All The Lecture 1-37

Lecture 2: Electrochemical Cells Definitions and Principles
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Lecture 2
Electrochemical Cells Definitions and Principles
Keywords: Electrodes, Cells, Liquid Junction.
Definitions and types of electrochemical cells.

Electrode: An electric conductor, the electrode metal and an ionic conductor,
electrolyte solution, form an interface at which electrode process occurs.
An
electrochemical cell contains two electrodes (anode and cathode); a liquid-liquid

junction separates two electrodes.
Anode is the electrode where oxidation occurs.

Cathode is the electrode where reduction occurs.
Types of electrodes:
Metal Metal ion
Cu / Cu++
Ion Ion (redox)
Pt / Fe+++, Fe++
Gas
Pt / H2, H+
Metal insoluble salt
Hg / Hg2Cl2 / KCl
Liquid Junction: Serves as galvanic contact between electrodes (can be a salt

bridge or porous membrane). Salt bridge, very commonly used an intermediate
compartment filled with saturated KCl solution and fitted with porous barrier at each
end or agar solidified incorporating saturated KCl. Salt bridge minimises liquid
junction potential (diffusion potential) that develops when any two phases such as
two solutions are contacted each other. This potential (if not corrected) introduces
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Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore
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errors and interferences in the measured cell potentials. With introduction of a salt
bridge, two liquid junction potentials are created; but they tend to cancel each other
(Fig.2.1).
Fig.2.1 Electrochemical cell with salt bridge
IUPAC sign convention for electrode potentials

Sign of the electrode potential, E 0
is positive when the half cell is spontaneous as cathode.
is negative when the half cell behaves as anode.
is a measure of the driving force for the half reaction.
E0 is referenced to standard Hydrogen Electrode.
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2H+ + 2e = H2
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E0 = 0.000V
Fe+++ + e = Fe++
E0 = +0.771V
E0 is independent of number of moles of reactant or product.

Positive means reaction is s spontaneous with respect to Hydrogen electrode.
In accordance with the recommendations of IUPAC, the present practice is to use
reduction potentials.
Ecell = Eright - Eleft
Standard hydrogen electrode (SHE) is the reference point.
Types of electrochemical cells
Galvanic
Electrochemical cells
Electrolytic
Table 2.1 Comparison of galvanic and electrolytic cells
Galvanic
Electrolytic
Chemical energy to electrical energy
Electrical to chemical energy
Spontaneous/Reversible/Thermodynamic
Non spontaneous/Kinetic cell /

irreversible
Cathode (+)
Cathode (-)
Anode (-)
Anode (+)
AG0 <O, E0cell >O
AG0 > O, E0cell < O
Eg: Dry cell

Daniel cell
Eg: Electroplating,
Impressed current cathodic
protection
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Definition of electrochemical cell

Electrodes (anode, cathode) in the presence of electrolyte.
Driving force for
electrochemical reaction is the potential difference between the electrodes, Ecell.

G = -nFEcell
n = moles of electrons in half reaction
F = 96500c
G0 = - RTlnK
Nernst relationship:
E = E0 +
Eh = E0 +
Eh = E0 +
ln
ln
log
at 250c
Where E0 is the standard electrode potential,
is the ratio between activities of
oxidized and reduced species.

Daniel cell is an example of a galvanic cell - contains zinc immersed in zinc sulfate
solution and copper in copper sulfate solution separated by a diaphragm or salt
bridge (Fig. 2.2).
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Fig.2.2 Diagrammatic representation of Daniel cell
(-)Zn | Zn++ (1M) || Cu++ (1M) | Cu(+)

+ Right Rule
Ecell =
(Right) -
(Left)
The sign of cell reaction potential (E cell) should be positive indicating spontaneous
reaction. Single vertical line denotes electrode solution interface. Double vertical
lines in the middle indicates liquid junction is eliminated.
Zn = Zn++ + 2e (Anodic) E0 = - 0.76 V
Cu++ + 2e = Cu0 (Cathodic) E0 = + 0.34V
Zn + Cu++ = Zn++ + Cu0 (Net reaction)
Zinc ions enter the aqueous phase leaving two electrons behind. (oxidation, polarity
of anode is negative): copper ions deposit by taking up two electrons (reduction,
polarity of cathode is positive).
at 1M concentration for Zn ++ and Cu++
Ecell = + 0.34 (-0.76) = + 1.1V
The cell is spontaneous
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For the reaction, Fe++ = Fe+++ + e

Eh = 0.771 + 0.059 log
(-)Pt
| Fe++ , Fe+++ || H+, H2 | Pt (+)

(a=1)
For the reaction 2H+ + 2e = H2

Eh = 0 +
at pH2 = 1,
log [H+]2
Eh = 0 - 0.059 pH
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Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells
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Lecture 3
Potential Measurements - Galvanic Cells, Concentration
Cells
Keywords: Potentials, Reference Electrodes, Concentration Cells.
Electrode potentials can be measured using a reference electrode in any desired

electrolyte at room temperature. Potential of a corroding metal or alloy (E corr) can be
measured in the corrosive media (Fig. 3.1).
Fig. 3.1 Measurement of electrode potential with reference to standard electrode.
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Brief description of a few generally used reference electrodes given below:

Often measured electrode potentials are referred to standard or Normal Hydrogen
Electrode (SHE or NHE) whose standard potential is 0.0V at partial pressure of
hydrogen and hydrogen ion activity both at unity
2H+ + 2e = H2
NHE consists of a platinum electrode immersed in a solution of hydrogen ion of
activity = 1. Hydrogen gas at 1 atmos. pressure is bubbled around the platinum
electrode. This is a universal reference standard (Fig 3.2).
Fig. 3.2 Hydrogen reference electrode
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Due to efforts and expenses involved in its construction and also due to difficulties in
handling H2 gas, NHE is not generally preferred. Instead more convenient and less
cumbersome standard reference electrodes such as Saturated Calomel Electrode,
silver/silver chloride or Cu/CuSO4 electrodes can be used.
Saturated Calomel Electrode (SCE).
Hg|Hg2Cl2 (Satd), KCl (x M)|| - - - - - - - - - - - (see Fig. 3.3)
Fig. 3.3 Saturated calomel electrode (SCE)
Hg2Cl2 + 2e = 2Hg + 2ClStandard potential = + 0.244V
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Silver / Silver chloride Electrode

Silver wire coated with AgCl
Solution of KCl saturated with AgCl
Similar electrode construction as that of SCE
Ag | AgCl (Satd), KCl (a = xM) || - - - - - - - - - (see Fig. 3.4)
AgCl + e = Ag + ClStandard potential = + 0.222 V
Fig. 3.4 Ag/AgCl reference electrode
Copper / Copper sulfate electrode

Cu++ + 2e = Cu (satd CuSO4)
Standard potential + 0.316 V
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Types of galvanic cells

a. Dissimilar electrode cells
b. Concentration cells
Important concentration cells
Salt concentration
Differential aeration
(Oxygen Concentration)
Differential temperature
Metallographic / mechanical
heterogeneities
Differences in residual stress levels
Dissolved oxygen concentration in water, soil etc frequently varies from region to
region due to various reasons. Such a difference in aeration produces a different
equilibrium potential.
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O2 + 2H+ + 2e = H2O
2
1
2
[O ] H
0.059
Eh = E +
log 2
[ H 2 0]
2
Higher oxygen concentration provides a more nobler potential. Oxygen-enriched
0
areas in a corroding metal serve as cathodes, while oxygen depleted regions act as
anodes (undergoing corrosion).
Eg: Rusting of iron in atmosphere (O2, moisture)
Fe = Fe++ + 2e (anodic reaction at O2 starved regions)
Net reaction: Fe++ + 2H2O = Fe (OH)2 + 2H+
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See the model for rusting of iron given in Fig. 1.1.

A diagrammatic arrangement of an oxygen concentration cell is illustrated in Fig.
3.5.
Fig.3.5 Oxygen Concentration cell
Similarly, metal ion concentration gradients at metal-solution interfaces can create a

potential difference and generation of anodic cathodic sites (Fig 3.6).
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Fig. 3.6 Salt concentration cell
Differential concentration cells

(-)M | M+(a1) || M+ (a2) | M(+)
E1 = E0M +
ln a1
E2 = E0M +
ln a2
Ecell = E2 E1 =
ln
Water line corrosion and corrosion of electric poles at the base are typical
examples. Electrical poles fixed to soil can buckle due to failure at the junction (pole
soil interface) due to prevalence of oxygen concentration cells. In water line
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corrosion, a steel specimen submerged in a beaker of saline water can experience

corrosion at the water line due to similar reasons.
Dissimilar electrode cells or bimetallic couples are separately discussed in Lecture 4.
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Lecture 4: EMF and Galvanic Series and Bimetallic Couples
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Lecture 4
EMF and Galvanic Series - Bimetallic Couples
Keywords: EMF Series, Galvanic Series, Galvanic Corrosion.
EMF Series
a) EMF series lists only metals (little engineering application). Alloys not
included
b) Electrode potentials listed calculated from thermodynamic principles
(corrosion potentials are more relevant).
c) Equilibrium potentials with concentrations at unit activity (Exact prediction
of galvanic coupling not possible).
d) Predicts only tendency to corrode (Role of passive films and oxidation
kinetics not predicted).
e) Effect of environment not predicted (Eg: Sn Fe couple as in Tin cans)
Galvanic series
a) Instead of standard electrode potentials, actually measured rest potentials of
metals and alloys in a given environment arranged with respect to nobility
and activity.
b) Practically measured potentials vs reference electrode.
c) Effect of coupling of metals and alloys on corrosion rate can be predicted.
Certain anomalies Eg: Stainless steels (active and passive)
Galvanic series is generally good for stagnant conditions and not for turbulent
conditions.
EMF and galvanic series are illustrated in tables 4.1 and 4.2.
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Table 4.1 EMF Series
E0,V(SHE)
Reaction
Au++++ 3e = Au
+1.42
Pt++ + 2e = Pt
+ 1.2
O2 + 4H+ + 4e = 2H2O
+1.23
Pd++ + 2e = Pd
+0.83
Ag+ + e = Ag
+0.799
O2 + 2H2O + 4e = 4OH-
+0.401
Cu++ + 2e = Cu
Sn+++ + 2e = Sn++
+0.34
+0.154
2H+ + 2e = H2
0.00
Pb++ + 2e = Pb
-0.126
Sn++ + 2e = Sn
-0.140
Ni++ + 2e = Ni
-0.23
Co++ + 2e = Co
-0.27
Cd++ + 2e = Cd
-0.402
Fe++ + 2e = Fe
-0.44
Cr++++ 3e = Cr
-0.71
Zn++ + 2e = Zn
-0.763
Al+++ + 3e = Al
-1.66
++
Mg
+ 2e = Mg
Noble
Reference
-2.38
Na+ + e = Na
-2.71
K+ + e = K
-2.92
Active
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Table 4.2 Galvanic Series in Seawater
Platinum
Gold
Silver
Hastelloy C
18 8 stainless steel (passive)
Noble
Graphite
Chromium steel > 11% Cr (passive)

Inconel (passive)
Nickel (passive)
Monel
Bronzes
Copper
Brasses
Inconel (active)
Nickel (active)
Tin
Lead
Lead-tin solder
18-8 Mo stainless steel (active)
18-8 stainless steel (active)
Ni-resist
Chromium steel<11% Cr (active)
Cast iron
2024 aluminium
Cadmium
Active
Steel or iron
Commercially pure aluminium

Zinc
Magnesium and its alloys.
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The EMF series is an arrangement of various metals in the order of their

electrochemical activities based on their standard oxidation-reduction potentials (E0).
The most active metal in the series will be having a high negative standard potential
while nobler metals possess relatively less negative (or more positive) standard
potential (E0). If we consider a couple of two metals in the EMF series, the one with
higher negative E0 will act as anode (and will corrode) compared to the other with a
relatively less negative E0 value (cathode).
There are several exceptions to the predicted activity of a metal (or couple) as
arranged in the EMF series.
Eg: Aluminium exhibits higher corrosion resistance due to Al2O3 layer present on
surface.
Chromium exhibits stable Cr2O3 layer and is used as alloying element for corrosion
resistance in stainless steels.
Many metals alter their potentials depending on the environment. Reversal in
polarity can occur in some environments, leading to changes in anodic (and cathodic)
behaviour.
Tin (Sn) is nobler to iron (Fe) in the EMF series. Internally tinned (tin-coated) steel
cans are used to preserve vegetable and fruit juices. Such a cathodic protection of
iron by tin is however only limited since many food constituents such as organic
acids can combine with Sn++ to form soluble tin complexes, resulting in lowering the
activity of stannous ions. The polarity of Fe Sn couple can reverse under these
conditions.
Fe++ + Sn = Sn++ + Fe
The cell polarity reverses when Ecell = 0
log
Sn
Fe
can be calculated and works out to be -10.30
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Ratio of
Sn
Fe
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must be < 5 x 10-11 for tin to become more active than iron.
ratio within the can must be very small for the reversal of polarity to occur.
Amenability of galvanic corrosion in bimetallic contacts can be predicted by the
EMF and galvanic series.
Bimetallic and Concentration cells are mainly responsible for galvanic corrosion.
Typical example is rusting of iron in a moist environment where oxygen
concentration gradients come into play.
Galvanic corrosion rates are influenced by two factors, namely distance and area
effects. Severity of corrosion is the highest near the junction of the bimetal contacts.
Area effect refers to ratio of anodic to cathodic areas and a larger cathode in contact
with a small anode is considered unfavourable area ratio. For a given current flow
in a galvanic cell, the current density is higher for a smaller electrode than for a
larger anode. Higher current density results in larger rates of anodic corrosion.
Examples demonstrating the area effect:
a. Copper plates (larger cathodes) connected by steel rivets (smaller anodes)
exposed to sea water.
b. Steel plates (larger anode) connected with copper rivets (smaller cathode)
exposed to sea water.
Case (a) represents unfavourable area effect leading to severe corrosion of steel
rivets. Case (b) represents favourable area effect. Larger anode and smaller cathode
results in negligible galvanic corrosion.
A graphical representation of area effect with respect to anodic corrosion rate is
illustrated in Fig 4.1.
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Fig 4.1 Graphical representation of area effect
Galvanising of steels for corrosion protection is a classic example of corrosion

