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@PHDTHESIS{Gindorf:29351,
author = {Gindorf, Christian},
title = {{U}ntersuchungen zur {C}hromfreisetzung aus metallischen
{I}nterkonnektorwerkstoffen für die
{H}ochtemperaturbrennstoffzelle},
volume = {3853},
issn = {0944-2952},
school = {Techn. Hochsch. Aachen},
type = {Dr. (FH)},
address = {Jülich},
publisher = {Forschungszentrum Jülich GmbH Zentralbibliothek, Verlag},
reportid = {PreJuSER-29351, Juel-3853},
series = {Berichte des Forschungszentrums Jülich},
pages = {IV, 100 p.},
year = {2001},
note = {Record converted from VDB: 12.11.2012; Aachen, Techn.
Hochsch., Diss., 2001},
abstract = {Metallic interconnect materials (chromium-based alloys and
chromium-containing steels) form volatile chromium species
under operating conditions of the Solid Oxide Fuel Cell.
These volatile Cr(VI) species are reduced to solid Cr(lII)
compounds at the triple phase boundary
cathode/electrolyte/oxidant after penetrating the cathode
material, leading to a degradation of the electrochemical
properties of the cell. In this work the vaporization of
volatile chromium species was studied by the transpiration
method. Transpiration experiments were carried out under
equilibrium as well as nonequilibrium conditions.
Equilibrium studies were carried out in air, using Cr203(s)
(powder) at different water partial pressures (between 0.7
mbar and 0.3 bar) and temperatures (between 400 °C and 950
°C). Thermodynamic calculations based on the measured
temperature dependence yielded an enthalpy of reaction of
OrH94s = 122.85 kJ/mol for the formation of the volatile
chromium species Cr02(OH)2(g) (dominating in the vapour over
Cr203(S) under these experimental conditions) .
Transpiration experiments under non-equilibrium conditions
were carried out at a water vapour pressure of p(H20) = 0.02
bar at temperatures of 850 °C and 950 °C. The chromium
vaporization rate of metallic interconnect materials forming
different oxide scales as well as the chromium vaporization
of different coated alloy samples (perovskite coatings on
Cr5FelY203 and X10CrAl18 substrates) were determined.
Perovskite coatings are used as a diffusion barrier against
volatile chromium(VI) species vaporizing from the
interconnect surface . In this work the chromium retention
potential of vacuum plasma sprayed coatings (scale thickness
25-30 [,m) was investigated by comparison of chromium
transport rates of coated and uncoated interconnect samples.
As a result of this experiments a chromium retention of more
than 99 $\%$ was found for protective perovskite coatings
(e.g. Lao.9Sro.,Cr03) under cathodic operating conditions of
the SOFC. Investigations of the scale morphology of
perovskite coatings revealed a time dependent densification
process. Due to that densification process possible values
of more than 99 $\%$ were observed after different annealing
times. The vaporization of volatile chromium(VI) species
from coated interconnect specimens is caused by cracks and
pores in the protective scale. This was confirmed by 53Cr
tacer experiments with protective perovskite scales based on
lanthanum chromfite which were carried out to obtain
chromium self diffusion coefficients . For the scale
composition of Lao.9Sro.1CrO3 at a temperature of 1000 °C a
chromium diffusion coefficient of 2.59 - 10-16 cm2/s was
determined. Considering a scale thickness of 30 [tm, from
this diffusion coefficient, a break through time of 550
years can be calculated. According to these results, grain
boundary diffusion as well as bulk diffusion are too slow to
compete with gas phase transport of chromium through the
protective scale. Considering the results of this work it is
possible to reduce the chromium deposition rate in the
cathode by a factor of more than two orders of magnitude if
the SOFC operating temperature is decreased by 100 °C from
950 °C to 850 °C and if proper substrate/coating
combinations are used},
cin = {IWV-2},
cid = {I:(DE-Juel1)VDB2},
pnm = {Werkstoff- und Bauteilentwicklung für die
Hochtemperatur-Brennstoffzelle},
pid = {G:(DE-Juel1)FUEK22},
typ = {PUB:(DE-HGF)11 / PUB:(DE-HGF)3},
url = {https://juser.fz-juelich.de/record/29351},
}