Jose Agustin Fuentes Omana. University of Queensland.

Cover: http://www.hwgii.com/Metal-Pretreatment/passivation-of-steel.html
Table of Contents
PASSIVITY ................................................................................................................................................ 5

1.- Introduction: ............................................................................................................................... 5

2.- Review of Phenomena Involved in passivity: .............................................................................. 5

2.1.- Electrochemical Basis for passivity: ........................................................................................ 5

2.2.- Corrosion Kinetics ................................................................................................................... 6

2.3.- Electrochemical Polarization:.................................................................................................. 6

2.3.1.- Polarization by Activation: .............................................................................................. 6

2.3.2.- Polarization by Concentration: ....................................................................................... 7

3.- Factors involved in passivity: ...................................................................................................... 7

3.1.- Oxidizer Concentration effects: .............................................................................................. 9

3.2.- Solution Velocity Effects: ........................................................................................................ 9

4.- Theories of passivity: ................................................................................................................ 10

4.1.- Metal modification: .............................................................................................................. 10

4.2.- Reaction Rate: ....................................................................................................................... 10

4.3.- Oxide Film Theory: ................................................................................................................ 11

4.4.- Adsorption Theory: ............................................................................................................... 11

4.5.- Film Sequence Theory: .......................................................................................................... 12

5.- Characteristics of Passive Oxide Films: ..................................................................................... 12

5.1.- Thickness: .............................................................................................................................. 12

5.2.- Electronic and Ionic Conductivity: ........................................................................................ 13

5.3.- Chemical Stability:................................................................................................................. 13

5.4.- Mechanical Properties: ......................................................................................................... 13

6.- Formation of the passive film: .................................................................................................. 14

7.- Breakdown of the passive film:................................................................................................. 15

8.- Passivity in Action – Anodic Protection: ................................................................................... 15

REFERENCES .......................................................................................................................................... 17
Table of Figures

Figure 2.1.- Activation 1)Polarization: (a) cathodic, (b) Anodic. 2)Concentration (c) Cathodic, (d)
Anodic (McCafferty, 2010). ..................................................................................................................... 6
Figure 2.2.- Evans diagram for zinc in hydrochloric acid (McCafferty, 2010). ........................................ 7
Figure 2.3.- Combined activation and concentration polarization (Ahmad, 2006). ............................... 7
Figure 3.1.- Typical anodic polarization curve for passivatable metals (Frankenthal, 2001). ............... 8
Figure 3.2.- Anodic polarization of iron for different pH, with the dissolution current, IFe (solid
curves) and the total current, I (dashed curves) (Macdonald, 1998). ................................................... 8
Figure 3.3.-Change of oxidizer concentration in corrosion of an active-passive alloy (Jones, 1996). .... 9
Figure 3.4.- Change of oxidizer concentration and its effects over corrosion rate in an active passive
metal and or alloy (Jones, 1996). ............................................................................................................ 9
Figure 3.5.- Effect of deaeration, aeration and stirring on corrosion of active-passive stainless steel in
neutral salt water (Jones, 1996). .......................................................................................................... 10
Figure 4.1.- Experiment used by Hittorf (Uhlig, 1979). ......................................................................... 10
Figure 4.2.- Schematic diagram of the removal of a passive film by alcoholic iodine. The bottom
portion of the figure shows a cross section after a brief immersion in the solution (McCafferty, 2010).
.............................................................................................................................................................. 11
Figure 4.3.- Initial Film and Passive film according to the Adsorption Theory (Uhlig, 1979)................ 11
Figure 5.1.- Pourbaix diagrams for different elements Top row: aluminium, chromium, and niobium.
Bottom row: zirconium, vanadium, and tantalum (McCafferty, 2010). ............................................... 13
Figure 5.2.- Nanoindentation used to study mechanicals properties of the passive films (Rodriguez-
Marek et al., 2003). ............................................................................................................................... 13
Figure 6.1.- Development of oxide protective film on iron by potentiostatic anodic polarization at
different potentials in pH 8.4 borate-buffer solution (a) Direct. (b) Inverse (Kruger, 2003). ............... 14
Figure 8.1.- Anodic protection vs Cathodic Protection (McCafferty, 2010). ........................................ 15
Figure 8.2.- Anodic protection for a storage tank (McCafferty, 2010). ................................................ 16
PASSIVITY
1.- Introduction:
The development of the human civilization has been linked to the technological advances in metal
handling and manufacturing. Metals were included in activities such as fishing, cooking, and hunting
enhancing results for the first inhabitants on the earth. Moreover, metal manufacturing limits the
progress of the civilization, since it is necessary to reach the next level. Advances in fields like
transportation, communication, mass production would have not been achieved, if not for reactive
metals (Fe, Ni, Cr, Al, Ti, Zr, etc...) that are kinetically stable under oxidizing conditions (Macdonald,
1998).

There is a particular phenomenon on metals that inhibits the oxidation process that will lead them to
the thermodynamically stable condition of their origin—the ores used to produce. Apart from gold,
in all metals and alloys, a thin oxide layer covers their surface once they are exposed to the
environment. In some cases, metals and alloys have particular properties that make possible to
resist corrosion. These protective “passive” layers are responsible for the passivity in metals.

A historical review of passivity (Uhlig, 1979) was written listing three 18th century scientists—
Lomonosov (Russia-1738), Wenzel (Germany-1782), and Keir (Great Britain-1790). They observed a
dramatic change in the reaction of iron in concentrated nitric acid, from being highly reactive to
becoming unreactive. This effect was first called passivity by Schönbein (Schœnbein, 1837).
Nowadays, passivity makes possible the development of industries such as food processing, assuring
that several products are manufactured avoiding contact with rust, which is harmful if consumed by
humans, to name just a case.

A lot of books have been written about passivation. Although, it is not known yet the film formation
mechanisms as the film would change to be analysed once it is isolated (McCafferty, 2010). In this
chapter, I describe what is involved in passivation, electrochemical principles of passivation and
present a review of the theories that tend to explain the formation and structure of the passivation
films.

2.- Review of Phenomena Involved in passivity:

Before we discuss the passivity in metals, it will be convenient review some concepts and
phenomena that are closely related to the passivity in metals.

2.1.- Electrochemical Basis for passivity:

In other to explain the phenomenon of passivation, consider the example of a corrosion cell of
aluminium given in the literature (McCafferty, 2010):

If the spontaneity of the reaction is calculated as the difference between reactants and products
( ):

-12*

Using the values in tables (Porbaix, 1974):

-12*

This value of is negative, so the reaction of aluminium with water occurs spontaneously.
Although, an oxide film covering the aluminium surface (hundred or thousand of angstroms in
thickness) is formed whilst the aluminium is in contact with water, and slows down the oxidation
reaction evolution up to stop. This film is known as the passive film made out of a passive oxide of
aluminium, which is the responsible of immunising this metal against corrosion. Now we define
passivity as:”the reduction in chemical or electrochemical activity of a metal due to the reaction of
metal with its environment so as to form a protective film on the metal surface.”(McCafferty, 2010).

2.2.- Corrosion Kinetics

To understand the phenomenon of passivity, it is convenient to explain which mechanisms are
involved in the kinetic of corrosion. The corrosion rate is defined as in the following relation, based
on Faraday’s Law (Jones, 1996):

Where i is called current density (Current Intensity/area), a is molar mass, n is electrons exchanged
and F represents the Faraday’s constant (96500 coulombs/equivalent). When a half-cell reaction is in
the equilibrium state, the rate of the reaction forward and reverse is the same, and it is defined i0 as
exchange current equivalent to the reversible rate at equilibrium, which is a parameter very
important in corrosion kinetics.

2.3.- Electrochemical Polarization:

The phenomenon called Electrochemical polarization is the change in electrode potential due to the
flow of a current (McCafferty,
2010).
In this chapter, two kinds
polarization are mentioned: 1)
Activation polarization is when
the rate of charge flow is
controlled by one of the half-cell
reactions. 2) Concentration
polarization is due to
concentration changes in
chemical species that participate
in the corrosion cell near an
electrode surface. When the
polarization is on the cathode,
by definition the potential C is
negative, and it is called cathodic
polarization. Likewise, when the
polarization is on the anode by
definition the potential C is
Figure 2.1.- Activation 1)Polarization: (a) cathodic, (b) Anodic. 2)Concentration (c) negative, and it is called cathodic
Cathodic, (d) Anodic (McCafferty, 2010). polarization.

2.3.1.- Polarization by Activation:

In Figure 2.1, cathodic polarization in (a) is represented. In a cathodic activation polarization, the
concentration of electrons on the cathode surface increase as they are supplied faster than they can
react with the solution. On the other hand, in an anodic polarization (b) the concentration of
electrons is depleted on the surface of the electrode. Thus, the electrons leave metal faster than the
Fe leaves the matrix. It must be taken into account that this reaction is slow.
The overpotential a and C are expressed by the Tafel relationships (Jones, 1996):
 In which >0 (anodic
polarization, surface charge
positive) and <0 (cathodic
polarization, surface charge
negative).Using these
relationships, it is possible to plot
the curves for zinc and
hydrochloric acid as in Figure 2.2,
using a graph E (potential) vs. i
(current density). On the same
graph, the cathodic evolution line
of the hydrochloric acid intersects
the anodic evolution line of the
zinc. At this point is the
equilibrium between both half-
cells (Ecorr, icorr). This analysis is
known as mixed potential theory,
and it will be useful to predict the
effect of perturbations on a
Figure 2.2.- Evans diagram for zinc in hydrochloric acid (McCafferty, 2010).
corrosion cell in equilibrium.

2.3.2.- Polarization by Concentration:

In a cathodic polarization by concentration, as we can see on Figure 2.1.c, into the electrical double
layer, H+ ions move more slowly than electrons fed on the metal surface. Consequently, the
population of e– is augmented on the metal surface by limiting the concentration of H+ ions. In
contrast, for anodic polarization by concentration we consider the case shown of Figure 2.1.d. The
products diffuse slowly away from the interface. Consequently, the surface becomes more positively
charged.
In both cases there is
no variation of the
current density due to
changes in the
potential. There will
be a current density in
which the system has
reached a limiting
value (see Figure 2.3).
The current at this
point is known as
Figure 2.3.- Combined activation and concentration polarization (Ahmad, 2006).
‘limiting current, or iL,’
stage at which the
potential does not affect the current density measured. This phenomenon is Mass transport
controlled, which is more frequent for cathodic oxygen reduction process (limiting O2 diffusion rate
in the solution).

3.- Factors involved in passivity:

First of all, we consider the definition of passivity according to Uhlig (Uhlig, 1979) as it follows: “A) A
metal is passive if it substantially resists corrosion in a given environment resulting from marked
anodic polarization. B) A metal is passive if it substantially resists corrosion in a given environment
 despite a marked thermodynamic
tendency to react”. Therefore, passivity in
metals is defined as a resistance to
corrosion under an anodic polarization,
even though thermodynamically is
possible the corrosion.

To study the passivity phenomenon,

consider the anodic polarization curve
shown in Figure 3.1 (Jones, 1996). In this
case, electrons are excerpted from the
metal which charges the surface
positively. The anodic oxidation rate ia
increased whereas the cathodic reduction
rate ic decreases, then the applied anodic
current density is . It is
important to consider that the anodic
Figure 3.1.- Typical anodic polarization curve for passivatable metals
(Frankenthal, 2001).
dissolution of the metal is irreversible and
it would affect the measurement
conditions.

As a potential that promotes anodic

polarization is induced (Figure 3.1), an
increase in the current density of the
material is observed. This region is called
active region. When it is reached certain
potential, the current density drops
dramatically up to ipass. It is deducted from
experimental results that this reduction in
the current density is caused by
development of the oxide protective film.
This potential is known as Flade potential
(Ep), when the material is experiencing an
active / passive transition. The current
density measured at Flade Potential is
known as critical current density for
passivation (ic). The passive current
density is detected when there is a
dramatically drop of the current and
remains relatively constant regardless the
increase of potential. At higher
Figure 3.2.- Anodic polarization of iron for different pH, with the potentials, transpassive region is
dissolution current, IFe (solid curves) and the total current, I (dashed
curves) (Macdonald, 1998). reached, the protective film breaks down
and the anodic rate increases.

In Figure 3.2, it is observed the change of ipass vs. pH for an anodic polarization of Iron (Macdonald,
1998). The trend observed is that the passive potential range shortens as the pH becomes more
acidic and the current density increases, which means that the corrosion rate increases.
 3.1.- Oxidizer Concentration effects:
Consider the Nernst Equation presented in the literature (Jones, 1996) to express the change of
potential due to Temperatures and / or concentrations of any chemical specie involved in the
corrosion cell:

From the chemical reaction:

From the expression for the Nernst equation

[H+], it is deducted that the potential is
proportional to the concentration of [H+]
which is the oxidizer of the reaction. Using
the mixed potential theory, we build the
graph with an anodic polarization curve of
the metal and a cathodic curve for different
concentrations of the solution as in Figure 6
(Jones, 1996). In the active region, comparing
lines 1 and 2, the current density increases as
the concentration increases. At
concentration 3, it is possible that the alloy
will presents some areas of the material
being passives and other actives. When the
lines 4, 5 and 6 cross with the passive
Figure 3.3.-Change of oxidizer concentration in corrosion of an active- material, it is seen a drastically drop in the
passive alloy (Jones, 1996). current density, which a value roughly iD. An
increase in the concentration as in 7 and 8
(transpassive area) will cause a raise in the
current density and eventually an advance in
the corrosion rate.
Plotting the results of corrosion rate vs.
Concentration of the solution Figure 7, an
increase in the corrosion rate is seen as the
concentration of the environment increases
in the active zone (points A, B and C). C cross
the anodic curve in 3 points, but the film will
not appear until the solution reaches
concentration D. Now, if we consider
dilution of the oxidizer agent, the corrosion
rate will remain at passive levels until the
Figure 3.4.- Change of oxidizer concentration and its effects over corrosion solution reaches the concentration B. The
rate in an active passive metal and or alloy (Jones, 1996).
reason is that the material held at higher
concentrations was able to develop the passive film and it will remain for lower concentrations than
were needed to promote its formation.

3.2.- Solution Velocity Effects:

To explain the effects of agitation on passivity, consider the polarization diagram of stainless steel in
seawater (Jones, 1996). There are two possible cathodic reactions: (1);
(2)
 The first cathodic reaction (Evolution of H2
in acid solutions) will prevail in deareated
solutions, and the material corrodes in the
active state. Once the solution is aerated,
the second reaction will prevail (Reduction
of dissolved Oxygen) and the line will cross
the passive anodic line around what is
called: “Borderline passivity conditions”
(Ecorr1) and in the passive region (Epass) (see
Figure 3.5). Any deformation or damage
on the passive film will cause localised
corrosion, so it is consider that the active
state will be predominant. As the agitation
Figure 3.5.- Effect of deaeration, aeration and stirring on corrosion of
active-passive stainless steel in neutral salt water (Jones, 1996). rate increases, the concentration in the
interphase metal-liquid is provided with
ions that will be available to consume the electrons provided by the metal. That will occur until it is
reached the agitation rate 4, in which the potential increases significantly to Epass and the corrosion
rate falls from i4 to ipass.

4.- Theories of passivity:

Uhlig pointed in his work the following statement about the theories proposed to explain passivity:
“Early theories of passivity probed at a variety of possibilities--they ranged from a peculiar electrical
state of iron as proposed by Herschel to an allotropic transformation proposed by Schönbein”. Since
the beginning, the protective oxide theory has been considered and defended. In this section we are
going to consider the main categories mentioned in the literature (Uhlig, 1979) since the first records
of passivity in metals: (I) metal modification, (2) reaction rate, (3) oxide film, (4) adsorption.

4.1.- Metal modification:

An experiment undertook by Hittorf supports the metal modification viewpoint (Uhlig, 1979). His
experiment is shown in figure 4.1. In 1900, metallic Chrome was made cathode and it became active
being dissolved into a deareated hydriodic solution, in form of Cr+2 (left hand side Figure 4.1). Cr was
reported to become passive once
the polarity was reversed, liberating
I2 (right hand side Figure 4.1).
Passive chromium was believed to
be in a strained state, which was an
attempt to support his results. As
Oxygen and ion I- are discharged at
a potential noble, the passive film
Figure 4.1.- Experiment used by Hittorf (Uhlig, 1979).
cannot be made out of chromium
oxide. Müller and Körnigsberger
(Uhlig, 1979) carried out optical reflectance test on passive iron, showing no existence of an oxide on
the surface. That experience reinforced theories that explain the passivity phenomenon not by an
oxide film formed.

4.2.- Reaction Rate:

This theory attempts to explain the passivity phenomenon and passivity properties by a mass
transport issue, regardless of hypothetical surface films. In 1900, Le Blanc proposed that these
passive properties were due to lethargic hydration of the anhydrous ions lying on the metal (Uhlig,
1979). This hydration controls their solubility in water. Uhlig considered this viewpoint for his passive
film model proposal, including the fact that the hydration depends on the metal surface and the
corrosive environment.
Schmidt and Rathert proposal was mentioned in the literature (Uhlig, 1979). It was suggested that
metals become active when hydrogen enters in contact with the metal, otherwise they remain
passive. The hydrogen was believed that attack metal patterns on the surface or catalyses chemical
reaction.

4.3.- Oxide Film Theory:

This theory was the most supported since Faraday’s experiments (Uhlig, 1979). Through
measurements of potential, Bennett and Burnham determined that the film on iron passivated by a
nitric acid solution was FeO3.
This specie was stabilized by
adsorption on the metal surface;
instead of the stoichiometric
iron oxides was the responsible
of the passivation phenomenon.
The description provided is
based on research carried by
Evans (Evans, 1927). On his work
using iron exposed to air and
oxygen environments at several
temperatures; it was shown that
visible changes were observed
Figure 4.2.- Schematic diagram of the removal of a passive film by alcoholic iodine. The
when the oxide film reaches the bottom portion of the figure shows a cross section after a brief immersion in the
thickness requisite to be solution (McCafferty, 2010).
detected. It was notorious that pure iron, once it was made active by abrasion, promotes passivity
when exposed to a dry air environment at the ordinary temperature for a couple of hours.
The following observations support the adsorption theory (McCafferty, 2010):

1. Oxide films have been removed partially out of the metal surface by potassium iodide, and
the films were analysed using for example electron microscopy (Evans, 1927). Iron flat pieces
were scratched ob a certain area. The film was extracted from this area as shows Figure 4.2.
On the same experiment, it was shown that the unscratched places appear relatively
immune. This fact provides evidence the flow of iodine into the metal was restricted by this
layer.
2. There have been numerous studies on the chemical composition of passive films using
modern surface analytical techniques, such as X-ray photoelectron spectroscopy (XPS).
3. Passive films were characterised and it has been detected the existence of Cr, Ni, and Mo, to
name but a few. Therefore, it is concluded that the chemical composition has a remarkable
effect on the passivity.

4.4.- Adsorption Theory:

The adsorption theory states that a monolayer
of oxygen is chemisorbed which leads to the
reduction of the metal activity (McCafferty,
2010). This monolayer is believed to protect
against further attack. According to this theory,
passivity is due to a mitigation of the reaction
kinetics at the metal passive film interface
instead of limiting the mass transport of ions and
atoms through a phase oxide (Uhlig, 1979).

It was proposed by the Author (Uhlig, 1979) that

an adsorbed oxygen film causes passivity for

Figure 4.3.- Initial Film and Passive film according to the Adsorption
Theory (Uhlig, 1979).
transition metals and their alloys on the metal surface. The partially empty d electron orbits enhance
the chemisorbed bond. Additionally, the adsorbed film promotes the reduction of the exchange
current density in the metal oxidation: M  Mz+ + ze-. Consequently, it enhances the anodic
polarization properties of metals passive. On the other hand, cathodic polarization inhibits the
adsorption of O and supplying interstitial hydrogen that displaces chemisorption of oxygen. Chloride
takes the place of adsorbed O at local sites which depletes the passivity of the metal. That promotes
arise of the exchange current density and anodic polarization will drop.

The following observations support the adsorption theory (McCafferty, 2010):

1. It was found that the charge electric needed to reach the passive state characterizes an
oxygen monolayer.
2. Iron and alloying transition metals such as Cr or Ni posses elevated adsorption enthalpies of
O2, which are similar to the heat needed for the oxygen to be chemisorbed.
3. The Flade potential measured for iron corresponds to the formation of a chemisorbed
monolayer.
4. Passivity depends highly on the alloy composition. It was believed that this fact was due to
electrons moving between d exterior metal sublevels, favouring the formation of an oxygen
monolayer.

4.5.- Film Sequence Theory:

Hackerman considered that an adsorbed film is responsible for huge potential variations associated
with passivity and protects metal against aggressive environments, which could not be provided by
an adsorbed monolayer (McCafferty, 2010). Therefore, Hackerman attempts to reconcile with the
film sequence theory both adsorptive and oxide film theories.

This theory has been supported by a study of the passive layer developed on iron Fe–24Cr alloy
(Frankenthal, 1967) using coulometric measurements. It was observed that a monolayer film was
firstly formed, although a more consistent and thicker film appeared afterwards, at higher potentials
than the prime passivation.