protection through proper galvanic (sacrificial) method.
Zinc is anodic to iron and hence corrodes away protecting the steel base metal
surfaces.
Consider a uniformly zinc coated steel surface exposed to a corrosive environment.
Even if portions of zinc coating are abraded away, the base steel will still be
protected! (Due to favourable area effect). See Fig 4.2.
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Fig 4.2 Pictorial representation of zinc coated steel surface in a corrosive environment
All coatings have defects in the form of pinholes and mechanical damage. Corrosion
of steels can be concentrated at coating defects (small anodes). For example, in a
carbon steel (anode) structure having contact with stainless steel (cathode), surface
coating of only the carbon steel could lead to disastrous corrosion due to
unfavourable area effect. The best alternative would then be, if one of two dissimilar
metals (alloys) in contact is to be coated, the more noble one should be coated (or
painted).
The following factors need be considered for prevention of galvanic corrosion.
a) Select combinations as close together in the galvanic series.
b) Avoid unfavourable area effect.
c) Insulate dissimilar metal contacts.
Corrosion currents can be generated due to several reasons in metals and
alloys, namely
a) Impurities
b) Grain orientation and grain boundaries
c) Differential thermal treatment
d) Surface roughness.
e) Alloying elements (Brass, Zn corrodes with respect to Cu)
f) Metallographic defects
g) Strain/stress
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Fig 4.3 Electrode potentials of some metals and oxidising reducing agents
With respect to arrangement of the electrode potentials for metals on the one
hand and those of various oxidising and reducing agents on the other, it becomes
easy to predict the relative oxidising or reducing power of various reagents with
respect to a desired metal / metal ion reaction (Fig 4.3). A wide selection of
strongly oxidizing species is available for oxidation of most of the metals
excluding perhaps the nobler metals such as gold and platinum.
Similarly,
reducing power of hydrogen with respect to precipitation of metal ions can also
be predicted. However, it may be borne in mind that not all equilibria are always
oxidizing or reducing.
Effect of pH and gaseous partial pressures on
oxidisability and reducibility need be taken into consideration.

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Lecture 5: Eh-pH Diagrams - Fundamental Aspects
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Lecture 5
Eh-pH Diagrams Fundamental Aspects
Keywords: Eh-pH Relationship, Water Stability, Oxidation, Reduction.
Eh and pH as environmental parameters in the electrochemical equilibrium diagram.

Eh-pH diagrams showing reactions and products at electrochemical equilibrium are
often referred to as Pourbaix diagrams. As shown in Fig. 5.1 below, there are four
regions in the diagram corresponding to oxidizing (acidic), oxidizing (alkaline),
reducing (acidic) and reducing (alkaline) environments.
The basic diagram for aqueous environment involves upper and lower, stability
limits for water, represented by the oxygen (universal oxidizing agent) and hydrogen
(universal reducing agent) reactions.
Fig. 5.1 Basic regions in a Eh pH diagram
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Stability limits of water

a) O2 + 4H+ + 4e = 2H2O
E0 = +1.23V
Eh = 1.23 0.059 pH (at po2 =1)

b) 2H+ + 2e = H2
E0 = 0.00V
Eh = 0-0.059 pH (at pH2 = 1)

These equilibria are plotted in Fig. 5.2. Above the oxygen line, oxygen liberation
occurs.
Below the hydrogen line, hydrogen liberation occurs.
Water is stable
between the two lines.

In neutral or alkaline solutions, the following reactions hold good.
2H2O + 2e = H2 + 2OHO2 + 2H2O + 4e = 4OHElectrochemical evolution of hydrogen represents water decomposition. At more
positive potentials, oxygen reduction or water oxidation takes place. Slope of both
lines correspond to 59 mV/pH.
Fig 5.2. Stability limits of water
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Three types of lines in the diagram

a) Those depending only on Eh, but independent of pH (Horizontal to the Xaxis).
b) Those dependent only on pH, but independent of Eh (Vertical to the Xaxis).
c) Those dependent on Eh and pH (Slanted with definite slopes).
The above types of reactions and general effects of Eh and pH on redox reactions
(oxidation, reduction) are illustrated in Fig. 5.3.
Fig 5.3. Effects of changes in Eh and pH
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The following aspects are noteworthy:

As the potential increases in the positive (noble) direction
Loss of electrons is favoured (oxidation).
Metal dissolution is favoured.
The system becomes more oxidizing.
Ratio of
Ox
increases.
Re d
When the potential decreases in the negative direction

Gain of electrons favoured (reduction).
The system is more reducing.
Metal deposition (plating) favoured.
Ratio of
Ox
decreases.
Re d
Increasing pH favours metal hydroxide precipitation. Still higher pH may lead to

solubilisation again (eg: dihypoferrite and aluminate)
Consider two redox reactions:
OX1 + n1e= Red1
OX2 + n2e = Red2
OX1 + Red2 = OX2 + Red1
As shown in Fig. 5.4, through Eh pH diagrams, one can predict oxidizability and
reducibility of different reactants.
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Fig 5.4 Role of oxidising and reducing agents
Oxidant OX1 can oxidise Red2 to OX2 while OX1 get reduced to Red1.
Relative positions of various oxidation and reduction reactions in the diagram
indicate possibilities of cell reactions as shown above. Oxidizability of various
metals such as gold, silver, copper, nickel, cobalt and iron by oxidants such as
oxygen, hydrogen peroxide, halides (chloride, bromide, iodide), permanganate and
dichromate can be predicted. Similarly, possibility of using hydrogen (and other
reducing agents) to reduce and precipitate metal ions such as Ag+, Cu++, Ni++, Zn++
and Fe++ can also be predicted based on relative positions of respective lines in the
diagram. For example, all metal-metal ion redox lines which are placed above the
hydrogen line can be thermodynamically reduced by hydrogen.
Iron can be used to displace copper from acidic solutions (cementation).
Cu++ + Fe = Cu + Fe++
E0 for Cu++ / Cu is + 0.34V, while E0 for Fe / Fe++ is -0.44V.
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Lecture 6: Construction of Eh pH Diagrams (Fe H2O O2 Diagram)
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Lecture 6
Construction of Eh pH Diagrams (Fe- H2O O2
Diagram)
Keywords: Iron Diagram, Corrosion Regions, Advantages and Limitations.
Construction of an Eh pH diagram based on thermodynamic data is illustrated

with respect to Fe-H2O O2 system. Seven major reactions which are
thermodynamically feasible are illustrated along with calculations leading to
simplified Eh pH relationships which are plotted on the electrochemical
equilibrium diagram. The diagram can be drawn for a given concentration of the
metal ion species. The lines will shift as a function of varying concentrations.
Assume Fe++, Fe+++ ion concentrations (activity), aH2O = 1, pO2 = 1, pH2 = 1.
Room temp 25oC.
Eh pH diagrams drawn for specific ion activities and partial pressures of
gases at room temperature.
1. Fe = Fe++ + 2e
E0 = - 0.44V
(Reaction dependent only on Eh, independent of pH)

Eh = - 0.44 +
log [Fe++]
For aFe++ = 1, Eh= - 0.44V

2. Fe++ + 2H2O = Fe(OH)2 + 2H+
(Reaction dependent only on pH, independent of Eh)
reaction =
f(FeOH) 2
+2
F0 f(H+) - F0f(Fe++) - 2
-115.57 + 2(0) (-20.30) 2(-56.69) = 18.11 (k.cal)

= - RT lnK
= - 1.364 log K
1
log K =
H
log
Fe
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= - 13.28
2
= - 13.28
2pH + log [Fe++] = 13.28

Log [Fe++] = 13.28 -2pH
pH = 6.64
3. Fe++ = Fe+++ + e
E0 = + 0.771V
(Eh dependent, but independent of pH)

Eh = 0.771 + 0.059 log
Eh = 0.771 (at unit activity)
4. Fe +++ + 3H2O = Fe (OH)3 + 3H+
(reaction dependent only on pH)
Log [Fe+++] = 4.81 3pH
pH = 1.6
5. Fe + 2H2O = Fe(OH)2 + 2H+ + 2e
(dependent both on Eh and pH)
First, estimate E0 for this reaction from reaction free energy values.
E0 = Eh = - 0.05 +
= -0.05V
log [H+]2
Eh = - 0.05 0.059 pH
6. Fe(OH)2 + H2O = Fe (OH)3 + H+ + e
Eh = 0.27 0.059 pH
7. Fe++ + 3H2O = Fe (OH)3 + 3H+ + e
Eh = 1.057 0.177pH 0.059 log [Fe++]
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The above Eh pH relationships as above are plotted on a graph one by one as

indicated below to yield the final Eh pH diagram depicting all the seven
reactions with respect to stability regions for the various cations and precipitated
hydroxide products (Fig. 6.1).
Fig. 6.1 Reaction wise plotting of Eh pH relationships
Domains of immunity, corrosion and passivation

From the Eh pH diagram, it can be seen that when Fe++ , and Fe+++ are stable,
the metal (Fe) is in the dissolved state, corresponding to regions of metallic
corrosion.
At more active potentials, iron is thermodynamically stable and
immune to corrosion.
In the regions where corrosion products such as Fe (OH)2 and Fe(OH)3 (or Fe3O4
and Fe2O3) are stable, the metal is oxidized with a surface film which can protect
it from further corrosion (passivity). Corrosion behaviour of the metal (Fe) in an
aqueous aerated solution can then be represented as a corrosion diagram.
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Corrosion diagram for the Fe-H2O O2 system is given below (Fig. 6.2).
Fig. 6.2 Corrosion diagram for iron
Regions of corrosion for iron (steels) are not only confined to the acidic region,
but also exist in the high alkaline region (beyond a pH of about 12) where
dissolution of iron as HFeO2- species can occur. Regions of immunity (where
metallic iron is stable thermodynamically) and passivation (stability phases for
iron oxides which form a protective passive layer) are shown.
Advantages and limitations of Eh pH diagrams.

Electrochemical equilibrium diagram shows conditions of solution oxidizing
power (potential) and acidity or alkalinity (pH) at room temperature for a known
activity of dissolved metal species. Stability regions for various solid (elemental
form and precipitated compounds) and ionized forms are demarcated.
This
diagram has applications in several disciplines such as:

Corrosion prediction and protection
Extractive metallurgy
Geology and geochemistry
Geomicrobiology
Fuel cells
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However, there are some limitations, such as:

a) The diagrams are thermodynamically (theoretically) determined only for
25oC.
Caution should be exercised to predict corrosion behaviour at
higher temperatures using this diagram.

b) Only thermodynamic amenability to corrosion and protection predicted.
Kinetic factors are not considered. Corrosion rates cannot be predicted.
c) No consideration for extraneous ions and effect of complexation.
d) Only pure metals are generally considered. Effects of impurities, alloying
and metallographic phases and heterogeneties are not considered.
Unstable phases not represented.
Modified Eh pH diagrams for various metals can be prepared taking into
consideration the effect of alloying additions and presence of complexing
agents.
Combined diagrams which take into consideration two or more
metals simultaneously present would be more useful. For example, effect of

chromium addition to steel to increase corrosion resistance can be represented
in a modified Fe Cr diagram.
Anodic and cathodic protection limits with reference to potentials and pH can
be predicted using the Eh pH diagrams.
Computer programmes and soft-ware kits are now available to construct EhpH diagrams for various metal systems.
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Lecture 7: Copper, Aluminium and General Corrosion Diagrams
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Lecture 7
Copper, Aluminium and General Corrosion Diagrams
Keywords: Copper Diagram, Aluminium Diagram, Eh pH Diagram for Metals.
Similarly, Eh pH diagrams for other metal systems can be drawn. Various

reactions pertaining to the Cu H2O O2 system along with the constructed
Eh pH diagram are illustrated below (Fig.7.1).
Fig. 7.1 Eh pH diagram for copper
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Construction of Al H2O O2 diagram
1. Al = Al+++ + 3e
Eh = - 1.66 +
log [Al+++]
2. 2Al + 3 H2O = Al2O3 + 6H+ + 6e

Eh = -1.55 0.059 pH
3. 2Al+++ + 3H2O = Al2O3 + 6H+

Log K = 6 log [H+] 2 log Al+++
For [Al+++] = 10-6M,
= - 6 pH 2 log Al+++
pH =
- log
= 3.9
4. Al + 2H2O = AlO2 - + 4H+ + 3e

Eh = - 1.26 + 0.02 log AlO2 - 0.079 pH
5. Al2O3 + H2O = 2AlO2- + 2H+

pH = 14.6 + log [AlO2-]
There are two solid species (Al and Al2O3 H2O) and two ionic species (Al+++ and
AlO2-).
Constructed Eh pH diagrams for the Al H2O O2 system are illustrated in Fig
7.2 and 7.3.
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Fig. 7.2 Stability phases in the aluminium diagram
Immunity: Totally immune from corrosion attack and safe to use in the region.
Cathodic protection may be used to bring the potential of a metal closer to that
region by imposing cathodic shift.
Passivation: Metal coated with an oxide or hydroxide film preventing all direct
contact between the metal itself and the environment.
Corrosion: Ionised form of aluminium is stable in this region and therefore
susceptible to corrosion attack.
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Fig. 7.3 Corrosion diagram for aluminium
3 regions: corrosion, passivation, immunity.

Al+++ / AlO2 - is stable
- corrosion
Aluminium oxide is stable
- passivity
Al is stable
- thermodynamically immune to corrosion.
Passivity?
Caused by thin oxide or hydroxide layer forming on metal surface, protecting the
metal from anodic oxidation.
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However, oxide will itself corrode under certain conditions.

Aluminium is an amphoteric metal (acid and alkali reactions)
if pH < 4
- Al+++ stable
if pH > 8.3
- AlO2 - stable
if 4 < pH < 8.3
- Al2O3 stable and thus protects the metal
If the potential is sufficiently low aluminium itself is immune to corrosion.

Eh pH diagrams as corrosion diagrams for several important metals such as
aluminium, copper, magnesium, nickel, titanium and zinc are illustrated in
Fig.7.4. A relative comparison of corrosion behaviour of the above metals in
terms of Eh and pH brings about very useful comparisons:
Nobler metals (copper, silver, gold and platinum) exhibit very large immunity
regions.
Active - passive metals such as titanium, and chromium exhibit a larger,
stable passive region.
Active metals such as magnesium exhibit a large corrosion region.
Behaviour of copper, nickel, zinc and aluminium which are widely used in
several environmental conditions with respect to corrosion and passivity as a
function of pH and redox potentials is very important in the development of
corrosion resistant
alloys and application of protection techniques.
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Fig. 7.4 Corrosion diagrams for various metals
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Exercise
1. Through computer search and reference books construct and study Eh
pH diagrams for various metallic systems such as:
Noble metals (gold, silver, platinum and palladium).
Active passive metals (chromium, titanium)
High temperature metals (molybdenum, Tungsten)
Active metals.
2.
a) Comment on combination Eh pH diagrams to represent alloy

behaviour in corrosion.
b) Role of inhibitors in corrosion prevention through modified Eh
pH diagrams.
c) Modified Eh pH diagrams to predict passive behaviour, cathodic
and anodic protection parameters.
3. Study computer generation and software programmes for Eh pH

diagrams.
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References
1. M. Pourbaix, Atlas of electrochemical equilibria in aqueous solutions,
NACE, Houston (1974).
2. D.C. Silverman and A. L. Silverman, Potential-pH diagrams as aids for
screening corrosion inhibitors and sequestering agents, corrosion, 66 No.
5, (2010).
3. P. B. Linkson, B.D.Philips, C. D. Rowles, The method of maximum
constriction. An imporved algorithm for the computer generation of
potential pH diagrams, Corrosion science, 19 (1979) p 613 -620.
4. Web information on software for corrosion prediction and generating of
Eh pH diagrams.
8
Lecture 8: Electrode Solution Interface Definition and Types of Polarization

NPTEL Web Course
Lecture 8
Electrode-Solution Interface Definition and Types of
Polarization
Keywords: Electrochemical Interface, Polarization, Anodic Control, Cathodic Control
Proportionality between current density (i) and reacted mass (m) in an

electrochemical reaction is stated by Faradays law.
m=
Corrosion rate
r=
Where n = number of electrons involved

a = atomic weight
t = time
F = Faraday constant (96500 coulombs / equiv)
Corrosion rate
r=
Where i = current density

A = surface area
Corrosion rate in mpy [mils (0.001 in) per year] is given as
r = 0.129
Where i = A/cm2
D = density, g/cm3
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Through above relationship, anodic current density in corrosion can be converted to

metal loss in mpy.
When electrode reactions take place, the potential will no longer be at equilibrium
due to current flow through an electrochemical cell-causing a change in the electrode
potential. This electrochemical phenomenon is termed POLARIZATION.
Polarization of anode anodic polarization
Polarization of cathode cathodic polarization
Corroding systems are not in equilibrium-deviation from thermodynamics.
Deviation of the potential from its reversible value is referred to as polarization. A
cell or electrode is said to be polarised when there is little or no change in current
with larger changes in potential.
An electrode is not in equilibrium when a net current flow from or to its surface.
Polarization can result from either a slow step in an electrode process or discharge of
ions at an electrode surface.
Distribution of anions and cations at a metal solution interface is shown as
electrical double layer (Fig. 8.1).
A compact layer (Helmholtz) closest to metal surface in which charge distribution
and hence potential varies linearly with distance (Fig. 8.2).
A more diffuse innter layer (G. C. layer) where potential changes exponentially.
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Fig.8.1 Double layer at electrode solution interface
Fig. 8.2 Potential distribution across distance
Processes at an electrochemical interface are schematically represented below :
Fig. 8.3 Transport processes at electrochemical interface
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Mass transport to metal surface involves forces such as convection, diffusion and
migration, depending on presence or absence of electric field and flow conditions.
Concentration polarization is controlled by diffusion gradients (Ficks law).
Activation polarization involves kinetic factors related to charge transfer, such as
activation energy barrier and equilibrium current density.
Transport processes at an electrode electrolyte interface are illustrated in Fig. 8.3.
Consider a solid-solution interface. Diffusion of electro-active ions from bulk to the
interface and interaction at electrode resulting from charge transfer.
diffusion
Charge transfer
++
++
(bulk)
M0
M
Slow step
(surface)
(concentration
(reduced)
(activation
polarization)
Total
Slow step
polarization)
conc
(Total
(concentration
polarization)
polarization)
act
(activation
polarization)
Polarization resulting from concentration gradients is termed concentration

polarization; while activation polarization is caused by a slow step in the electrode
reaction (electrode reaction requires activation energy in order to reach the final
state)
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Examples of activation polarization include:

Hydrogen overvoltage (overpotential)
H+ + e = Hads
2Hads = H2
2H+ + 2e = H2
E0 = 0.00 V
For this cathodic reaction, there will be deviation from the reversible value to more
negative values and that deviation is the overvoltage.
AE
= Eapp -
Erev
(Overpotential)
Similarly, we come across oxygen overvoltage, chlorine overvoltage etc.

2OH- = O2 + H2O + 2e
The contribution to polarization due to IR drops is referred to as Resistance
polarization
So Total polarization T = Act + Conc + resist
When polarization occurs mostly at anodes, corrosion reaction is Anodically
Controlled - Anodic process at electrode is accelerated by moving the potential in
the positive direction.
When polarization occurs mostly at cathodes, it is Cathodically controlled Cathodic process accelerated by moving the potential in the negative direction.
Resistance control when electrolyte / electrode resistance is so high that the current
is insufficient to polarise either of the electrodes.
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Fig. 8.4 Anodic, Cathodic, Mixed and Resistance control
Mixed control refers to the condition where both anode and cathode are polarized.
Schematic illustrations of anodic, cathodic, mixed and resistance controls are given
in Fig 8.4.
6
Lecture 9: Development Of Metal-tolerant Acidithiobacillus Ferrooxidans
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Lecture 9
Development Of Metal-tolerant Acidithiobacillus ferrooxidans
Keywords: Metal Tolerance, Multimetal Tolerance, Serial Subculturing
Multi-metal toxicity
How to quantify metal tolerance in relation to unadapted and adapted strains of
At.ferrooxidans?
A comparison index termed Toxicity Index (TI) can be used which is the ratio of the
period required for complete iron oxidation by a strain in presence of a given
concentration of toxic metal ion to that required by an unadapted strain in the absence of
the toxic metal.
For a normally 9K grown strain of At.ferrooxidans, it takes upto 42-45 hours for
complete ferrous ion oxidation. Considering a sampling period of 8 hours, a strain can be
considered fully metal tolerant if the TI is in the range of 1-1.2.
For TI higher than 1-1.2, the added metal ion is considered toxic to the organism. [41]
Ferrous ion oxidation ability of different strains of At.ferrooxidans in the presence and absence
of varying concentrations of toxic metal ions such as ferric, cupric and zinc is illustrated in table
9.1.
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Course Title: Metals Biotechnology
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Table 9.1: Iron oxidation rates for At.ferrooxidans in the presence and absence of toxic metal ions.
Time for complete

Type of strain
Toxic metal ion
ferrous oxidation in
TI
9K medium
Normal strain grown
----
42h
Fe+++ 5g/L
74h
1.8
10g/L
140h
3.3
Cu++ 5g/L
45h
1.1
10g/L
80h
1.9
Zn++ 10g/L
45
1.1
20g/L
50
1.2
40g/L
95
2.3
in 9K medium
Unadapted strain in
the presence of
different toxic metals
Relatively, among the three types of toxic metal ions, ferric ions confer higher toxicity, followed
by cupric ions for the growth of At.ferrooxidans with respect to ferrous ion oxidation. Zinc ions
are relatively less toxic compared to ferric and cupric ions for a given metal ion concentrations.
For a strain preadapted to 10 g/L of ferric ion, the toxicity index decreases from 3.3 to 1.1
if exposed to a 9K medium containing upto 10g/L of cupric ions.
Such a Fe+++ ion preadapted strain aquires tolerance towards higher concentrations of
copper and zinc also.
Iron oxidation behavior of metal-tolerant At.ferrooxidans are illustrated in table 9.2.
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Table 9.2: Iron oxidation behavior of metal-tolerant At.ferrooxidans
Type of strain
Toxic metal ion
Time for complete

Fe++ oxidation(h)
TI
At.ferrooxidans
5g/L of Fe+++
50
1.2
preadapted to 25g/L
10g/L of Fe+++
85
2.0
10g/L of Cu++
45
1.1
25g/L of Cu++
45
1.1
20g/L of Zn++
45
1.1
++
40g/L of Zn
60
1.4
At.ferrooxidans
5g/L of Fe+++
50
1.2
preadapted to 40g/L
10g/L of Fe+++
85
2.0
10g/L of Cu++
45
1.1
25g/L of Cu++
No significant iron
----
of cupric ion
of ZnSO4
oxidation
20g/L of Zn++
42
1.0
++
42
1.0
40g/L of Zn
Preadaptation to 25g/L of cupric ions, reduces toxicity index towards ferric ion toxicity
and enhances also both copper and zinc tolerance.
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Preadaptation to 40g/L of Zinc ions, on the other hand did not significantly enhanced cupric ion
tolerance (eg: 25g/L of Cu++)
Multimetal tolerance in At.ferrooxidans is illustrated in table 9.3
Table 9.3: Multimetal tolerance in At.ferrooxidans
Metal ion concentration, g/L

Type of strain
+++
Fe
Normal unadapted
Cu
++
++
Zn
Time for complete

Fe++Oxidation
TI
20
120
2.9
40
Insignificant iron
---
oxidation
5
10
---
125
3.0
25
---
Insignificant iron
----
oxidation
10
20
115
2.7
10
40
Insignificant iron
---
oxidation
10
20
130
3.1
10
40
Insignificant iron
---
oxidation
Preadapted to 10g/L of Fe+++
Preadapted to 25g/L of Cu++

Preadapted to 40g/L of Zn++
---
25
40
Insignificant oxidation
---
25
40
Insignificant oxidation
---
---
25
40
55
1.3
25
40
58
1.4
---
25
40
No significant oxidation
---
25
40
No significant oxidation
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Metal ion toxicity in the presence of multiple toxic metal ions presents a different picture.
If the concentration of any metal ion in the mixture attains the inhibitory concentration level
when present alone, the biological iron oxidation would be impeded even of the other metals (as
binary or ternary mixture) are present in lower non-inhibitory levels.
Effect of ternary metal ion combinations in a solution is more detrimental (inhibitory) to
bacterial growth than similar levels when present as a binary combination.
Metal toxicity exhibited by a single metal ion (when present alone) is retained even when more
than one (binary or ternary) metal is present simultaneously.
At.ferrooxidans preadapted to 25g/L of copper sulfate was found to exhibit reasonable tolerance
to all metals such as copper, ferric and zinc, even when present in binary or ternary
combinations. The observation implies that copper adapted strains of At.ferrooxidans may be the
best suited for bioleaching of multimetal concentrates containing copper, zinc and iron sulfides.
To demonstrate the advantages of preadapted metal-tolerant At.ferrooxidans in bioleaching,
copper dissolution and zinc dissolution from their respective concentrates were monitored using
different types of bacterial strains as illustrated in fig.9.1 and 9.2. As expected, use of copper
adapted strains resulted in higher copper extraction from a chalcopyrite concentrate and that of
zinc-adapted strains produced highest zinc recovery from a sphalerite concentrate. Unadapted
cells were relatively inefficient in the bioleaching of both concentrates. Zinc-adapted cells were
unable to tolerate higher dissolved copper in solution. [38, 39, 41]
On the otherhand, copper-adapted cells were capable of tolerating higher zinc concentrations.
Besides the adaptation of the bacterial cells to dissolved toxic metal ions, preadaptation through
continuous growth in the presence of the metal concentrates themselves would be beneficial. It
has been experimentally established that preadaptation of bacterial cells to the concentrate
substrates is essential to ensure more efficient bioleaching. (see Figs 9.1 to 9.3).
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A Copper adapted bacteria)

B Unadapted cells)
C Control)
40
% Cu
30
B
20
10
0
0
20
40
60
Period, d
Fig. 9.1:Bioleaching of chalcopyrite-pyrite multiconcentrate using adapted and unadapted strain of

At. ferrooxidans.
++
20
(A) At.ferrooxidans preadapted to 40 g/L Zn

++
(B) At.ferrooxidans preadapted to 25 g/L Cu
(C) Unadapted strain
(D) Control
Zinc (g/L)
15
10
C
D
0
0
10
15
(days)
Fig. 9.2: Bioleaching of sphalerite concentrate with different strains of At.ferrooxidans.
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++
(A) At.ferrooxidans preadapted to 25 g/L Cu

++
(B) At.ferrooxidans preadapted to 40g/L Zn
(C) Unadapted strain
(D) Control
Copper (g/L)
1
B
C
D
0
0
10
15
Days
Fig. 9.3: Bioleaching of chalcopyrite concentrate using different strains of At.ferrooxidans.
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References(Lectures 8-9):
36. I.A. Chisholm, L.G.Leduc and G.D.Ferroni, Metal resistance and plasmid DNA in
Thiobacillus ferrooxidans, Antonie Van Leeuwenhoek, 73, (1998), pp 245-254.
37. O.H Tuovinen, S.I.Niemela and H.G.Gyllenberg, Tolerance of Thiobacillus ferrooxidans
to some metals, Antonie Van Leeuwenhoek, 37, (1971), pp 489-496.
38. A.Das, J.M. Modak and K.A. Natarajan, Surface Chemical Studies of Thiobacillus
ferrooxidans with Reference to Copper Tolerance, Antonie van Leeuwenhoek, Journal
of Microbiology, 73 (1998), pp 215-222.
39. K.A. Natarajan, K. Sudeesha and G. Ramananda Rao, Retainability of copper tolerance
in Thiobacillus ferrooxidans Antonie van Leeuwenhoek, 66 (1994) pp. 303- 306.
40. M.N. Chandraprabha and K. A. Natarajan, Mechanism of arsenic tolerance and
bioremoval of arsenic by Acidithiobacillus ferrooxidans, J. Biochem Tech. 3(2), (2011),
pp 257-265.
41. A.Das, J.M. Modak and K. A. Natarajan, Studies on multi-metal ion tolerance of
Thiobacillus ferrooxidans, Minerals Engineering, 10, (1997), pp 743-749.
8
Lecture 9: Exchange Current Density Polarization Relationships
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Lecture 9
Exchange Current Density Polarization Relationships
Keywords: Exchange Current, Tafel Relation, Concentration Profile.
A conceptual potential-current diagram depicting corrosion of zinc in an acid

solution is given below (Fig. 9.1). Note that at the corrosion potential, E corr, there is a
mixed equilibrium.
Fig. 9.1 Potential current diagram depicting acid corrosion of zinc
Considering a reversible hydrogen electrode, under equilibrium conditions, rate of

oxidation (H2 2H+ + 2e) should equal the rate of reduction (2H+ + 2e = H2).
Activation polarization (slowing down of the reaction) is a result of a slow step in the
reaction.
For example, for hydrogen evolution at cathode, the reactions involve several steps.
(i) H+ + e = Hads
(ii) Hads + Hads = H2
(iii)Then evolution of hydrogen molecules.
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Any of the above steps can control the rate of the reaction and result in activation
polarization.
Concept of exchange current density

When a metal in solution is at equilibrium, it implies rates of dissolution and
deposition reactions are equal. When the above two reactions (anodic and cathodic)
are in equilibrium, the rates (equal and opposite) of each of the two reactions are
referred to as exchange current density.
Expressing reaction rates in terms of current density,
roxid = rred =
based on Faradays law.
where roxid and rred are equilibrium oxidation and reduction rates.
io is termed exchange current density which is the rate of oxidation and reduction at
equilibrium. There is no net current under the above conditions even through the
concept is a useful method of representing rates at equilibrium.
ic = ia = io
inet = ia ic = 0
A Kinetic expression for io is given as
io = nFAKS (
Where KS is rate constant for the redox reaction

= transfer coefficient
A = Area
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Exchange current density (io) is dependent on

a) Nature of the redox reaction
b) Electrode composition / surface
c) Concentration ratio of oxidized and reduced species
d) Temperature.
Table 9.1 Approximate exchange current densities (io) for hydrogen reduction on various metals.
Metal
Io(A/cm2)
Pb, Hg
10-13
Zn
10-11
Sn, Al
10-10
Ni, Ag, Cu
10-7
Fe, Au
10-6
Pd, Rh
10-4
Pt
10-2
For example, io for H+ / H2 reaction on platinum is about 10-2A/cm2 and for mercury
it is about 10-13 A/cm2, which means it is easier to reduce hydrogen ions from acidic
electrolyte on a platinum electrode unlike on mercury, which possesses a high
Hydrogen-overvoltage. Exchange current densities are determined experimentally.
The relationship between activation polarization (overpotential) and the rate of the
reaction (ia and ic) is given below as Tafel relationship.
act =
log
For Anodic polarization act =

For Cathodic polarization act =
and
are termed Tafel constants.

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Magnitude of io will indicate as to whether the redox reaction is reversible or

irreversible. Lower io denotes higher overpotential, while higher io indicates lower
overpotential (which means the reaction tends towards reversibility).
Concentration polarization
Concentration profile at a solid-solution interface is given in Fig. 9.2:
Fig. 9.2 Concentration distance profile at electorde solution interface
C0 = surface concentration of electroactive species.

Cb = Bulk concentration.
= diffusion layer thickness (thickness of the concentration gradient)
E1 = E0 +
ln Cb
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E2 = E0 +
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ln C0
= E| - Erev
=
ln
Ficks law of diffusion states

= - AD
Where
= amount of species diffusing in unit time.
D = Diffusion coefficient
= concentration gradient
=
= m (Cb C0)
=-A
(Cb C0)
i = nF
iL (or id) = nFA
(Cb C0)
(see Fig 9.3)

iL = nFA
Cb
(C0 0 when current reaches

steady state)
Fig. 9.3 Depiction of limiting (diffusion) current
Eapp = E0 +
lan Cb
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Where m = mass transfer rate constant.
= mcb
C0 = Cb
ln
Total =
act +
=-
log
conc
red
ln
conc
+ 2.3
log
Fig. 9.4 Combined cathodic polarization
Total cathodic polarization is the sum of activation and concentration polarization as

shown in Fig. 9.4. Concentration polarization is generally absent in case of anodic
polarization of metal dissolution.
a
log
6
Lecture 10: Polarization Techniques Corrosion Rate Determination
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Lecture 10
Polarization Techniques Corrosion Rate Determination
Keywords: Corrosion Rates, Polarization Diagrams, Linear Polarization Resistance.
A weighed sample coupon of metal introduced into the corrosion process and
after desired exposure period removed, cleaned of all corrosion products and
reweighed. Weight loss can be converted to average corrosion rate (mpy) using
Faradays law.
There are ASTM standards G1, G4 and G31 for preparing,
cleaning and evaluating corrosion test specimens, conducting corrosion coupon

tests in plant equipment and laboratory immersion corrosion testing.
Using corrosion coupons for weight loss (corrosion rate) measurements has
advantages such as cheap and simple, permits analysis of corrosion products and
can easily be done in a laboratory or on a service equipment. However, it
requires long term exposures to be more accurate as short-term tests can yield
misleading information. Different shapes of corrosion coupons, such as flat, ring
type or cylindrical can be used. Coupons can be placed in industrial equipment
using holders (electrically isolated) .
Polarization techniques to determine corrosion rate

Tafel extrapolation and polarization resistance are two methods to measure
corrosion rates.
Polarization methods are faster experimental techniques
compared to classical weight loss estimation. Tafel relationship with respect to

activation controlled anodic and cathodic processes has been discussed earlier.
For an electrochemical reaction under activation control, polarization curves
exhibit linear behavior in the E Vs log ( i ) plots called Tafel behavior. Typical
polarization behavior of metals in acid solution in the presence and absence of
oxygen are illustrated below.
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Typical cathodic polarization curves with respect to Tafel behaviour are also
given. Extrapolation of cathodic and anodic Tafel slopes back to the corrosion
potential (Ecorr) are shown. Intersection point corresponds to corrosion current
density (icorr) or corrosion rate (Fig. 10.1).
ia = ic = icorr (mixed potential theory)
At least one decade of linearity in Tafel extrapolation is desirable to ensure good
accuracy. When concentration polarization and ohmic resistance come into the
picture, accuracy in Tafel extrapolation becomes more and more difficult. Steady
state polarization curves need be obtained to be more representative of corrosion
reactions.
Potentiostatic and galvanostatic methods need be compared to
ascertain the choice of a better technique to determine corrosion rates.

There are some demerits in Tafel extrapolation. Since polarization curves are not
reversible and are influenced by experimental and environmental conditions,
Tafel constants can vary from system to system. Often anodic curves may not
exhibit linear behavior near Ecorr.
Polarization of a metal in deaerated acid solution
To determine values of Ecorr and icorr, extrapolated linear sections from the
anodic and cathodic curves are used as shown in Fig. 10.1.
Anodic reaction M = M+++ 2e
Cathodic reaction 2H+ + 2e = H2
Ecorr and icorr values can be directly determined from the cross-over point (Fig.
10.2).
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Fig 10.1 Polarization behaviour of a metal (M) in deaerated acid solution
At the corrosion potential, Ecorr, rate of cathodic reduction is equal to rate of

anodic reaction (metal corrosion).
Tafel constants ( a and c ) are calculated from the anodic and cathodic slopes
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Fig 10.2 Tafel plot to estimate Tafel constants
A plot of overpotential against log i showing exchange current density is

Fig 10.3 Overpotential vs log i Tafel plot
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Current against overpotential for a reversible reaction such as the ferric ferrous
couple on a noble electrode surface is shown in Fig. 10.4.
Anodic and cathodic curves along with the resultant current behavior for
reversible reaction is illustrated.
Fe+++ + e = Fe++
Fig 10.4 Polarization plot for a reversible reaction
Polarization behaviour of a metal (M) in a stagnated aerated electrolyte at near

neutral pH is illustrated in Fig 10.5. Total cathodic current corresponds to the
sum of the currents for both hydrogen and oxygen reduction reactions and has to
be balanced by the single anodic reaction current. Depending on the level of
electrolyte agitation the magnitude of the limiting current for the oxygen
reduction will vary.
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Fig 10.5 Polarization behaviour of metal M in unstirred aerated near neutral solution
Another graphical example of electrochemical measurement of corrosion rate

through Tafel extrapolation is illustrated in Fig. 10.6. At the corrosion potential
(Ecorr), the rate of hydrogen reduction is equal to rate of metal dissolution.
Corrosion rate (icorr) in terms of current density can be estimated. Tafel constants
(a and c) can be calculated from anodic and cathodic portions of the Tafel plots.
Fig 10.6 Tafel extrapolation method
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Linear polarization resistance

Change potential by about 10-20 mV from Ecorr and measure corresponding
current (i).
Plot a linear graph for (Eapp Ecorr) Vs i.
iapp (anodic) is positive while iapp (cathodic) is negative.
The slope of the potential current density plot near Ecorr is defined as
POLARIZATION RESISTANCE (Rp).
Rp = E / i (E O)
For reactions under activation, Rp can be related to icorr as:
-icorr = B / Rp
Log Rp = log B log icorr
When B = a c / 2.3(a + c)
See Fig. 10.7
Fig 10.7 Linear polarization curve
The extent of linearity of the potential current plot depends on a and c values.
Tafel slopes are necessary to calculate B.
Since B varies within a factor of 2 around a value of 0.065 V for long range Tafel
constants, corrosion rate (icorr) can be estimated within a factor of 2 (even of Tafel
constants are not available).
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A Three-electrode cell is used for measurement of polarization resistance in a

laboratory. Linear polarization corrosion probes are used in chemical process
and water treatment industries for online monitoring, The probes are either threeelectrode or two-electrode types. These techniques permit accurate measurement
of even very low corrosion rates (< 0.1 mpy).
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Lecture 11: Mixed Potentials Concepts and Basics
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Lecture 11
Mixed Potentials Concepts and Basics
Keywords: Mixed Potential, Charge Conservation, Corrosion Potential
Principle of charge conservation:

Total rate of oxidation must be equal to total rate of reduction.
i.e. Sum of anodic oxidation currents must be equal to sum of cathodic reduction
currents.
General Anodic reaction M = M++ + 2e
Cathodic reactions can be different depending on environmental conditions.
a) Evolution of hydrogen from acid or neutral solution

2H+ + 2e = H2 (acid)
2H2O + 2e = H2 + 2OH- (neutral or alkaline)
b) Reduction of dissolved oxygen in acid or neutral solution.

O2 + 4H+ + 4e = 2H2O (acid)
O2 + 2H2O + 4e = 4OH- (neutral)
e) Reduction of dissolved oxidizers such as ferric ions

Eg: Fe+++ + e = Fe++
To understand the combined effect of various reducible species on the corrosion of a

metal (M), it is essential to use the zero current criterion,
iaM = icH(M) + icO2(M) + icFe+++(M)
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Take for example, the case of an active divalent metal, M corroding in an acid
electrolyte.
M = M++ + 2e (anodic reaction)
2H+ + 2e = H2 (cathodic reaction)
M + 2H+ = M++ + H2 (net reaction)
The metal corrodes with the evolution of hydrogen. There are two half-reactions as
shown above and they cannot coexist as separate entities on the same metal surface.
Each half reaction has its own electrode potential and exchange current density (see
Fig. 11.1).
Fig 11.1 Anodic and cathodic half cell reactions occurring simultaneously on a corroding metal, M.
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Each electrode polarizes (shifts in potentials in anodic and cathodic directions) to an

intermediate value (between the two half-cell potentials).
Since such a polarized potential is a mixture of the two half cell potentials, it is
referred to as MIXED POTENTIAL (See Fig. 11.2).
Fig 11.2 Polarization of anodic and cathodic reactions to yield a mixed potential
Ecorr is corrosion potential which is a mixed potential.
At Ecorr, rates of anodic and cathodic reactions are equal.

ic= ia = icorr, at Ecorr
icorr is the corrosion rate of the metal in the acid, and also represents the rate of
hydrogen liberation at the metal surface.
With a knowledge of
and io for the system, corrosion rate of the metal in the acid
solution can be estimated.

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From actual practice, corrosion of zinc or iron in hydrochloric acid can be

represented as detailed above. A mixed potential due to anodic oxidation of zinc (or
iron) and reduction of hydrogen ions from the acid (with liberation of hydrogen gas
on the metal surface) could be realized.
However, kinetic parameters including the exchange current density for the redox
reaction at the given metal surface need be considered in assessing the corrosion
behavior (and rate) of the metal in the corrosive medium.
Comparing the corrosion rates for zinc and iron (when present separately) in dilute
hydrochloric acid solutions, zinc dissolution is expected to be higher than that of iron
from a thermodynamic view point (E0zn/zn++ = -0.76V compared to E0 for Fe | Fe++ =
- 0.44V). The corrosion rate of iron will however be higher than that of pure zinc,
when immersed in similar concentrations of hydrochloric acid due to differences in
their exchange current densities for hydrogen liberation reaction. Exchange current
density for hydrogen reduction on zinc is lower than that on iron (see Table 9.1).
Engineering systems are heterogeneous and complex. The zero current criterion
( ia= ic) in such multi-electrode systems in a corrosive environment becomes all
the more relevant.
Consider two electrodes X and Y with one reduction reaction in an acid
solution.
iaX + iaY = icH(X) + icH(Y)
Relative areas of the anode and cathode are important in the prediction of anodic
corrosion rates and current density (current / unit area) need be considered.
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Corrosion rates need to be estimated based on kinetic parameters such as

overpotential and exchange current density.
Driving force for corrosion in fact depends on the overpotential and not essentially
on their electrode potential differences.
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Lecture 12: Mixed Potential Theory Bimetallic Couples
NPTEL Web Course
Lecture 12
Mixed Potential Theory Bimetallic Couples
Keywords: Bimetallic Couples, Area Ratio, Exchange Current Density.
Application of the mixed potential theory to some bimetallic systems can now be
considered.
Iron Platinum couple

A very noble metal coupled to a very active metal, when significantly enhanced
corrosion of iron in a corrosive medium can be expected.
iaFe= icH(Pt)
+ i H(Fe) - Pt
ia
c
Where ia and ic represent anodic and cathodic current densities and A is relative
surface area.
Since corrosion rate of platinum in the couple can be neglected due to its very high
nobility,
iaFe= icH(Pt)
+ i H(Fe)
c
Pictorial representation of half cell reaction with respect to corrosion of iron when
present alone and when present in contact with platinum (assuming equal areas) is
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Fig 12.1 Corrosion of iron in the absence and presence of platinum (as bimetallic couple) in acid medium.
Presence of platinum in the couple is very significant due to the following factors:
a) Provides additional cathodic surfaces for hydrogen reduction.
b) Exchange current density for hydrogen reduction on platinum is very much
higher than that on iron (
for Pt is 10-2 A/cm2 compared to 10-6
A/cm2 on Fe)
c) If the area ratio of platinum to iron (larger cathode in contact with smaller
anode), is increased, the effect of coupling with platinum on the corrosion
rate of iron will be magnified.
The corrosion rate of an active metal such as iron or zinc thus depends on
a) What cathodic metal they are coupled with in relation to the exchange current
density for the reduction reaction.
b) pH and nature of the cathodic reactant
For example, if the Fe-Pt couple (having higher cathode to anode surface
area ratio) is exposed to neutral pH solution where oxygen reduction is the
cathodic reaction (instead of H2), the expected effect of noble metal (Pt)
would be not so significant since the exchange current densities for oxygen
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reduction on both the surfaces are nearly same. Also, if lead metal is coupled
with iron instead of platinum in acid solution, the effect of coupling on
anodic oxidation of iron would be rather negligible, since the exchange
current density for hydrogen reduction on lead is very much lower than that
on iron.
Iron Zinc couple

Understanding the behavior of the iron-zinc couple in a corrosive environment is
important since galvanizing is universally used to protect steel structures from
corrosion. The role of zinc as a sacrificial anode is of industrial significance.
To analyze the corrosive behavior of iron in presence of zinc,
iaFe = icH(Zn)
icH(Fe) iaZn
It is known that iaZn>>icH(Zn)
Enhanced Zinc oxidation rate would lower the rate of corrosion for iron.
The effect zinc depends on the ratio of icH(Zn) / iaZn and iron will be protected as long
as this ratio is smaller.
The relative areas of the two metals in a couple influence its galvanic behavior.
Increasing cathodic surface areas for a fixed anode area will increase the anodic
corrosion rate proportionately. Similarly, if the anodic surface areas are increased for
a constant cathode area, anodic oxidation rate can be lessened.
Effect of exchange current density for the cathodic reaction on two noble metals
(gold and platinum) on the corrosion behavior of an active metal such zinc can now
be examined.
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From the EMF series, E0Au/Au+++ = + 1.42V

E0Pt /Pt++ = + 1.2V
Gold is nobler than platinum,
However, in the galvanic series, the above position is seen to be reversed (platinum
nobler than gold). Behavior of two types of noble metal-active metal couples on the
anodic corrosion behavior in an acid solution can be understood taking into
consideration Au Zn and Pt Zn couples.
Exchange current density for hydrogen reduction on platinum and gold are 10 -2
A/cm2 and 10-6 A/cm2 respectively. Under the circumstances, higher corrosion rate
(icorr) for zinc can be expected when coupled to platinum than when contacted with
gold (cathodic surface area remaining similar in both cares).
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Effect of cathodic surface area on the corrosion rate of an anodic metal is illustrated
in the figure given below. An active metal M is coupled to a noble metal N in an
acid solution. Two surface areas for the noble metal N is considered, namely, 1cm2
and 10cm2.
Fig 12.2 Effect of change in cathodic surface area on the corrosion rate of an active metal
Corrosion rate for M is the highest when coupled to 10 cm2 of N compared to 1 cm2
of N (see Fig. 12.2).
Unlike the case with coupling of an active metal with a very noble metal (such as
platinum or gold) effect of coupling of two corroding metals in a corrosive acid
medium can also be analyzed in the following lines (assuming equal areas).
a) The combined potential of the couple (eg:- Fe Zn) will lie in between the
uncoupled corrosion potentials of the two metals.
b) The corrosion rate of the most active one among the couple (Zn in case of
coupling with Fe) will always be enhanced, with a simultaneous decrease in
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the corrosion rate of the relatively noble metal (iron for example in contact
with zinc).
c) It is generally true in case of all galvanic couples that their corrosion behavior
is determined by their electrode potentials, exchange current densities,
relative surface areas and magnitude of overpotentials.
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Lecture 13: Mixed Potential Theory Activation and Diffusion Controlled Processes
NPTEL Web Course
Lecture 13
Mixed Potential Theory Activation and Diffusion
Controlled Processes
Keywords: Bimetallic Couples, Area Ratio, Exchange Current Density.
Effect of added oxidant

The driving force for corrosion is generally increased by the addition of a strong
oxidizer such as ferric ions (ferric ferrous redox couple).
Ecorr (corrosion potential) of the active metal is shifted in a nobler direction.
Corrosion rate is enhanced.
Hydrogen evolution rate decreased in the presence of oxidizer (eg: in acid
solution).
In the presence of an oxidizer such as the Fe+++/Fe++ couple in an acid medium two
possible cathodic reactions, namely,
2H+ + 2e = H2 and
Fe+++ + e = Fe++ need be considered.
The respective exchange current densities for the above cathodic reductions on the
corroding metal will determine the corrosion rate.
If for example, the exchange current density for ferric ion reduction is lower than
that for hydrogen evolution, the addition of ferric ion oxidizer will not have any
significant effect on the corrosion rate of the anodic metal in an acid medium.
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Effect of multiple reducible species on anodic corrosion is shown in Fig. 13.1.
Fig 13.1 Effect of multiple reducible species on the corrosion rate of an anodic metal.
Anodic and cathodic currents are proportional to concentrations of the redox species.
Rate of cathodic reduction can be thus related to concentration of cathodic reactant

such as hydrogen, oxygen, ferric ions etc.
For example, ic is proportional to [H+]n
With increase in pH, hydrogen ion concentration decreases in solution (and vice
versa).
= 10
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For oxygen, from a solution concentration of about 10 mg/L if through deaeration, it

is reduced to 0.01 mg/L, the cathodic reaction rate could be altered by a factor of 103.
Effect of changes in cathodic reactant concentrations on the corrosion rate of an

anodic metal is shown in Fig. 13.2.
Fig 13.2 Effect of changes in cathodic reactant concentrations on the corrosion rate of a metal.
Diffusion controlled cathodic processes

If one considers the effect of concentration polarization also along with activation
polarization for the cathodic process, effects on anodic oxidation rates need to be
seen in a different light.
There are instances when the cathodic process can be diffusion controlled (due to
concentration gradients at the solid-solution interface).
An example is metallic corrosion in sea water where oxygen diffusion controls the
cathodic process.
O2 + 2H2O + 4e = 4OH3
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Solution velocity influences the corrosion rate of metals when the cathodic process is
diffusion controlled (unlike in activation controlled systems) since limiting
(diffusion) current is affected (see Fig. 13.3).
Fig 13.3 Effect of concentration and velocity on diffusion controlled polarization
However at higher solution velocity, the cathodic reduction process becomes

activation controlled.
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The influence of solution velocity on the corrosion rate of a normal metal under a
diffusion controlled cathodic process in depicted in Fig. 13.4.
Fig 13.4 Change of corrosion rate with solution velocity for a normal metal.
Corrosion rate increases with solution velocity as long as the cathodic process is
under diffusion control and it becomes independent of velocity at higher velocities
when the cathodic reaction is under activation control.
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Lecture 14: Prevention Strategies Design and Coatings
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Lecture 14
Prevention Strategies Design and Coatings
Keywords: Corrosion Prevention, Designs, Protective Coatings.
There are a number of methods to control corrosion. The choice of any one control
technique depends on economics, safety aspects and other technical considerations.
Design
Materials selection
Protective coatings
Inhibitors and environmental alterations
Corrosion allowances
Engineering design with a view to corrosion abatement is important. For example, a
simple aspect such as providing drainage, as for an automobile side panel. Choice of
appropriate materials keeping in mind the probability of corrosion in the existing
environmental conditions is very critical.
Among the materials available for
selection; titanium, copper alloys, stainless steels, carbon steels and aluminium and
its alloys are often chosen.
Proper design of equipment

In the design of equipment, fittings such as baffles, valves and pumps to be
considered
Elimination of crevices
Complete drainage of liquids
Easy to clean
Facilitate easy access to inspection and maintenance
Avoid bimetal contacts Insulation of Joints.
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General choice of metals and alloys for corrosive applications is given in Table 14.1.
Table 14.1 Choice of materials for corrosive environments
Material
Environment
Nickel and alloys
Caustic solutions
Monel
Hydrofluoric acid
Hastelloys
Hot hydrochloric acid
Stainless steels
Nitric acid
Lead
Dil. sulfuric acid
Tin
Water
Titanium
Hot strong oxidizing

acids/liquids
Carbon steels are readily available cheaply and can easily be formed and worked into
different shapes. Carbon steels can undergo different types of corrosion, such as
rusting, hydrogen embrittlement and galvanic corrosion. Galvanization is commonly
used to protect structural steels.
Protective coatings, cathodic protection and
inhibitor are extensively used to improve the structural life of carbon steels.
Stainless steels are generally immune to corrosion in mild environments. However,
they may experience pitting, crevice and stress corrosion cracking in aggressive
environments such as sea water, chemical processing etc. Ferritic and austenitic
stainless steels are used in thin wall tubing in heat exchangers and also in many
industrial and marine applications.
Type 304 stainless steel is used in valve parts,
pump shafts and fasteners. Duplex stainless steels (Cr Mo alloys of iron) are used
in chloride and high temperature environments. Martensitic stainless steels possess
good mechanical strength.
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Nickel and alloys are used in chemical process industries. Nickel copper alloys as
monel possess resistance to nonoxidizing acids. Nickel-chromium-iron alloys
passivate in presence of oxidizers. Addition of molybdenum increases chloride
resistance.
Copper and its alloys are quite resistant to non-oxidizing aqueous and many
atmospheric environments. Brass undergoes dezincification. Aluminium and naval
brasses are more resistant.
Bronzes and aluminium bronzes are resistant to
impingement. Copper-nickel alloys exhibit good resistance to impingement and

stress corrosion.
Corrosion resistance of aluminium alloys vary widely depending on type of alloy
addition and environments.
Titanium and alloys show stable, protective oxide film (passivation). Very good
corrosion resistance in hot acids and many other corrosive environments.
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Some general approaches for corrosion prevention are detailed in Tables 14.2 and
14.3.
Table 14.2 Corrosion protection methods and processes
Approach
Process
Removal of oxidizers
Boiler water
Corrosion inhibition
Inhibitors & pH control
General corrosion prevention
Anodic and Cathodic protection
Coatings:
Metallic
Organic
Nonmetallic
Electroplating, galvanizing, metal spray or immersion.

Claddings and paints.
Anodizing, Conversion coatings.
Metal modification
Alloying
Change in surface /
environment conditions
Removal of corrosives (maintenance)

Proper designs
Avoid crevices
Provide drainage
Avoid bimetallic joints
Since general corrosion is predictable, design considerations can include preventive

measures whenever and wherever possible.
Some examples:
Wall thickness control

Control of process stream composition
(Elimination of chlorides)
Prevention of acid contacts - neutralization.
Minimization of vapor condensations and collection.
Prevention of leakage of corrosives.
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For carbon steels: Cathodic protection combined with coatings.

Channel and angle sections positioned to collect and drain water,
liquids and debris.
Table 14.3 Corrosion types with prevention strategies
Type of corrosion
Prevention Strategies
Stress corrosion cracking
More resistant alloys. Remove tensile stress,

control of environment (elimination of
chlorides)
Corrosion fatigue
Eliminate cyclic stress and corrosive

environment.
More rigid design to reduce stresses due to
vibrations.
Avoid stress concentration in design.
Hydrogen embrittlement
Choice of less susceptible alloy / coatings.

Avoid cathodic protection (steels in acid
Environments)
Galvanic Corrosion
Selection of metals / alloys closer in galvanic

series. Favorable cathode to anode ratio.
Coating taking care not to create smaller
anodes with larger cathodes, insulation of
dissimilar joints.
Crevice corrosion
Proper design of junctions and joints to

minimize crevices. Welded joints preferable to
rivets and bolts. Pitting and crevice corrosion
are enhanced in stagnant / slow flowing
solution. Provide drainages.
Erosion corrosion and cavitation
Design to reduce velocity and turbulence,

avoid abrupt changes in flow directions.
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Coatings
Barrier between corrosive environment and metal.
Coatings may serve as sacrificial anodes (zinc on steels ) or release
substances that resist corrosion.
Metal coatings - Noble coat - Silver, copper, nickel, chromium, tin, lead on
steels
(ensure pore - free, uniform, adherent coating; favorable anode /
cathode ratio to minimise galvanic attacks).

Sacrificial coatings Zinc, aluminium, cadmium on steels. (steel is cathodic
to plated metal).
Coatings can be applied through hot dipping, hot spraying, electroplating, electroless plating, vapour deposition and metal cladding.
Aluminium, stainless steel, titanium, platinum etc can be cladded on various metallic
substrate for enhanced corrosion protection (physical or chemical).
Other types of surface treatments.

Modification of substrates through ion implantation and laser processing.
Inorganic coatings: glass, cement, ceramic and chemical conversion coatings.
Chemical conversion: Anodizing, oxide, chromate, phosphatizing.
Organic coatings: Paints, lacquers, varnishes (Resin, solvent + pigment in the coating
liquid). High performance organic coatings used in petroleum industries.
Development of corrosion resistant synthetic resins.
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Types of paint coatings

Good adhesion, flexibility, impact resistance and protection from chemicals,
moisture, and atmospheric conditions.
Lacquer synthetic resins (vinyl chloride, acrylic, rubber).
Latex (Acrylics and Vinyls)
Oil-based and Epoxy coatings (good bending, hard and flexible)
Coal tar epoxy.
Poly urethanes, polyester and vinyl ester (hard, brittle or elastomeric).
Organic zinc rich coatings (organic barrier + galvanic Zn protection)
Co-polymeric protective coatings.(thermoplastic copolymer - aromatic
coatings).
Anti - corrosion paints various types additives to improve corrosion resistance,
durability and impermeability.
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Lecture 15: Prevention Strategies Inhibitors and Surface Engineering
NPTEL Web Course
Lecture 15
Prevention Strategies - Inhibitors and Surface Engineering
Keyword: Inhibitors, Passivators, Surface Engineering.
Inhibitors are chemicals which adsorb on metal surfaces. A corrosion inhibitor can
act in several ways:
Arrest or slow down anodic or cathodic reactions by blocking active sites on
metal surfaces.
Eg: Amines, thiourea, benzoate, antimony trichloride.
Promote surface passivation (active-passive metals and alloys).
Eg: Chromate, nitrite, red lead, calcium plumbate.
Formation of a surface layer blocking exposure of the bare metal to corrosive
medium. Eg: Phosphate, silicate, bicarbonate, hexametaphosphate.
Hexylamines or sodium benzoate radiator fluids in cooling circuits of engines.
Antimony trichloride De-scaling of steels in sulfuric acid.
Volatile (vapour phase) inhibitors (Amines) -Metal (steel) articles or equipment
during transport.
A classification of inhibitors based on their functionality is given below:
Passivating inhibitors
Cathodic inhibitors
Organic inhibitors
Precipitation inhibitors
Volatile corrosion inhibitors.
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Two types of passivating inhibitors.

Oxidizing anions Chromate, nitrite and nitrate that can passivate steel in
absence of oxygen.
Nonoxidizing ions phosphate, tungstate and molybdate that require oxygen
to passivate steel.
Inhibitors to be used in just the required concentration.
Higher concentration Over protection? or corrosion?
Lower concentration do not protect!
Inhibitors generally used in quantities less than 0.1% by weight.
Cathodic inhibitors:
Slow down cathodic reaction or selectively precipitate on cathodic areas.

Act as poisons, precipitates or as oxygen scavenger.
Compounds of As and Sb make combination of and discharge of hydrogen
difficult. Ions of Ca, Zn or Mg precipitate as oxides to form protective layers.
Oxygen scavengers prevent cathodic depolarization due to O2 (Na2 SO3).
Organic inhibitors Both anodic and cathodic effects.
Adsorption depending on charge of inhibitor.
Precipitation inhibitors: Film forming compounds block anodic and
cathodic sites. (E.g.: calcium, magnesium precipitation of silicates and
phosphates).
Vapour phase inhibitors used during transport in closed environment.

Morpholine, Hydrazine.
Vapor condenses and hydrolyzed by moisture to liberate protective ions.
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Corrosion inhibitors used in:

Chemicals processing
Petroleum refining
Cement and concrete
Pulp and paper
Oil and gas production
Metals
Utilities
Effect of addition of cathodic, anodic and mixed inhibitors on the corrosion rate of a
metal is illustrated in Fig. 15.1, 15.2 and 15.3. Influence of the inhibitors on the
anodic and cathode reactions, respectively could be seen. As can be seen, cathodic
inhibitors selectively influence the cathodic polarization, bringing down corrosion
rates. Similarly, anodic inhibitors specifically interfere with the anodic oxidation
reactions, decreasing icorr values. On the otherhand, mixed inhibitors influence both
anodic and cathodic reaction rates.
Fig 15.1 Role of cathodic inhibitor on corrosion rate of a metal.
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Fig 15.2 Role of anodic inhibitors on the corrosion rate of a metal
Mixed inhibitors (amines, selenides)
Fig 15.3 Role of mixed inhibitors on the corrosion rate of a metal
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General inhibitors used in some industrial operations are listed in Table 15.1
Table 15.1 Industrial uses of inhibitors
Recirculation cooling water -
Silicates, chromate, nitrate, polyphosphates
Automotives coolants
Benzoate, borax, phosphate, nitrite

Mercaptobenzothiazole.
Steam condensates
Ammonia, amines (benzylcyclohexamine).

Octadecylamine (long chain aliphatic)
Sea Water and brines
Chromates, nitrite etc.
Pickling acids
Phenylthiourea, mercaptans, quinoline,

Pyridine, various long chain amines.
Oil refining and production -
Primary, amido-, quaternary amines

Imidazoline.
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Surface modification approaches for corrosion protection of steels.

Modification of surface region of engineering alloys through diffusion of different
elements and formation of a layer having desirable chemical composition,
microstructure and properties.
Thermo-chemical treatments Physical and chemical
Vapour deposition.
Coatings by plasma spraying
Electrospark deposition
Ion implantation
Sputter deposition of selected elements and compounds.
Surface layers developed by such materials, can be classified as:
Overlay coatings
Diffusion coatings
Recast layers
Thermo-chemical treatment for surface modification of steels nonmetals or metals
introduced into metal surfaces by thermo - diffusion after chemical reaction and
adsorption.
Caburizing, nitriding, carbonitriding, boronizing, chromising and aluminizing are
some popular methods. Other examples include surface modification by Electrical
Discharge Machining to remove surface material-Melted zones are transformed to
recast layers with specific structures.
Surface modification by electrical discharge treatment in electrolyte where a high
energy thermal process is involved at surfaces leading to melting, vaporization,
activation and alloying in an electrolyte.
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Laser surface engineering for corrosion protection

a) Microstructure modification
Laser surface melting
Laser shock peening.
b) Chemical composition and microstructure modification.
Laser cladding
Laser surface alloying
Pulsed laser deposition
Laser based thermal spray
Types of surface engineering
Coatings sputtering, CVD, spin coat,
Passivation
Chemical treatment
Plasma treatment
Surface derivitization
Laser treatment
Plasma deposition
Polymerized coatings
Fluropolymers and siloxanes
Scratch - resistant coats
Paint adhesion
Electropolishing 316 stainless steel, Nitinol (oxide enrichment).
Conversion coatings
Oxidation, passivation
Chromate, phosphate, black oxide
Pore surface engineering.
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Lecture 16: Cathodic Protection Principles and Classification
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Lecture 16
Cathodic Protection Principles and Classification
Keywords: Cathodic Protection, Equipotential Surface, Impressed Current, Sacrificial Anode.
Sri Humphrey Davy s pioneering work (1824) on protecting the copper sheathing on wooden
hulls in the British Navy by sacrificial zinc and iron anodes is considered to be the earliest
example of application of cathodic protection.
Copper-sheathed ship hulls protected by sacrificial blocks of iron.
Zinc alloy as sacrificial anode. Galvanising Typical example of sacrificial anode to protect
steels.
Various definitions
Reducing or eliminating altogether corrosion by making the metal a cathode by application of
either an impressed DC current or attaching the metal to a sacrificial anode.
Corrosion occurs at anodic areas if all anodic areas can be converted to cathodic areas, the
entire structure will become cathode and corrosion is stopped.
Corrosion occurs at the regions where current discharges from metal to environment (soil, water)
(anodic areas). There is no corrosion at regions where current enters from the environment to
metal (cathodic areas).
Objective should then be to force the entire structure to collect current from the environment
(making it cathodic entirely).
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Current flow depends on factors such as:

a. Resistivity of environment and
b. Degree of polarization of anode and cathodic areas.
Cathodic protection is achieved by supplying electrons to the structure being protected.
Driving force for corrosion is the potential difference. Equipotential surface - No driving force
(no current flows). In Fig. 16.1, the above principles underlying cathodic protection are
illustrated diagrammatically.
Fig 16.1 Basic concept of cathodic protection.
Reactions
M = M++ + 2e (anodic, corrosion)
2H+ + 2e = H2 (cathodic Acid Solutions)
O2 + 2H2O + 4e = 4OH- (cathodic-neutral to mild alkaline)
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Principles governing cathodic protection are illustrated in Fig. 16.2 below.
As per mixed
potential theory, the zero current criterion is shown. An equilibrium is established on metal (M)
in which anodic oxidation rate is equal to cathodic reduction rate [E corr and icorr(A)]. By cathodic
polarization of the metal with an applied DC current (iapp), initial corrosion potential is seen
shifted to a lower value [icorr(B)]. Complete stoppage of corrosion, requires polarization of the
metal to the reversible potential of the metal (E oM).
Fig 16.2 Electrochemical principles governing cathodic protection
Principles of cathodic protection of a metal (steel, for example) in neutral aerated water or sea
water are shown in Fig. 16.3. Diffusion controlled cathodic oxygen reduction is the cathodic
reaction marked by a limiting current. Applied current and corrosion rate are limited by the
limiting (diffusion) current density. Current requirements can be further reduced by surface
coatings.
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Fig 16.3 Electrochemical aspects of cathodic protection in neutral sea water.
Two methods of cathodic protection

a) Use of sacrificial anodes.
b) Impressed current method.
Fig. 16.4 and Fig. 16.5 illustrate the two types of cathodic protection, namely, sacrificial anode
and impressed current methods.
Fig 16.4 Sacrificial anode method
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Fig 16.5 Impressed current method
Factors to be considered in the design and execution of cathodic protection installations.
Impressed current system

a) How much current necessary for complete protection?
b) Source of DC Current.
c) Installation, Design, erection and maintenance.
d) Auxiliary anodes choice, size, number, installation.
e) How to assess elimination of corrosion through entire structure?
There are a few limitations based on current flow reaching all through protected conducting
structure. For example, in a pile-up of pipes, current may not efficiently reach pipe surfaces
placed in between. Internal pipe surface may not receive protection. Similarly, portions of pipe
lines above ground, valves etc, cannot receive complete protection.
The above conditions are generally referred to as electrical shielding.
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Current necessary for protection need be just sufficient; neither less nor excess.
Excess current may do harm!
Lower current do not protect!
Requirements of galvanic sacrificial anodes

a. Potential between the anode and the corroding metal structure should be large enough to
overcome the anode-cathode cells.
b. Sacrificial anode to have sufficient Electrical Energy Content (EEC) which predicts its
life.
c. Good current efficiency relevant to anodic corrosion.
EEC can be estimated and expressed as ampere hours/weight (kg or lb)
Eg: Pure Zinc that possesses high EEC of 372 ampere hour / pound.
This means if the zinc sacrificial anode has to discharge continuously one ampere, on pound of
its weight would be consumed in 372 hours. Lower current discharge will prolong its life
further.
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Lecture 17: Cathodic Protection Influencing Factors and Monitoring
NPTEL Web Course
Lecture 17
Cathodic Protection Influencing Factors and Monitoring
Keywords: Coated Surfaces, Protection Criterion, Anode Materials, Pipeline Protection.
For large structures such as underground pipe lines, impressed current cathodic
protection is used, while for smaller structures such as house-hold water tanks, ships
hull etc, sacrificial anodes can be effectively used. Painting of steel pipe lines and
tubes can significantly reduce protection current requirements and thus save cost.
Approximate current requirements for cathodic protection of steel pipes are given
below:
Uncoated in flowing sea water
10-15 mA/ft2
Well-coated in water
0.01-0.003 mA/ft2
Excellently coated and exposed to water

or under soil
0.0003 or less mA/ft 2
As can be seen above, good surface coating significantly reduces protection current
requirements.
Electrochemical basis for protection criterion can be assessed:
Protection of steel is taken as example:
Fe = Fe++ + 2e
E0 = - 0.44 V
When polarized to half cell potential of above reaction, corrosion rate reduces to 0.
Rate of forward and reverse reaction are same when net reaction rate is zero.
Eh = - 0.44 +
log [Fe++]
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Fe++ + 2OH- = Fe (OH)2

