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Pasivity

It is the property underlying the


useful natural corrosion resistance of
many structural metals, including
aluminum, nickel and stainless steels.
Some metals and alloys can be
made passive by exposure to
passivating environment or by anodic
polarization at sufficiently high current
densities.
Faraday’s Experiment (1840s)
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
Definition of Passivity

 Two types of passivity have been defined by


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).
Galvanostatic Polarization
Galvanostatic Polarization Curve
Potentiostatic Polarization
Potentiostatic Anodic Polarization Curve
Flade Potential
Flade Potential

 If -φF is the potential for the reaction then

F  Fo  0.059 pH

 Where φFo is the Flade potential at pH = 0. This


equation is valid for Fe, Ni, Cr and alloys of Fe
Flade Potential and Stability of Passive Film

 Stability of passivity is related to the Flade potential

 The lower the φFo, 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
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.
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
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
Mo → M++ + 2e-

 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.
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.
 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.