The stages involved in the formation of the passivation film are:

1. Chemisorption of O2.
2. Two adsorbed oxygen atoms Oads are formed by split O2 molecule.
3. Development of the specie Oads.
4. Invasion of metal ions into the formed monolayer located on the metal surface.
5. Three-dimensional oxide film development.

Additionally, when damage occurs, the passivity film must be capable of regenerating by itself
getting through the steps 1-5.

5.- Characteristics of Passive Oxide Films:

In this section we will present properties inherent to Passive oxide films (Schultze and Lohrengel,
2000).

5.1.- Thickness:
The thickness of passive layers varies from monomolecular films for platinum and gold up to
substantial films that could reach micrometers (essentially from nanometres to micrometers). The
thickness of the passive films is function of the corrosive environment, the metal, and the conditions
were the film has been developed.
It is possible to determine the thickness of passive films by chemical, electrochemical and
spectroscopic techniques, considering a homogenous thickness with stoichiometry and density
uniform, as a first estimate. The rate of the passive film growth will be discussed later in this chapter.

5.2.- Electronic and Ionic Conductivity:

Good electronic conductivity is observed in passive layers on the transition metals such as Iron,
Chromium, Nickel, etc, which are less than 100 Å (less than this thickness, the film is considered
thin). In passive films on iron, according with the literature, it was demonstrated that reactions that
involves electron transference like Fe(CN)64–/ Fe(CN)63– were supported (McCafferty, 2010). There is
extensive support that passive films on Fe, Ti, or Sn contain excess of free electrons, whereas on Cu
or Ni contains excess of holes as a charge carriers (McCafferty, 2010). On the other hand, metals like
Al, Ta, and Pb exhibit barrier passive films thicker and generally their electronic conductivity low. In
order to avoid the interaction of the metal surface with aggressive ions such chlorine, passive films
ion conductivity should be low.

5.3.- Chemical Stability:

There are some conditions that must be present so passive films remain on the surface: the passive
film must present practically
insoluble and be stable for
an ample of electron
potentials. The conditions,
on which passive films
remain stable, could be
predicted using the Pourbaix
diagram, in which is possible
to predict which conditions
would be preferable for a
metal to be protected by
passivity. As seen in Figure
5.1, the passive film on Nb is
more stable than aluminium
and Chromium, this latter
Figure 5.1.- Pourbaix diagrams for different elements Top row: aluminium, chromium, and
shows a narrower range of
niobium. Bottom row: zirconium, vanadium, and tantalum (McCafferty, 2010). condition in which the
passive film remains stable.

5.4.- Mechanical Properties:

Metals in service are going to face
situations such as dilation,
scratching, abrasion or
deformation. Passive film that
covers the material should be able
to show properties needed to
avoid a breakdown of the film.
Eventually, this breakdown will
lead a localised corrosion due to
the formation of concentration
cells on the area where the
breakdown lies. Nevertheless,
being thin films that cover the
Figure 5.2.- Nanoindentation used to study mechanicals properties of the passive
films (Rodriguez-Marek et al., 2003). metal makes them very difficult to
study.
Different methods were used to study mechanicals properties of passive films. Methods such as
nanoindentation technique and use of bulk circumferentially notched tensile bars (CNTBs)
(Rodriguez-Marek et al., 2003); bending beam method (Kim and Seo, 2003); or simply clamping the
upper end of a thin foil of the metal and observing the motion of the lower end through a telescope
(Vermilyea, 1963) were used to measure the stress in metals such as: 304 stainless steel, nickel,
tantalum, niobium, aluminium, zirconium, titanium, and tungsten.
There are some interesting outcomes that could be useful in designing structures and/or process
where passivity plays an important role. Bubar and Vermilyea undertook tests using straining
technique, by which tantalum oxide layers has shown excellent ductility, being deformable as much
as 50% before fracture (Bubar and Vermilyea, 1966). Oxide films on zirconium, 304 stainless steel,
and iron also behaved considerable ductile, but oxide films on aluminium behaved as brittle under
stress (Bubar and Vermilyea, 1966, Bubar and Vermilyea, 1967).