Calculated potential (based on solubility product) is -0.59V (SHE) which
corresponds to about -0.90V (vs Cu/CuSO4).
Accepted criterion for protection of steel in water is -0.85V (vs Cu/CuSO4).
Potential of structure to environment is generally measured using Cu/CuSO 4
reference electrode. Test coupons made of same metal and previously weighed can
be electrically connected to protected structures. These coupons are also exposed to
same cathodic current in the corrosive environment. Estimation of weight losses of
such coupons is a better proof of cathodic protection.
Table 17.1 Potentials for Cathodic protection (Cu/CuSO 4 electrode)
Iron and Steel
-0.85 to -0.95 V
Lead
-0.6 V
Copper and alloys
-0.5 to -0.66 V
Aluminium
-0.95 to -1.2 V
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Anode materials that can be used as ground-beds in impressed current cathodic

protection are given Table 17.2
Table 17.2 Anode materials for impressed current cathodic protection
Material
Cast Iron
Average
consumption rate
kg/A-year
57
Steel scrap
5-8
Aluminium
45
Graphite
0.6 1.0
Lead
-----
Platinum
-----
Magnesium, zinc and aluminium and their alloys can be used as sacrificial anodes.
Design considerations for both impressed current and sacrificial anode systems have
some common steps.
a) Area to be protected
Exposed areas of the structure in coated system, exposed area at breaks and
deteriorated coatings.
b) Polarised potential Current density based on area need be estimated.
c) Current demand Current density demands depend on the environment and
nature of surface coating.
d) Anode consumption Required number and weights of anode materials
determined from known consumption rates for the desired current demand.
Anode number and distribution for the protected structure can be thus
estimated.
Anode resistance and design output current can then be estimated.
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Monitoring of effectiveness of pipeline protection

Most widespread method is based on potential measurements of a cathodically
polarized structure with reference to a standard electrode. A potential of -0.85V (Cu
/ CuSO4) is sufficient for protection of steel in soil and natural water environments.
It may however be borne in mind that the above criterion is not optimum and
situations may arise when more negative (upto 1.0V) may be required or even
lower (-0.7V) potential may suffice for protection. Interference from IR components
can introduce errors in pipeline potential measurements. Elimination of IR drop can
be achieved using switch off method. Potential measurements in chosen control
points in a pipeline are frequently insufficient to ensure effective protection. Close
Interval Potential Survey (CIPS) is an intensive monitoring technique based on
connecting a thin cable to a pipeline to monitor frequent potential readings all the
way. Special computer software together with appropriate instrumentation can be
used for gathering and processing the data. Another technique called Direct Current
Voltage Gradient (DCVG) method enables protection evaluation and also detection
of defects in insulation. Potential gradient is monitored in the soil with a sensitive
potential measurement meter using two reference electrodes kept at both sides of the
pipeline at shorter distances.
Corrosion coupons (probes) are generally used for monitoring of cathodic protection.
A schematic representation of a coupon probe connected to a cathodically protected
pipeline is illustrated in Fig. 17.1 . The arrangement allows measurement of switchoff potential without any interruption of pipeline protection.
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Fig 17.1 Circuit for monitoring cathodic protection.
Different types of simulation probes are available for determination of :

a) Level of protection in sections in casing pipes.
b) Polarization resistance and depolarization rate.
c) Insulation coating resistance.
d) Any interference on neighbouring underground installations.
e) Corrosion rate of protected structures.
Such probes need be located in various geological locations through a running
pipeline. Recently kinetic cathodic protection criterion has been proposed to allow
maintenance of metal corrosion rate at a desired level. There are several pipeline
corrosion rate control methods including both physical and electrochemical
techniques, which allow determination of effective protection in chosen regions of
structures.
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Table 17.3 Corrosion rate control in pipelines.
Electrochemical
Impedance
spectroscopy
Electrochemical noise
Harmonic synthesis
Polarization curves
Polarization
resistance
Physical
Electrical resistance
Radiography
Ultrasonic
Weight loss determination
There are several developments in cathodic protection instrumentation.
Use of
thyristor controlled rectifiers will enable automatic control of current output

depending on corrosive environment requirements.
There is also a possibility of controlled potential cathodic protection to suit specific
structures. For example, in sea-going vessels, the hull is subjected to variations in
flow velocities leading to alteration in limiting current density (with respect to
oxygen reduction).
Such limiting current fluctuations significantly influence
cathodic protection current requirements from time to time. In such environments,

controlling the potential (rather than current) would be more beneficial. Controlled
potential protection is extensively used for ship hulls incorporating anode
reference electrode attachment along with automatically controlled power supply
unit.
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Lecture 18: Design Aspects of Cathodic Protection
NPTEL Web Course
Lecture 18
Design Aspects of Cathodic Protection
Keywords: Cathodic Protection Design, Choice of Protection, Engineering Aspects.
Advantages and uses of cathodic protection:

Compared to alternative protection methods, cathodic protection is applied by
simply maintaining a DC power circuit and its effectiveness can be
continuously monitored.
Generally applied to coated structures to protect areas where coatings are
damaged-enable longer life span for existing structures.
Can avoid other design considerations for corrosion resistance (such as
corrosion allowance) if cathodic protection is pre-specified.
Can be applied to all metallic structures / including concrete).
Application for protection of exterior surfaces of

Ship hulls
Pipelines
Storage tank bases
Seashore structures
Off shore platforms
and internal surfaces of
Large diameter pipelines.

Storage tanks (water and oil)
Water circulation systems
Can be applied to copper base alloys (water systems), lead sheathed
cables, aluminium alloys and reinforced concrete structures (buildings, bridges,

sea shore, and marine structures).
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Basic requirements:
For galvanic protection (sacrificial anode)
Sacrificial anodes
Direct connection to the structure.
Minimum resistance between anodes connection.
For impressed current protection
Inert anodes (backfill ground-bed)
DC power supply.
Well insulated, minimum resistance and secure conducting connections
Background information for choice of cathodic protection type and design
considerations:
Structures physical dimensions (surface area).
Size, shape, material type and locations.
Electrical isolation and elimination of short circuits.
Corrosion history in the area with respect to environment.
Resistivity survey information.
Information on pH, potential between structure and environment, current
requirements per unit area.
For ensuring reliable and cost-effective protection, the following aspects need be
ascertained.
Electrical continuity minimize iR drop.
Coatings to minimize current requirements.
Structure isolation introduction of isolation joints (insulating flanges).
Availability of test stations with facilities for monitoring and data
aquisition.
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Current requirements for complete protection can be assessed through.

Actual tests on existing structure using a temporarily organized cathodic
protection setup.
Based on prior experience and theoretical calculations based on coating
efficiency.
Suggested formula
Total protective current = (Area in ft 2) (required current density) x (1.0 coating
efficiency)
Table 18.1 Current requirements for cathodic protection of uncoated steels
Approximate current requirements (mA/ft 2) for uncoated steel

Soil at natural pH
0.4 1.5
Highly acidic soil
3 15
Fresh water (static)
16
Flowing water with oxygen
5 15
Seawater
5 - 10
Total current requirements can be estimated by multiplying current density

requirements with surface area
Choice between the two methods of cathodic protection depends on
Conditions at site
Current density requirements
Soil resistivity
If the soil resistivity is lower and current requirements are less than about
1mA/ft2, galvanic anodes can be used.
For larger resistivity and current
requirements, impressed current protection may be opted for.
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Design aspects for galvanic anode cathodic protection

Soil resistivity assessment Site of lowest resistivity to be chosen for
location of anode.
Choice of anode material Data from commercially available anodes to
be carefully assessed.
Table 18.2 Properties of some sacrificial anodes.
Metal
Potential (Cu / CuSO4)
Density, g/cm3
EEC (amp h / Kg)
Aluminium
1.15 V
2.7
2700
Magnesium
1.55 V
1.7
1230
Zinc
1.10 V
7.1
780
Aluminium and magnesium alloy anodes can also be chosen:

Open circuit potentials for various anodes to be known to facilitate
selection. Similarly, for protection of steel, its potential in soil or water
need be known. Net driving potential between the metal to be protected
and the sacrificial anode in the environment to be the criterion. This will
involve the polarized potential of the steel (protected) when contacted
with the anode such as magnesium.
Estimate number of anodes required for desired protection and to
compensate resistance limitations (anode to electrolyte and lead wire
resistance as well as structure to electrolyte resistance).
Based on the knowledge of ground-bed resistance and life expectancy of anodes,
requirement of number of anodes is calculated.
Design aspects for impressed current cathodic protection
Soil resistivity
Estimation of required current density. Actual current requirements can be
assessed using a provisional test setup, where battery-power supply can be
used. Effectiveness of insulating joints (as in a pipeline) can be tested.
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Selection of appropriate ground-bed anode (high silicon, chromium

bearing cast iron commonly used). Backfill materials such as coal-coke
breeze, calcined petroleum coke or graphite can be chosen for ground-bed
anodes for protection of subsoil steel structures such as pipelines.
Number of anodes to meet current density and design requirement.
Selection of anode sites and calculation of total circuit resistance.
Selection of suitable DC power system.
Table 18.3 Comparison between the two cathodic protection systems.
Galvanic
Impressed current
No external power
External power supply required
Driving potential fixed
Adjustable applied potential current
Used in low resistivity environment
Can be used even in high resistivity

environment
Lower maintenance
High maintenance
Cannot originate stray currents
Can cause stray current problems
Used for small and well - coated
Suitable for larger structures (coated or
structures
uncoated)
REFERENCES
1. Cathodic protection Guide. www.npl.co.uk (from web)
2. J.
P.
Guyer,
Introduction to
cathodic protection,
2009,
CED
enginerring.com (from web)

3. J. B. Bushman, Impressed current cathodic protection system design,
Bushman and Associates. Ohio (from web)
4. NACE literature on cathodic protection criteria: NACE, Houston (1989).
5. J. H. Morgan, cathodic protection, NACE, Houston, 1987.
6. D. A. Jones, Principles and prevention of corrosion, Prentice Hall, N. J.
(1996).
7. A.W.Peabody, Principles of Cathodic Protection, Chapter 5, NACE Basic
Corrosion Course, NACE, Houston (1970)
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Lecture 19: Stray Current Corrosion
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Lecture 19
Stray Current Corrosion
Keywords: Stray Current, Electrical Bonding, Insulated Couplings
Stray currents are currents flowing from external sources. Any metallic structure,
such as a buried pipeline represents a low resistant current path and is thus
vulnerable to the effect of stray currents.
Stray-current effects are encountered in several impressed current cathodic
protection systems. This is very common in industrial protected systems, such as
oil production industries having innumerable buried pipe lines. Current leakage
from auxiliary anodes associated with cathodic protection systems can enter
unintentionally to a near-by unprotected structure and leave from the surfaces
creating severe corrosion (see Fig. 19.1).
Fig 19.1 Stray current leakage from a cathodic protection system to a nearby pipeline.
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Other sources of stray currents include DC electric power traction, welders,

electroplating units and ground electric DC power.
If there is a current path due to a low resistance metallic object (for example, a
pipe line or another metallic structure), current leakage from an impressed current
protected system will enter such unprotected structure before returning to the
protected object. Regions from where current leaves are susceptible to straycurrent corrosion.
A solution to such a problem is through electrical bonding of the near-by
structure. Simultaneously additional anodes and increasing DC power capacity
can accord full protection to all structures in the vicinity. Properly insulated
couplings can help reduce the problem (see Fig. 19.2).
Fig 19.2 Proper design through additional anodes to prevent stray current corrosion.
When impressed current protection systems are installed, anode ground beds
should be so located that stray current from them cannot make entry into other
near-by structures.
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Direct stray currents can cause anodic, cathodic or a combined interference.

