Lecture 22:Passivity Design of Corrosions Resistant Alloys

NPTEL Web Course

Lecture 22
Passivity Design of Corrosion Resistant Alloys
Keywords: Alloy Design, Pitting Potential, Oxidizers.

For the development of corrosion-resistant alloys through passivity criterion, two

approaches then become possible.
a) Increase ease of passivation by reducing icrit or making Epp more active.
Anodic dissolution behavior can be changed by alloying (to decrease icrit)
Examples are titanium, chromium alloying additions, molybdenum, nickel
tantalum and columbium.
b) Increase cathodic reduction rates.

Alloying with noble metals having high exchange currents for the reduction reaction.

Metals with active Epp such as titanium and chromium and alloys containing these
metals which possess high exchange current densities for hydrogen reduction can
undergo spontaneous passivation.

Effect of alloy additions on the corrosion resistance of titanium is given in Table

22.1.
Table 22.1 Average corrosion rate of titanium after alloying addition.

Alloying addition

Corrosion rate (mpy) in 15%

boiling HCl

Ti (not alloyed)

4400

Addition of 0.5% Au

135

Addition of 0.5% Pt

110

Addition of 0.6% Ir

85

1
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 22:Passivity Design of Corrosions Resistant Alloys

NPTEL Web Course

Effect of oxidizer concentration and solution velocity on the corrosion rate of a

normal metal has already been discussed (lecture 13). It will be interesting to
understand the role of oxidizer and solution velocity on the behavior of an activepassive metal or alloy.

For an active-passive metal exposed to a diffusion controlled cathodic reaction, the

corrosion rate will increase upto certain velocity levels, beyond which the corrosion
rate decreases rapidly to a very low value on the onset of passivity and would
remain at passive state for still higher velocities.

Effect of oxidizer concentrations (ferric, chromate etc) on the electrochemical

behavior of active-passive alloys can also be compared with those of normal metals
under similar conditions. Corrosion rate of an active-passive alloy initially increases
with oxidizer concentration (while in its active state). As soon as passive state is
reached, the corrosion rate steeply decreases to a very low value and remains at this
low corrosion passive level. With still further increase in oxidizer concentration,
corrosion rate further increases due to transpassive behavior.

It is however, interesting to note that, once the passive film has been formed, it is
retained at oxidizer concentrations even lower than that needed for passive film
formation.

It may however be kept in mind that to maintain passivity, oxidizer concentration

should be same or higher than the required minimum to induce spontaneous
passivation. There is also a region of borderline passivity in which any surface
disturbance (scratching) will destabilize passivity, leading to increase in corrosion
rate. The following conditions need to be kept in mind to judge passive behavior of
an alloy.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 22:Passivity Design of Corrosions Resistant Alloys

NPTEL Web Course

Corrosion rate is proportional to anodic current density in the active state

irrespective of whether the alloy is passive type or not.
Rate of cathodic reduction must exceed icrit to ensure lower corrosion rates.
Border line passivity to be avoided.
Avoid breakdown of passive films in oxidizing environments due to
transpassivity.
Stable passive state in oxidizing conditions is essential.

Detrimental role of chloride concentrations and temperature on the passive region

and critical anodic current density is illustrated in Fig. 22.1.

Fig. 22.1 Effect of increasing chloride and temperature on passive behavior.

Chloride ions breakdown passivity or even at times prevent passivation of Fe, Cr, Ni,
Co and stainless steels. They can penetrate oxide films through pores and influence
exchange current density (overvoltage). Breakdown of passivity by chloride ions is
local and leads to pitting corrosion. However, chloride ions have no significant
effect on the polarization curve of titanium, unlike that of stainless steels.

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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 22:Passivity Design of Corrosions Resistant Alloys

NPTEL Web Course

Anodic polarization of active-passive metals and alloys can be established either

potentiostatically or galvanostatically.

The differences in the nature of the

polarization curves in either case are illustrated in Fig. 22.2. Only potentiostatic
approach allows a detailed study of the important parameters influencing passivity.
Galvanostatic methods are not adequate for establishing the active-passive behavior.
Above icrit, the curve no longer follows the anodic curve in the passive region;
suddenly jumping into the transpassive region with oxygen evolution.

Feg 22.2 comparison of potentiostatic and galvanostatic anodic polarization curves.

Theories of passivation
Major theories that have been proposed are the
Oxide film theory and
Adsorption theory
The oxide theory attributes corrosion resistance of passive metals and alloys to the
formation of a protective film on the metal surface; the film can be as a monolayer.
There are different opinions expressed about the potential at which the oxide film is
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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 22:Passivity Design of Corrosions Resistant Alloys

NPTEL Web Course

formed, mechanisms of formation, causes of passivity and film thickness. Early

theories proposed formation of a primary layer of lower conductivity and high
porosity. As the current increases in the pores, passive layer is formed at a potential
closer to the Flade potential. A stable passive film is free from porosity and presents
a protective barrier between the metal and the corrosive environment. There are
similar hypotheses regarding monolayer oxide formation.
The adsorption theory is based on chemisorbed films.

Oxygen adsorption on

surfaces can reduce corrosion activity. Uhlig proposed in 1946 that an adsorbed
oxygen film is the primary source of passivity. The observed Flade potential of
passive iron is too noble by about 0.6V to be explained by any known oxides of iron
at equilibrium. It is consistent with a chemisorbed film of oxygen, which is formed
preferentially on transition metals due to interaction of oxygen with uncoupled
electrons to form a stable bond. Adsorbed oxygen atoms significantly decrease the
exchange current density, thus increasing anodic polarization, favorable for
passivation.
An alternative passivity mechanism could be direct film formation, dissolution and
precipitation and anodic deposition.
Several models also have been proposed to explain growth kinetics of surface oxide
films.

Anodic polarization curve is time-dependent in both active and passive

regions. Passive current density (ipass) should be proportional to the rate of passive
film formation and rate of its growth in thickness.
ipass = K
Logarithmic law of passive film formation has been derived taking into consideration
continuous adsorption.
Film thickness ( X) = A + B log t
Inverse logarithmic rate law,

= A B log t

5
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore