ChE 4751

Corrosion Science and Engineering

Md. Jahirul Islam

Lecturer
Department of Chemical Engineering
Dhaka University of Engineering and Technology, Gazipur
PASSIVITY

© Md. Jahirul Islam , Lecturer

Faraday’s Experiment (1840s)

© Md. Jahirul Islam , Lecturer

 Faraday’s Experiment (Contd..)

We can have some observations from this set of experiments:

 Corrosion of a metal, showing active-passive behavior, in the passive state is very low
 In the active state, the corrosion of the same metal would be 104 to 106 times more
 The passive state may not be always stable. The unstable state of passivity in the above
experiments is demonstrated by the effect of scratching of passive iron in the same
environment
 We should be able to use this passivation phenomenon in different metal/alloy-
environment situations but ought to be very careful about the unstable nature of the
phenomenon
 Because of the prospect of important engineering applications, passivity has been studied
and researched extensively since its first demonstration

© Md. Jahirul Islam , Lecturer

 Passivity
• A passive metal is one that is active in the Emf Series, but that corrodes
nevertheless at a very low rate.
• Passivity is the property underlying the useful natural corrosion resistance of
many structural metals, including aluminum, nickel, and the stainless steels.
• Some metals and alloys can be made passive by exposure to passivating
environments (e.g., iron in chromate or nitrite solutions) or by anodic
polarization at sufficiently high current densities (e.g., iron in H2SO4).

© Md. Jahirul Islam , Lecturer

 Definition of Passivity
Two types of passivity have been defined b Uhlig and Revie:
 Type 1 — "A metal is passive if it substantially resists corrosion in a given
environment resulting from marked anodic polarization" (low corrosion rate,
noble potential).
 Type 2—"A metal is passive if it substantially resists corrosion in a given
environment despite a marked thermodynamic tendency to react" (low
corrosion rate, active potential).

© Md. Jahirul Islam , Lecturer

 Potentiostatic polarization curve

Figure : Experimental setup for Potentiostatic

polarization studies

Figure 6.1. Potentiostatic anodic

polarization curve for iron in 1N H2SO4
© Md. Jahirul Islam , Lecturer
 Galvanostatic polarization curve

Figure : Experimental setup for Galvanostatic polarization

studies
Figure 6.2. Galvanostatic anodic polarization curve
for iron in 1N H2SO4
© Md. Jahirul Islam , Lecturer
Flade Potential

Figure 6.3. Decay of passivity of iron in 1N

H2SO4 showing Flade potential, ∅𝐹

© Md. Jahirul Islam , Lecturer

 Flade Potential

 The potential ∅F at which the active state is re-established after initial slow
drop in potential is known as the flade potential

 Stability of passivity is related to the Flade potential, assuming the following

schematic reaction to take place during anodic passivation:

 If - ∅F is the potential for the reaction and O · M refers to oxygen in the

passive film on metal M, then

Where ∅0F is the Flade potential at pH = 0. This equation is valid for Fe, Ni, Cr and
alloys of Fe

© Md. Jahirul Islam , Lecturer

 Flade Potential

 The positive value of ∅0

F for iron (0.63 V) indicates considerable tendency for the
passive film to decay [reverse reaction of (6.2) ], whereas an observed negative
value of ∅0F = −0.2V for chromium indicates conditions more favorable to passive
film formation and, hence, greater stability of passivity.

0
 The lower the ∅F , easier it is for passivation to occur and bigger is the stability of
the passive film formed.

 For Cr-Fe alloys, value ranges from 0.63V for pure iron (Cr-0%) to –0.10 V for
25% Cr. Thus increasing Cr content increases the stability of passivation

 The potential (P in Fig. 6.1 ) at which passivity of iron initiates (passivating

potential) approximates, but is not the same as, the Flade potential because of IR
drop through the insulating layer first formed. This effect is absent on decay of
passivity.
© Md. Jahirul Islam , Lecturer
 Behavior Of Passivators

 It is interesting to note that the same Flade potential is reached

whether Fe is passivated by anodic polarization in H2SO4 or passivated
by immersion in Conc. HNO3

 Fe can be passivated in solutions of chromates (CrO4= ), nitrites (NO2-),

molybdates (MoO4=), tungstates (WO4=), etc. These inorganic oxidizing
agents hence are called passivators.

 Passivators act as anodic inhibitors. They cause corrosion of the metal

to shift in the noble direction. They themselves get reduced at the
anodic sites on the metal surface producing current density necessary
for passivation.

© Md. Jahirul Islam , Lecturer

 Theories of Passivity: Oxide-Film Theory
 This theory holds that the initial corrosion product e.g. a metal oxide
provides the diffusion barrier thus reducing corrosion.
 The oxide layer virtually separates the metal from the surrounding
environment.
 Effectiveness of this barrier in reducing corrosion depends on the nature
and the properties of the “protective” film.
 A visible PbSO4 film on Pb exposed to H2SO4 and FeF2 film on steel
immersed in aqueous HF are two examples of such protective film.
 Films formed on Cr or stainless steels by anodic polarization are too thin
and invisible
© Md. Jahirul Islam , Lecturer
 Theories of Passivity: Adsorption Theory
 According to this theory, passivity is achieved by a chemisorbed film of O2
or other passivating agents.
 This layer displaces the adsorbed H2O molecules from the metal surface
and prevents anodic dissolution by hydration of metal ions. The adsorbed
O2 decreases io and increases anodic polarization (overvoltage) for the
anodic reaction.
 Some authors do point out that the oxide-film theory and the adsorption
theory are not contradictions, rather they supplement each other. The
adsorbed film while getting thicker gradually changes to an oxide film. Thus
these authors mention a combined oxide-film adsorption theory of passivity.
© Md. Jahirul Islam , Lecturer
 Passivity and Chloride Ions

 Chloride ions and to a lesser degree other halogen ions break down
passivity or prevent passivation in Fe, Cr, Ni, Co and stainless steels
 According to the oxide-film theory, Cl- ions penetrate the oxide film through
pores or discontinuities. Chloride ions may also colloidally disperse the
oxide film thus increasing its permeability.
 According to the adsorption theory, chloride ions adsorb on the metal
surface faster than dissolved O2 or OH-. While in contact with the metal
surface, Cl- ions favour hydration of metal ions and help the metal ions go
into solution. Whereas adsorbed O2 decreases the rate of metal dissolution.

© Md. Jahirul Islam , Lecturer

 Passivity and Chloride Ions

 Thus adsorbed Cl- ions increase io, decrease overvoltage for anodic
dissolution of the metal. This is so effective, that iron and the stainless
steels are not passivated in aqueous environments containing appreciable
amount of Cl- ions.
 Breakdown of metal passivity by chloride ions is local and hence leads to
pitting type of attack.

© Md. Jahirul Islam , Lecturer