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Oxide
MO
Gas
O2
Cations
Cation Vacancies
Electrons
Anions
aM
pO
2GMO
RT
x
M = M2+ + 2e
or
2
M + O = MO + 2e
GMO
a"M = 1 exp
(p"O )
RT
O
M2+ + 2e + 12 O 2 = MO
or
1 O + 2e = O 2
2
2
o
Overall reaction: 2M + O 2 = 2MO; GMO
B i i
(
+ Zi F
)
N A x
x
ji = C i vi =
kTBi = Di =
Ci Bi i
(
+ Zi F )
N A x
x
N A RT i
Ci ( Z i F ) 2
Replace Bi in ji
ji =
i i
+ Zi F
2 2
Z i F x
x
c c
+ Zc F
2
2
x
Z c F x
(A.)
(B.)
je =
e
+ Ze F
x
Z F x
2
e
(B.)
c c e e
1
=
+
x
F ( c + e ) Z c x Z e x
c Z c e
c e
Z F ( c + e ) x Z e x
2
c
Zc F x M c + e
dx
dt
CM mol cm-3
Comparison with the parabolic rate equation
dx k
=
dt
x
1
2
Zc F 2 C M
c e
d M
c + e
c c e e
1
i
=
+
+
x
F ( c + e ) Z c x Z e x ( c + e )
jc =
c e c Z c e c i
+
Z c2 F 2 x Z e x Z c F
i Stop =
e M
Zc F
i
1
k = k OC
i Stop
o
M = G MO
For chromia at 900oC: e = 10-2 (ohm cm)-1 Park & Natesan, 1990
Go = -820,000 J/mole
For a 1 m thick oxide: iStop = -140 A/cm2
For a typical Fuel Cell current density of 1 A/cm2,
k = k OC
(Note: if Park & Natesans 2-probe data are correct there could be a
substantial effect of current on chromia growth.)
-0 5
y = 2.61E-11x
-0 5
-0 6
g2/cm4
6
-0 6
y = 1.23E-11x
-0 6
-0 6
Nickel
Sr-doped Nickel
0 0 0 0
0 0 0 0 0
0 0 0 0
0 0 0 0 0
seconds
2
0 0 0 0
0 0 0 0 0
0 0 0 0
0 0 0 0 0
0 0 0 0
0 0 0 0 0
Surface Micrographs
Nickel 900C
p
RT O2
ln C
V0 =
4 F pO2
Repeat Components
Electrolyte YSZ
Anode Ni/YSZ
V 0.7volts
2
i
1
Amp
/
cm
Cathode La/Sr-Manganite (LSM)
Interconnect Metallic
Alloy
Exhaust
Experimental Arrangement
Thermocouple
H2-3%H2O
Air
Air
H2-3%H2O
Air
Air
Materials:
Materials:
1010mil
milthick
thickAg
Agtube
tube
Variables:
Variables:
o
Temperatures,
o
Temperatures,700,
700,600,
600,500
500C;
C;
Simultaneous
2+3%H
2O
Simultaneousexposures
exposurestotoHH
2+3%H2O
and
andair;
air;
Diagram of Apparatus
Crofer - 2
E-brite - 1
0.50
E-brite - 2
AL453 - 1
AL453 - 2
ZMG232 - 1
0.40
ZMG232 - 2
0.30
0.20
0.10
0.00
0
200
400
600
800
1000
1200
Exposure (Cycles)
1400
1600
1800
2000
Time vs. Mass Change / Area for Crofer, E-brite, AL453, & Ni (700 C, Ar/H2 /H20)
0.70
Crofer - 1
Crofer - 2
E-brite - 1
0.60
E-brite - 2
E-brite - 3
AL453 - 1
0.50
AL453 - 2
Ni
0.40
0.30
0.20
0.10
0.00
0
200
400
600
800
1000
Exposure (cycles)
1200
1400
1600
1800
2000
Cr2O3
MnCr2O4
Cr2O3
Si rich oxide
Dry Air
2000 cycles
Si rich oxide
Internal Al2O3
Internal Al2O3
Wet Air
1017 cycles
MnCr2O4
Cr2O3
Internal Al2O3
SAG
2000 cycles
Si rich oxide
Degradation Mechanism
O2(g)= 2[O]Ag
Reaction Steps
[O]Ag
Ag/Fuel interface
2. (O2) g = 2(O)Ag
[H]Ag
Air
H2(g)
-6
log p(Cr)
log p(Mn)(A)
-8
log p(La)
log p(Mn)(B)
Cr2O3
-10
MnCr2O4
-12
LaCrO3
-14
-16
-18
0.7
Note:
0.75
0.8
0.85
0.9
3
1/T*10 (K-1)
0.95
1.05
MnCr2O4
with ~1.5%
Sr and ~2.6%
La
MnCr2O4
Cr2O3
Crofer (side in
contact with cathode)
~74.9% Fe
~20% Cr
~2.2% La
~2% Mn
~0.9% Sr