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Passivation usually is the result of the presence of a thin protective oxide or oxy-
hydroxide passive film on the metal surface.
Concentrated
HNO3
2
Passivity
Passive
Metal Film
Composition and thickness of the
Solution
passive film are functions of potential
and solution composition.
O M OH2
O OH For alloys, usually one element is
enriched in the film (films on Fe-Cr
O M OH2
alloys are enriched in Cr).
O OH
3
Stainless Steel
Under most conditions, iron is
not very corrosion resistant.
Wt. % Cr
Jones
• At the active-passive transition, the current density can decrease by many orders of
magnitude.
• The current density in the passive region, ipass, is often relatively independent of potential.
• Passive films may break down at the very high potentials, allowing high currents to pass
again. This is called the transpassive region.
• Transpassive current may be associated with oxygen evolution or dissolution - it is different
from currents associated with pitting. 5
Passivity
For certain systems, the critical potential values observed in
measured polarization curves may relate to boundaries in the
related Pourbaix diagram:
E ipass Transpassive
Etrans
Passive
icrit
i0H2/H+
Epp
ErevH2H+
Ecorr Active
ErevM/M+ Cathodic
i0M/M+
icorr
log i
6
Passivity
Pourbaix diagrams are useful as guides in suggesting regions of passivity.
This shows that the range of passivity for stainless steels is increased over
that of Fe because of the influence of the added Cr.
Jones
Jones
8
Passivity
Faraday experiment explained
Conc. nitric
Dilute nitric
HER
log i 9
Passivity
Alloys with different electrochemical behavior would be preferred for
environments with different oxidizing power:
Jones
10
Kinetics of Passivity
Metal ions oxidized at a fresh metal surface can:
• Cross double layer as solvated ion corrosion
• Form new solid phase:
• Deposit from solution of poorly-soluble ion to form nonprotective film
• Direct formation of film on surface without metal ions passing into solution
passivity
Steady state is when the rate of oxide growth = rate of dissolution = passive current density.
The current at a constant potential, or rate of passive film thickening, typically decreases
linearly in a log i/log t plot with a slope of about -1:
Jones
x = A + B log t (5) 12
Kinetics of Passivity
At a constant potential, each decade of time and current density is seen to be
accompanied by an equal amount of film growth.
However, passive film growth data also fit inverse logarithmic kinetics:
1/x = A’ - B’ log t (6)
13
Theories of Passive Film Growth
Ions moving through the oxide must overcome an activation energy G* to jump distance
2a. At equilibrium, the rate in the forward direction equals the rate in backwards
direction:
G *
i f i b nFk exp
RT (7)
Now apply an anodic overpotential V that is distributed linearly across the oxide of
thickness x resulting in an electric field of V/x.
The portion of that field along the jump path is 2aV/x. Therefore, the activation energies
in the forward and reverse directions each change by aVnF/x.
BV BV BV
i A exp A exp 2A sinh (9)
x x x 14
Theories of Passive Film Growth
There are two limiting approximations to Eqn 9:
BV dx
1) High field, V/x is large: i = A exp
x dt
This is the Field Assisted Ion Migration (FAIM) theory in which film growth is limited
by ion migration driven by the high field in the oxide.
Integration of this equation leads to an expression that approximates inverse logarithmic
film growth, and thus fits the data rather well.
15
Theories of Passive Film Growth
Other theories predict direct logarithmic growth.