Lecture 21: Passivity Application of Mixed Potential Theory

NPTEL Web Course

Lecture 21
Passivity-Application of Mixed Potential Theory
Keywords: Activation Controlled Reduction Process, Diffusion Control, Spontaneous
Passivation

Increasing temperature and hydrogen ion concentration (high acidity) tend to

increase the critical current density for passivation.

Similarly, chlorides are

detrimental to passivity.
To understand, mixed potential behavior for active passive metals and alloys, it is
essential to introduce cathodic reduction processes superimposed on the anodic
polarization curve.

Three different activation controlled reduction processes with

different exchange current densities are superimposed on the passivity curve as

shown in Fig. 21.1.

Fig 21.1 Effect of activation controlled cathodic processes on stability of passivity.

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

Lecture 21: Passivity Application of Mixed Potential Theory

NPTEL Web Course

Three different cases are apparent:

1) Only one stable potential at M where the mixed potential theory is satisfied.
High Corrosion rate at M.
Eg:- Fe in dil H2SO4, Ti in dil H2SO4/ HCl.
2) Three points of intersection R, P and N where rate of oxidation is equal to
rate of reduction. Point P is not in stable state. Only N and R are stable.
N in active region (high corrosion rate) and R in passive state (lowest
corrosion rate).
This system may exist in either active or passive state.
Eg:- Cr in dil HCl or H2SO4.
Stainless steel in H2SO4 (containing oxidizers).
3) The most desirable condition-spontaneous passivation - Only stable potential
S in the passive region.
Eg:- Cr noble metal alloys in H2SO4 or HCl.
Ti noble metal alloys in dil H2SO4.
18 8 stainless steel in acid (containing Fe+++, O2)
Achievement of condition (3) is essential for the development of corrosion resistant
alloys.
The position of the current maximum or nose of the anodic curve is important.
Spontaneous passivation occurs only if the cathodic process clears the tip of the
nose of the anodic curve.

For a stated reduction-curve, values of Epp and icrit will then decide whether a metal
or alloy will spontaneously passivate or not.

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

Lecture 21: Passivity Application of Mixed Potential Theory

NPTEL Web Course

Total cathodic current density at Epp should be equal to or greater than icrit to achieve
spontaneous passivation.
Such a criterion can be stated in terms of a passivity index (PI) defined as
PI =

ic ( atE pp )
icrit

For PI 1, Spontaneous passivation occurs and

for PI < 1, no spontaneous passivation occurs, even though as in condition (2), a
stable passive region may exist.

A comparison of the behavior of two active-passive alloys under an activation

controlled cathodic system is depicted in Fig. 21.2.

Fig 21.2 Active passive alloys under activation controlled cathodic process.

Alloy A corrodes readily at potential X, while alloy B spontaneously passivates at Y.

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

Lecture 21: Passivity Application of Mixed Potential Theory

NPTEL Web Course

The above two alloys are exposed to a cathodic process under complete diffusion
control as shown in Fig. 21.3.

Fig. 21.3 Active passive alloy behavior under diffusion controlled cathodic reaction

Alloy A spontaneously passivate at potential X, while alloy B exhibits two stable

states, namely, active at Q and passive at Y.

Two significant factors emerge out of the above observations.

a) To achieve passive behavior where cathodic reduction is activation
controlled, a metal or alloy with an active E pp is superior.
b) If the reduction process is diffusion controlled, a metal or alloy having a
small icrit will passivate faster.

(Ref: N. D. Greene, Predicting behavior of corrosion resistant alloys by

potentiostatic polarization methods, Corrosion (NACE), 18, pp 136 1432 (1962).

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