductivity behaviour can be explained

Gao.203 form the GdFeO3-type orthorhombic perovskite

with a thermically activated ,,hopping-mechanism,, of the

structure, but contrary to the gallium doped lanthanum

electronic defects. The calculated activation energy for the

chromites the substoichiometric samples Yo.9Cro.sGao.203,

conductivity of the samples is shown in Table 1. The

Yo.~Cro.sGao.~O3, Gdo.9Cro.~Ga~).203 and Gdo.sCro.sGao.803

were formed incompletely. To illustrate this all XRD
patterns of the yttrium chromites are presented in Fig. 2.

conductivity behaviour of the substoichiometric samples

is strongly influenced by the second phase.
The conductivity of the samples in air is shown in

x - Y3GasO~2

tll

[x

Yo8Cro.,Gao.203

5
"W"~ YogCor~Gao=O
-.-.
(.-

"~

--

I~

YCro.,Gao~O3

10

20

30

40

50

60

70

80

2e (CuK~)/deg.

Fig. 2. XRD pattern of Yt_~Cr0.sGa0.203 (x = 0, 0.1, 0.2) and

YCrO 3.

26

iltl[I

28

30

32

GdCrosGao203

34

36

38

40

42

44

46

48

. . .
50 52 54

56

2|

Fig. 3. XRD pattern of GdCr0~Gao203 and Gd0,jCr0sGa020~.

348

Ionics 6 (2000)

Table 1. Activation energy of the conductivity of Yl-xCr0.8Ga0.20~and Gdj_~Cr0.sGa0.203.

S/~
0.1

Y t_aCrg8G%,?O~
0

12.6

15.2

0. I

11.0

0.1

16.2

0.2

11.2

0.2

17.4

YCrO~

11.2

GdCrO3

8.4

Figs. 4 and 5. As expected the pure yttrium and gadolinium chromite show the highest conductivity. With
gallium doping the conductivity decreases due to the dilution of the charge carrier (Cr3+/Cr4+) by the valence
stable Ga3+-ions.
For the inhomogeneous samples a different bebaviour
has been found. The substoichiometric yttrium chromite
samples show a higher conductivity than the stoichiometric one. Probably the second phase (Y3GasOj2) produces a conductivity rise caused by a composite effect. In
such case small grains of the second - worse conducting phase surround a grain of the major phase and the conductivity increases.
From the stoichiometric GdCro.sGao.203 to the substoichiometric Gdo.9Cro.~Ga~.203 the conductivity decreases
because the amount of the second phase (Gd3Ga5 O12)
might be not enough to produce a composite effect. But
in the Gdo.sCrosGao.203-sample which shows a higher
conductivity than GdCrosGao.203, the second phase proS/~
'

--

900
'

-0-t~lll,_ 9

800

700

600

500

'.

800

700

600

500

Ej(kJ/mol)

EJ(kJ/mol)

104

900

Gdl_~Cro,~Ga/~,~O~

1000

1000

~-

9[] YCrO3
YCro.sGao20~ i
XA yooCro6Gao=03

---O-

Yo6Cro,Gao.20a

10

11

duces a composite effect.

3.3. Cell Voltage Measurements. For the investigation of

the HC sensitivity a galvanic cell with the chromites as
measuring electrode and a Pt air reference electrode was
used (Fig. 1). If electrode materials, e.g. Pt, are catalytically active for the conversion of combustible components (C3H~), the gas is equilibrated at the electrode and
the cell voltage follows the Nernst equation. The electrodes show a Nernstian behaviour. HC sensitive electrodes are catalytically inactive for the conversion of
hydrocarbons and show a non-Nernstian behaviour. In the
ideal case, the cell voltage depends on the HC content in a
non-equilibrated gas mixture. In the real case, the electrode potential will be also influenced by the oxygen
content, resulting in a mixed potential. In a very simple
model [1] the electrode potential should be determined by
the following two competing electrode processes (1 +2):
;O2(g)+9V~) ~+18e-

)
(

9 0 0 (ZrO2)

C3H6 ( g ) + 9 0 o (ZrO2)-+ 3CO 2 (g)

v
b

+3H20(g)+9Vo~ +lSe -_.

- - -llk_

13

Fig. 5. Electrical conductivity as a function of temperature

for Gd~_xCr0.~G%20~ (x = 0, 0.1, 0.2) and GdCrO~.

g
G-

12

104K/T

9
~ O 2 ( g ) + C 3 H 6(g) - ~ 3 C O 2 ( g ) + 3 H 2 0 ( g )

_......

(1)
(2)

(3)

These reactions present the main processes only. In

10"2

1~0

1~1

ld2

1~3

104K/T
Fig. 4. Electrical conductivity as a function of temperature
for Y~_~Cr0,Ga0.20~(x = 0, 0.1,0.2) and YCrO 3.

reality, the processes are much more complicated and will

be also influenced, e.g. by adsorption, desorption and by
several surface reactions. But with this model it is
possible to describe the non-Nernstian or HC sensitive
behaviour. If the electrode reaction (2) is faster than the
oxygen electrode reaction (1) the electrode potential is

Ionics 6 (2000)

349

x>l

Z<I

;'.=1

1100 ~ N~, C~He with 1.5 Vof% 02

000 ~
700oC
q
9oo -4

70D Nz, CaH~with 15 VoI% O2

9 YCr
YCrO
a o203 I
--El-o~Ga
--&- Yo~CroeGao=Oa
--X-- YoeCr~eGao=O~

800 1
7OO
E 600

700~

600 -

~ ~ ' - La~1768Ga~ [1] i

o - - Yo~CroeGao20~
|
9- Odo,Cio~Gao,% I
I

400300

D -----

~ ,

500 >

500
400
300

A~o

/
/
/
/ j,_7~j,_----~

200
100 -

200 1
100 _ _ 1 1 _ _ 1 1 . . , _ = ~ = ~ = 1 ~ - ~ - - - ~ - - - ~

0.0

01

02

O0

03
04
(C~H~) / Vol-%

05

06

strongly affected by the C3H 6 concentration. You have an

HC sensitive electrode.
The aim of this investigation was the determination of
the propylene characteristic of our chromite electrodes. If
such an electrode shows HC sensitive behaviour, the cell
voltage dependence on the gas C3H 6 concentration over a
wide range should be nearly linear. But the measurements
show that the propylene characteristic of the yttrium and
gadolinium chromite electrodes at 700 ~ is not compro'able with an HC sensitive electrode (Figs. 6 and 7),
The behaviour is similar to an equilibrium electrode. It
seems that combustion of propylene happens on the
electrode surface: the gas is nearly equilibrated and the cell
voltage signal depends strongly on oxygen partial
pressure at the electrode. In Fig. 8 the propylene characteristic of Lao.gCro.~ Gatl.203- and (Y,Gd)o.gCro.~Gao.203-

k>1

).=I

2,<I

N~,C=H~with 15 Vol-% O;
700~

~ooo
900

BOO
70Oi
~BO0!
~

500-

4002

--[3-- GdCroeGa~20 a

300

_A_

Gdo ~Cr~8Gao~O ~

200
100

ill

i--

00

0.1

02

0.3
(C~H6)Nol -%

Fig. 7. Propylene characteristic

Gdo.,>Cro.sGao.203.

04

0~1

07

Fig. 6. Propylene characteristic of Yj_,Cro.~Gao.20 ~ (x = 0 ,

0.1, 0.2) and YCrQ.

1100 ~

.-.

0.5

of GdCr0.sGa0.203 and

'

0'2

0'3
'
e(C3H6)NoI -%

Fig. 8. Propytene characteristic

Y0.gCr0.sGa0.:O3and Gd0.gCro.sGa0.203.

0'4

0'5

06

of Lao,gCr0.,~Gao.203,

electrodes are presented. The reason for the different propylene characteristic of Lao.9Cro.sGao.203- and (Y,Gd)o.9Cro.sGao.203-electrodes might be the formation of a second
phase, which probably influences the sample morphology
and not least the electrode surface. So it can be said, that
contrary to the assumption yttrium and gadolinium chromites systems although similar to lanthanum chromites
are not usable as electrode material in potentiometric HC
sensors.
4.

Conclusions

The yttrium and gadolinium chromites are semiconductors. The stoichiometric samples form the homogeneous GdFeO3-type orthorhombic perovskite phase
only. The nominal substoichiometric yttrium and gadolinium chromites will be formed incompletely: a
second phase with garnet structure was found. The
conductivity of the Y~_,Cro.sGao.:O~ is strongly influenced
by the second phase. The substoichiometric samples
show a higher conductivity than the stoichiometric
YCro,Gao.203. This behaviour is caused by a composite
effect, produced by the second phase. GdCro.~G%203
shows similar conductivity as YCro.~ Gao.20 > But the
conductivity of the Gdo.9Cro.sGao.203 substoichiometric
samples decreases. Only for Gdo.s Cro.sGao.:O3 the conductivity rises. Probably in this sample the amount of the
second phase is high enough for a composite effect. In
comparison to the lanthanum chromite yttrium and gadolinium chromite are not usable as electrode material for
potentiometric HC sensors. Their propylene characteristic
is comparable to the behaviour of an equilibrium electrode
in a galvanic cell based on solid electrolyte.

350

Ionics 6 (2000)

5.

References

[1]

S. Jakobs, R. Hartung, U. Lawrenz, P. Sandow, U.

Sch6nauer, U. Guth; Ionics 2, 451 (1996).
H. Runge, U. Guth, Int. Conf. On Solid State
Ionics; SSI 11; Honolulu (1997); proceedings in
press.
K.-P. Sandow, S. Jakobs, D. Westphal, S.
Thiemann, R. Hartung, U. Sch6nauer, U. Guth;
Ionics 2, 435 (1996).

[2]

[3]

[4] G. Sallavuard, G. Szabo and R.A. Paris; C.R. Acad.

Sc. Paris, t. 268, Serie C-1051, (1969).
[5] M. Marezio, J.P. Remeika and P.D. Dernier; Inorg.
Chem. 7, 1337 (1968).

Paperpresented at the 6th Euroconference on Solid State

lonics, Cetraro, Calabria, Italy, Sept. 12-19, 1999.
Manuscript rec. Oct. 4, 2000; acc. Nov. 20, 2000.