6.- Formation of the passive film:

Once the metal under an anodic polarization is into the
passivity region, a passive film will be formed covering
the metal surface. Kruger described three possible
processes that could be the responsible for the
formation of passive films (Kruger, 2003). These
processes are intimately related with the film sequence
theory described in section 4.5, which accepts the fact
that a monolayer of oxygen is chemisorbed initially, and
it is suggested their development as follows:

a) Chemisorption of Oxygen film and / or a

squashed 3D (more than one atomic layer) film: M + H2O
 MOads + 2H+ + 2e- and M + H2O  MO(oxide) + 2H+ +
Figure 6.1.- Development of oxide protective film on iron 2e-.
by potentiostatic anodic polarization at different b) Dissolution precipitation producing a passive
potentials in pH 8.4 borate-buffer solution (a) Direct. (b)
Inverse (Kruger, 2003). layer by formation of an oxide, oxyhydroxide, or
hydroxide film in the two-step process: M  Mz+ + ze- /
Mz+ + zH2O  M(OH)z + zH+. Anodic reaction of metal ions in solution forms an oxide film
containing the metal ion in a higher oxidation state as shown by: M  Mz+ + ze- / 2Mz+ + (z +
x)H2O  M2O(z+x) + 2(z + x)H+. + 2xe- .

In the literature is proposed two different models to express the rate of film formation:
Galvanostatic anodic oxidation and Potentiostatic anodic oxidation.

In a Galvanostatic anodic oxidation, the change of potential vs. time is measured at a constant
current. Once plotted, the curved obtain shows that the potential increases firstly during an
induction time, τp, reaching Ep. The relationship between τp and the current density reached at Flade
potential, ic, is τp = k(i - ic)n, where k and n are constants. For iron n=-1 (Kruger, 2003). On the other
hand, a potentiostatic anodic oxidation is carried out measuring the change of the current vs. time
at constant potential on the metallic surface. The authors suggested that in potentiostatic
passivation, dissolution and film formation competing (Ebersbach et al., 1967), and the passivation
development rate behaves according to the expresion i = (idiss + ifilm) (1 - θ), where idiss is the current
density once the dissolution of the passive film is reached, ifilm film formation current density, and θ
is the relation between the surface covered by the passive layer and the total surface considered.

The dissolution of the passive films in acid solutions is needed to take into account since is the
process that is competing with the passive film formation as mentioned in the last paragraph. At
Flade potential, the boundary between the active and passive states lies (Kruger, 2003). It was
observed when Flade found that the potential decayed continuously and then remained stable
before reached more actives values.

7.- Breakdown of the passive film:

It is most commonly accepted the following definition “Breakdown is the destruction of the
passivating film by chemical or mechanical action, most frequently localized at specific sites”
(Frankenthal, 2001). Breakdown allows that the corrosive environment attacks the surface of the
metal, promoting the development of pitting and crevice corrosion; or forms of corrosion that are
detected via instruments such as intergranular attack, or stress-corrosion cracking. That could be
avoided if the passive film had the property to regenerate itself quickly enough to cover the surface.

The reasons for the local breakdown of this film are listed as below (Schultze and Lohrengel, 2000):

 In a dielectric breakdown, the oxide film is not able to bear high field strength.
 Corrosion or radiation inflicts on particular areas of the passive film.
 Invasion of the film by aggressive ion such as chlorine.
 Hydrogen could be incorporated into the matrix, evolving hydrogen gas that leads the
reduction, dissolution of the passive film. The passive film could flak off allowing corrosive
environment to be in contact with the metal surface.

Some factors that must be considered to prevent failure in service due to breakdown of the passive
film (Frankenthal, 2001):

 Alloy composition: There are steels containing enough nickel and chromium that provides
resistance against localised corrosion.
 Properties of the passive film: composition, thickness, mechanical, electronic and ionic
properties.
 Formation of the passivity film: conditions that the metal surface was exposed during
passivation such as solution of passivation, passivation time, potential of passivation and
temperature.
 Non-uniform composition of the film will lead to breakdown since alloys that strengthen the
passive film are lacked in some regions.
 Avoiding tensile stress that could cause fractures in the passive film, leading to localised
corrosion.
 Avoiding crevices in which a aeration cell could be developed and eventually leads to
localised corrosion. This principle must be considered during the design stage.

