You are on page 1of 19

Ellingham Diagram

Growth rates of selected oxides


CoO>NiO>Cr2O3>Al2O3

Thermodynamic stabilities of selected


oxides Al2O3>Cr2O3>CoO>NiO

Effect of Electrical Current on Oxidation Rate


Metal
M

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

(p'O ) M/MO = exp

M2+ + 2e + 12 O 2 = MO
or
1 O + 2e = O 2
2
2

o
Overall reaction: 2M + O 2 = 2MO; GMO

Oxidation Under Open Circuit Conditions


vi =
1

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

Consider a scale growing by cations moving outward.


jc =

c c

+ Zc F
2
2
x
Z c F x

(A.)

(B.)
je =


e
+ Ze F

x
Z F x
2
e

Electrical Neutrality (C.)


Z c jc + Z e je = 0

(B.)

c c e e

1
=
+

x
F ( c + e ) Z c x Z e x

The cation flux now becomes:


jc =

c Z c e
c e

Z F ( c + e ) x Z e x
2
c

Considering ionic equilibrium and integrating across the oxide


M
1
c e
jc = 2 2
d M

Zc F x M c + e

The relation between jC and scale growth rate is


jc = C M

dx
dt

CM mol cm-3
Comparison with the parabolic rate equation
dx k
=
dt
x

where k is the parabolic rate constant in cm2s-1.


k =

1
2
Zc F 2 C M

c e
d M
c + e

Oxidation in the Presence of an Impressed Current


Equations (A) and (B) are unchanged. Equation (C) is written:
Z c Fjc + Z e Fj e = i

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

Note: If the external oxygen pressure is 1 atm,

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.)

Parabolic Rate Constants


900C dry air
1

-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

Parabolic Rate Constant


Nickel
2.61x10-11 g2/cm4s
Sr-doped Nickel 2.23x10-11 g2/cm4s

0 0 0 0

0 0 0 0 0

Surface Micrographs

Nickel 900C

Sr-doped Nickel 900C

Planar SOFC Configuration

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

Oxidized Ni-50 Cr Alloy


Cr-Rich Second Phase has Dissolved in the Cr-Depleted Zone
Cr2O3
Cr-depleted zone

Alloy

Exhaust

Experimental Arrangement

Thermocouple

H2-3%H2O

Air

Air
H2-3%H2O

Courtesy of Dr. Prabhakar


Singh, PNNL

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

Dry Air Exposures 700oC


Time vs. Mass Change / Area (700oC, dry air)
0.60
Crofer - 1

Crofer - 2

E-brite - 1

0.50

E-brite - 2

M ass Change / Area (mg/cm2 )

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

Simulated Anode Gas (Ar-4%H2, H2O)


Exposures 700oC
o

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

Mass Change / Area (mg/cm2 )

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

Microstructural and Phase Identification


Crofer 700oC
MnCr2O4

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

H2(g) = 2[H]Ag 1. (H ) = 2(H)


2 g
Ag

Ag/Fuel interface

2. (O2) g = 2(O)Ag

Ag/ Air Interface

[H]Ag

3. 2(H) Ag + (O)Ag = (H2O) g Bulk Ag


[O]Ag+[H]A==H2O(g)

Air

H2(g)

Bulk Degradation Related to :


1.Dissociation and dissolution of H and O in the bulk metal
2. Interaction between dissolved H & O to form High pressure H2O gas
3. Nucleation and growth of steam bubbles/voids at GB/defects
Courtesy of Dr. Prabhakar Singh, PNNL

Partial pressures of CrO3 in Equilibrium with


Cr2O3, MnO-saturated MnCr2O4, and LaCrO3
Pressure of CrO3

-6
log p(Cr)

log p(Mn)(A)

log pCrO3 (atm)

-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

similar reductions would be achieved in the pressure


of CrO2(OH)2

Crofer oxidized in contact with LaSrMnO4


(cathode) for 88hrs at 900oC in air + 0.1atm H2O
Cr2O3 with ~2%
Sr, ~4% La, and
~4.7% Mn

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

Crofer (side opposite


cathode)

After exposure, the cathode


contained ~0.9% Cr and ~1.8% Al