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 Cations Cation Vacancies Electrons Anions aM 1 pO
2

Gas O2

2GMO (p'O ) M/MO = exp 2 RT

O

x M = M2+ + 2e or M + O 2 = MO + 2e

GMO a" = 1 exp M (p" ) RT O

O 2

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 =

Ci Bi i ( + Zi F ) N A x x

kTBi = Di =

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.)

(B.)
je =

e + Ze F x Z F x
2 e 2

Electrical Neutrality (C.)

Z c jc + Z e je = 0

 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 c2 F 2 ( c + e ) x Z e x

Considering ionic equilibrium and integrating across the oxide

jc =
M 1 c e d M 2 2 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.

1 k = 2 2 Zc F 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
e M
Zc F x

i Stop =

Note: If the external oxygen pressure is 1 atm,

i k = k OC 1 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 E - 5 0

y = 2.61E-11x

- 5 0

- 6 0

g2/cm4
6 E

- 6 0

y = 1.23E-11x

- 6 0

Nickel
2 E - 6 0

Sr-doped Nickel

0 0 0 0

0 0 0 0 0

0 0 0 0

0 0 0 0 0

seconds
2 5 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

Parabolic Rate Constant Nickel 2.61x10-11 g2/cm4s Sr-doped Nickel 2.23x10-11 g2/cm4s

Surface Micrographs

Nickel 900C

Sr-doped Nickel 900C

Planar SOFC Configuration

A RT pO2 ln C V0 = 4 F pO2

Repeat Components Electrolyte YSZ Anode Ni/YSZ

V 0.7volts

i 1Amp / cm 2 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

Air

Air
H2-3%H2O

Materials: Materials: 10 mil thick Ag tube 10 mil thick Ag tube Variables: Variables: Temperatures, 700, 600, 500oC; Temperatures, 700, 600, 500oC; +3%H2O Simultaneous exposures toto H +3%H O Simultaneous exposures H2 2 2 and air; and air;

Courtesy of Dr. Prabhakar Singh, PNNL

Diagram of Apparatus

Dry Air Exposures 700oC

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

Crofer - 2

0.50

E-brite - 1

E-brite - 2

AL453 - 1

M ass Change / Area (mg/cm2 )

AL453 - 2

0.40

ZMG232 - 1

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

Time vs. Mass Change / Area for Crofer, E-brite, AL453, & Ni (700 C, Ar/H2 /H20) 0.70
Crofer - 1
o

Crofer - 2

0.60

E-brite - 1

E-brite - 2

E-brite - 3

Mass Change / Area (mg/cm2 )

0.50

AL453 - 1

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 [O]Ag [H]Ag

Reaction Steps
H2(g) = 2[H]Ag 1. (H ) = 2(H) 2 g Ag
2. (O2) g = 2(O)Ag Ag/Fuel interface Ag/ Air Interface

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
-6
log p(Cr)

Pressure of CrO3
log p(Mn)(A) Cr2O3 MnCr2O4 LaCrO3 log p(La) log p(Mn)(B)

-8 log pCrO3 (atm) -10 -12 -14 -16 -18 0.7 0.75 0.8

0.85 0.9 3 1/T*10 (K-1)

0.95

1.05

Note:

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