8.- Passivity in Action – Anodic Protection:

In this section, a practical use of the passivity theory and
experimental trends will be presented. The principle
behind the anodic protection is based on the anodic
polarization curve for a metal. If the metal surface is
remained at a potential in which the passive layer is
formed, the metal will be protected for the passive film.
The condition that the metal must meet is that it must
be able to be passivated. In figure 8.1, potential
managed in cathodic and anodic protection are
compared. There are several possibilities to be Figure 8.1.- Anodic protection vs Cathodic Protection
(McCafferty, 2010).
considered in order to promote the conditions on which
the material develops the passive film. The options to be considered are (McCafferty, 2010):
 (1) Inhibitors against oxidizers, for instance chromates, molybdates, or nitrates,

(2) Enhancing material against corrosion using alloys, for example stainless steels,

(3) Noble metal alloying, e.g., Pd−Ti alloys,

(4) Protection using impressed potential.

Considering the economical factor, use of stainless steel is not necessary favourable and also alloying
with noble metals could be expensive. Inhibitors on the surface could abandon the surface and
contaminate the liquid stored. Therefore, impressed potential systems are suitable for this case, as it
is presented in figure 8.2. The aim is to maintain surface of the storage tank in the passive region
using a suitable potential. The cathode must be
capable of bearing oxidizing environment.
Materials suggested include platinum-clad brass,
copper, and 304 stainless steel. In the literature,
it is suggested reference electrodes such as
platinum and metal/metal oxide
electrodes(McCafferty, 2010).

Due to the hazard intrinsic in handling sulphuric

acid, anodic protection is found suitable for
metals under these conditions. Other processes
protected by this method include paper and raw
materials industry and in the storage of chemical
fertilizers and alkaline liquids(McCafferty, 2010).
Figure 8.2.- Anodic protection for a storage tank (McCafferty,
2010).
 REFERENCES
AHMAD, Z. 2006. Principles of Corrosion Engineering and Corrosion Control, Burlington, Elsevier
Science & Technology.
BUBAR, S. F. & VERMILYEA, D. A. 1966. Deformation of Anodic Oxide Films. Journal of The
Electrochemical Society, 113, 892.
BUBAR, S. F. & VERMILYEA, D. A. 1967. Deformation of Passive Films. Journal of The Electrochemical
Society, 114, 882.
EBERSBACH, U., SCHWABE, K. & RITTER, K. 1967. On the kinetics of the anodic passivation of iron,
cobalt and nickel. Electrochimica Acta, 12, 927-938.
EVANS, U. R. 1927. CXL.-The passivity of metals. Part I. The isolation of the protective film. Journal of
the Chemical Society (Resumed), 0, 1020-1040.
FRANKENTHAL, R. P. 1967. Electrochemical Society 114, 542-547.
FRANKENTHAL, R. P. 2001. Passivity and Breakdown. Elsevier Ltd.
JONES, D. A. 1996. Principles and prevention of corrosion, Upper Saddle River, NJ, Prentice Hall.
KIM, J. D. & SEO, M. 2003. Effect of Applied Potential Steps on Stresses of Anodic Oxide Film on
Nickel. Journal of The Electrochemical Society, 150, B193.
KRUGER, J. 2003. Passivity: Passive-Film Formation and Dissolution. ASM International.
MACDONALD, D. D. 1998. Passivity: The key to our metals-based civilization. 34th Convention of the
South African Chemical Institute. Durban, South Africa
MCCAFFERTY, E. 2010. Introduction to corrosion science, New York, Springer New York.
PORBAIX, M. 1974. Atlas of Electrochemical Equilibria in Aqueous Solutions. In: ENGINEERS, N. A. O.
C. (ed.). Houston Texas.
RODRIGUEZ-MAREK, D., BAHR, D. F. & PANG, M. 2003. Mechanical measurements of passive film
fracture on an austenitic stainless steel. Metallurgical and Materials Transactions A, 34,
1291-1296.
SCHŒNBEIN, C. F. 1837. Experimental researches on a peculiar action of iron upon solutions of some
metallic salts. Philosophical Magazine Series 3, 10, 267-276.
SCHULTZE, J. W. & LOHRENGEL, M. M. 2000. Stability, reactivity and breakdown of passive films.
Problems of recent and future research. Electrochimica Acta, 45, 2499-2513.
UHLIG, H. H. 1979. Passivity in metals and alloys. Corrosion Science, 19, 777-791.
VERMILYEA, D. A. 1963. Stresses in Anodic Films. Journal of The Electrochemical Society, 110, 345.