Anodic interference is generally found in close proximity to a buried anode. The
pipeline will pick up current and will be discharged at a distance farther away
from the anode. In the current pickup site, the potential of the pipe will shift in
negative direction and is thus beneficial as cathodic protection.
Sometimes,
overprotection could be created by such potential shifts. On the other hand,

cathodic interference is produced in close proximity to a polarized cathode; the
potential shifting in a positive direction where current leaves the structure
(causing corrosion damage). In combined interference, current pickup occurs
close to anode and discharge occurs closer to cathodically polarized areas. The
damage could be higher in this case since current pickup (overprotection) and
discharge (corrosion) are both detrimental.
Stray current corrosion control in DC rail transit systems.
Fig 19.3 Stray current corrosion of a pipeline from a DC rail transit system.
Consequences of transit stray current from DC traction are illustrated in Fig. 19.3.
Stray current from the rails enters part of a water pipeline through soil and after
traversing through the pipeline path, leaves at another end.
Regions in the
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pipeline where current enters are protected, while those from where current
leaves to reenter the rail line suffer unintentional corrosion.
The question arises?
How much corrosive stray current is harmful?
It is estimated that for one ampere of stray current discharged from the transit
system to earth, complete perforation of one square inch (0.25 inch wall
thickness) steel pipe can occur within about a week.
Besides unintentional severe corrosion of nearby structures such as pipelines. DC
stray currents can result in
Free cathodic protection to regions where stray current enters a
structure.
Reduction in effectiveness and life of cathodic protection systems.
Breakdown of reinforced concrete structures.
Electrical shocks and loss of electrical grounding.
As a control measure, track-to-earth potentials under multi-loads can be
monitored through computer simulations and predictive modeling. On the other
hand, controlling transit stray current at the source itself will be preferable. The
following suggestion in this regard is noteworthy.
Reasonable spacing of traction substations.
Continuously welded rails.
Stray current collector Track slab rebar - epoxy coated.
Use of high resistivity concrete for track slab.
High track to earth resistance.
Insulated track designs are available.
Apart from this, pipeline designers and engineers can also keep in mind the
potential for stray current and monitor pipeline currents and potentials frequently.
Routine surveillance is required.
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Lecture 20: Passivity Definitions and Influencing Parameters
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Lecture 20
Passivity Definitions and Influencing Parameters
Keywords: Definition of Passivity, Flade Potential, Anodic Polarization, Critical
Anodic Current Density.
In the Eh pH diagrams, resistance to metallic corrosion is indicated at stability

regions where either the metal remains thermodynamically stable (immunity) or
the metal surface is covered with an oxide / hydroxide layer (passivity).
Passivity is due to the formation of thin, impermeable and adherent surface films
under oxidizing conditions often associated with anodic polarization.
Only
certain metals and alloys exhibit active-passive behavior, which is essentially an

acquired property.
Faraday in the 1840s showed that iron reacted rapidly in dilute nitric acid, but
was visibly unattacked in concentrated (fuming) HNO3. An invisible surface
oxide film formed in concentrated acid was found to be unstable in dilute acid
and through scratching, the surface oxide could be removed.
Definitions of passivity as proposed by Uhlig are given below:
1. A metal active in the EMF series or an alloy composed of such metals is

considered passive when its electrochemical behavior becomes that of an
appreciably less active or noble metal.
2. A metal or alloy is passive if it substantially resists corrosion in an
environment where thermodynamically there is a large free energy
change associated with its passage from the metallic state to appropriate
corrosion products.
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Examples for definition 1 are Cr, Ni, Ti, Zr and stainless steels.
Examples for definition 2 are lead in sulfuric acid, magnesium in water and iron in
inhibited pickling acid.
Two types of passivity thus exist.

a) A metal is passive if it resists corrosion under anodic polarization (noble
potential, low corrosion rate).
b) A metal is passive if it resists corrosion in spite of thermodynamic
amenability to react (active potential, low corrosion rate).
The Eh pH diagram for the Fe H2O O2 system can be superimposed on that for
chromium to understand the role of chromium as an alloying addition in steel for
enhanced corrosion resistance (Fig. 20.1). Chromium forms very stable, thin and
resistant surface films in less oxidizing conditions. Chromium addition is the basis
for stainless steels and other corrosion resistant alloys.
Fig 20.1 Eh pH diagram for iron superimposed on the chromium diagram (enhanced passivity range due to stable
Cr2O3)
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Since chromium is capable of forming a very stable oxide at much lower potentials,
alloying with chromium (minimum 12%) leads to development of corrosion resistant
stainless steels and cast irons. Other metals that can form passive surface films
include aluminium, silicon, titanium, tantalum and niobium.
Electrochemical basis of active-passive behavior is illustrated in Fig. 20.2
Fig 20.2 Potentiostatic Anodic polarization curve
Epp Primary passive potential, above which passive film becomes stable.
icrit = Critical passivating anodic current density, at which passivity is induced.
ipass Passive current density.
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On increasing the potential beyond the passive region, the passive film breaks down
and anodic corrosion current further increases in the transpassive state. Oxygen
evolution at the anode occurs at higher potentials.
Based on the above, it is possible to establish

a) Passive potential region.
b) Passive corrosion rate and
c) Necessary conditions to achieve and maintain passivity.
Decay of passivity on interruption of anodic current is characterized by Flade

potential.
If the potential as a function of time is monitored after interrupting the applied

current, the potential value first changes to a value more noble on the hydrogen
scale, then slowly changes and finally rapidly decays towards the normal active
value. The noble potential reached just before rapid decay was found by Flade to be
more noble, the more acid the solution in which passivity decayed (Fig. 20.3).
Fig 20.3 Decay of passivity showing Flade potential
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EF = E0F 0.059 pH (for Fe, Ni, Cr and alloys of Fe).

Stability of passivity is related to E F. The lower the E0F, the easier it becomes for
passivation and higher film stability. For Cr Fe alloys, the value ranges from 0.63
V to -0.10V with 25% chromium addition.
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Lecture 21: Passivity Application of Mixed Potential Theory
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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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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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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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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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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
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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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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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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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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
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Lecture 23: Anodic Protection
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Lecture 23
Anodic Protection
Keywords: Anodic Protection Range, Protection Design, Aggressive Environment.
Anodic protection refers to prevention of corrosion through impressed anodic

current. This method of protection tested and demonstrated by Edeleanu in 1954
however can be applied only to metals and alloys that exhibit active-passive
behavior. The interface potential of the structure is increased to passive domain.
If an active-passive alloy such as stainless steel is maintained in the passive region

through an applied potential (or current) from a potentiostat, its initial corrosion rate
(icorr) can be shifted to a low value at ipass as shown in Fig. 23.1.
Fig 23.1 Polarization curves depicting principles of anodic protection
As per mixed-potential theory,

Applied anodic current density = oxidation current density reduction current
density.
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Anodic protection is more effective in acid solutions than cathodic protection.

Current requirements for cathodic protection in acid solutions are several orders of
magnitude higher than that necessary for complete anodic protection. Cathodic
protection currents in acid solution can also lead to hydrogen liberation and
embrittlement of steels.
Anodic protection unlike cathodic protection is ideally suited for protection of

active-passive alloys in aggressive environments such as high acidity and corrosive
chemicals. Hence anodic protection is the most preferred choice for protection of
chemical process equipment.
Anodic protection parameters include.

a) Protection range range of potentials in which the metal/alloy exhibits stable
passivity.
b) Critical anodic current density.
c) Flade potential.
Potential corresponding to middle of the passive region can be taken as optimum for
anodic protection. While choosing the desirable protection potential, an assessment
of the aggressiveness of the environment need be made. Since chloride ions are
detrimental to passivity, higher chloride concentrations can decrease the protection
range. Metals and alloys having relatively larger pitting and protection potentials
can only be chosen for very aggressive chemical environments. Higher temperatures
can deleteriously influence the protection potential.
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Anodic protection of inner surface of a steel acid storage tank is shown in Fig. 23.2.
Fig. 23.2 Anodic protection of inner surface of a steel acid storage tank
A. Auxiliary cathode
B. Reference electrode
C. Anode connection to the tank
Inert cathode materials having large surface area preferred-Recommended cathode

materials for acid and corrosive industrial liquids include platinum-clad brass,
chromium-nickel steel, silicon cast iron, copper, Hastelloy C and nickel-plated steel.
Various types of reference electrodes such as Calomel, Ag/AgCl, Hg/HgSO 4 and

platinum are used depending on the chemical environment.
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The DC power supply used in anodic protection is more or less similar to the one
used in cathodic protection. There should be provisions for varying applied currents
and also to reduce the minimum current output. Electronic controls to maintain and
adjust current (or potential) in continuous (uninterrupted) mode could be very
advantageous.
Anodic protection can substantially reduce corrosion rate of active-passive alloys in

very aggressive environments. For example, anodic protection of 304 stainless steels
exposed to aerated sulfuric acid (5M) containing about 0.1 M chlorides could reduce
corrosion rate from an unprotected value of about 2000 m/year, to about 5 m/year.
It has been widely applied to protect chemical storage tanks, reactors, heat
exchangers and even transportation vessels.
A comparison between anodic and cathodic protection is given in Table 23.1:
Table. 23.1 Comparison of cathodic and anodic protection methods

Factors
Suitability
Cathodic protection
To all metals in general.
Anodic protection
Only to those exhibiting activepassive behavior
Environment
Only for moderate corrosion Even

aggressive
environment.
corrosives.
Cost benefit
Low investment, but higher Higher investment, but

operative costs..
operative costs.
Operation
chemical
low
Protective currents to be More precise electrochemical

established through initial estimation of protection range
design and field trials
possible.
It has been mentioned in earlier discussions on passivity that the magnitude of anodic
current density required for maintaining passivity is much lower than that required to
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passivate the metal or alloy. Such a beneficial aspect can be used with advantage of
low cost in anodic protection systems.
Approximate current density requirements for anodic protection in some aggressive

environments are given in Table 23.2:
Table. 23.2 Current density for passivation and maintenance in different corrosive environments (Alloy S30400,
room temperature)
Environment
Average current density

for passivation mA/cm2
for maintaining A/cm2
30-40% H2SO4
0.5
22
70% H2SO4
4.9
Strong H3PO4 at high temp

20-25% NaOH
2 x 10
4.2
-5
4.3
1.2 x 10-4
9
Ref: Anodic protection (Web-PowerPoint and PDF).
5
Lecture 24: MIC Definitions, Environments and Microbiology
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Lecture 24
Microbially Influenced Corrosion (MIC) Definitions,
Environments and Microbiology
Keywords: Microbial Corrosion, Microorganisms, Biofouling.
Introduction
Microbially-influenced corrosion (MIC) occurs in environments such as soil, fresh
water and sea water and accounts for more than 30 percent of all corrosion damage
of metals, alloys and several building materials. Microorganisms of interest in MIC
belong to many types such as sulfur-sulfide oxidising, sulfate-reducing, iron
oxidising, acid producing, manganese fixing and ammonia and acetate producing
bacteria and fungi. The role of Sulphate Reducing Bacteria (SRB) in MIC has been
extensively studied. Microbial activities under natural conditions influence many
electrochemical reactions directly or indirectly. Microbe-metal interactions involve
initial adhesion, biofilm formation and colonisation, generation of polymeric
substances and inorganic precipitates and subsequent corrosion.
Microbiological as well as physico-chemical and electrochemical aspects of

microbially-influenced corrosion are analysed critically. Monitoring, diagnosis and
prevention of MIC is illustrated along with suggested remedial strategies.
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Seawater, fresh water and soil as corrosive media

Sea water is an aggressive corrosive medium for biofouling and microbiallyinfluenced corrosion (MIC). It contains about 3.4% salt and is a good electrolyte that
can lead to galvanic and crevice corrosion. The rate of corrosion in seawater is
influenced by oxygen content, temperature, velocity and microorganisms. Galvanic
series for metals and alloys in flowing seawater could be used to predict potential
corrosion involving metallic couples.
Similarly, fresh water and sub-soil environments are conducive for microbial life
leading to biofouling and MIC.
With reference to biofouling, copper and copper-base alloys are more resistant
compared to other ferrous alloys.
Definition and practical significance

The role of microorganisms in the deterioration and failure of materials can be
classified into Biofouling, Biodeterioration and Biocorrosion or Microbiologicallyinfluenced corrosion(MIC). The above terms could be complementary in their
ultimate consequences. Biofouling refers to adhesion of micro- and macro-organisms
onto material surfaces in marine, fresh water and soil environments leading to
formation of fouled layers. Deterioration of nonmetallic materials like glass,
concrete, cement, rubber, wood and plastics in the presence of microbes is termed
biodeterioration. Corrosion of metals and alloys induced by the activities of
microorganisms is defined as Microbially-influenced corrosion (MIC). The general
definition for corrosion can be invoked in this case also by adding the superimposed
microbiological forces.
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Microorganisms are omnipresent and grow and reproduce at amazingly rapid rates in
soil, water and air. The organisms exhibit extreme tolerance to hostile environments
such as acidic and alkaline pH, low and higher temperatures as well as pressure
gradients. Aggressive environments are generated by microorganisms, promoting
direct or indirect corrosion. As early as in 1891, corrosion of lead sheathed cables
was suspected to be caused by bacterial metabolites.
Sulphur and iron sulphide
accumulation at the interior and exterior portions of water pipes were attributed to
the action of iron-sulphur bacteria during early 1900s.
Anaerobic corrosion of
bacteria was first reported in 1931. Tubercle formation due to microbial growth and
reaction products has been reported almost forty years ago.
However, a better
understanding of MIC processes based on microbiological and electrochemical

mechanisms, became available only since the last three decades.
The practical significance of microbial corrosion can be seen from Table 24.1, where
some industrial situations susceptible to microbial corrosion are listed. The extent of
microbial corrosion processes is evident from the fact that many of the commercially
used metals and alloys such as stainless steels, nickel and aluminium-based alloys
and materials such as concrete, asphalt and polymers are readily attacked by
microorganisms. Protective coatings, inhibitors, oils and emulsions can be
biodegraded.
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Table 24.1 MIC in industrial environments
Nuclear and thermal power plants
Cooling water tubes and pipes, sub-sea pipe

lines, stainless steel and carbon steel, copperalloys, aluminium-alloys
Subsoil pipe lines
Steels
On-shore, off-shore oil and gas processing.
Steels, Aluminium alloys
Chemical industries
Pipelines, Tanks, Condensers, Joints, heat

exchangers.
Civil engineering
Concrete in marine, fresh water and sub-soil

conditions, bridges, buildings.
Water treatment and metal working
Heat exchangers and pipes, Breakdown of oils,

emulsions and lubricants
Aviation (Defence and Civil)
Aluminium fuel tanks
Mining and metallurgical operations
Underground machinery and engineering

materials.
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A few cases of microbially-influenced corrosion reported more specifically in

systems or components in power plants are listed in Table 24.2.
Table 24.2 MIC in power plant materials
Heat exchanger tubing
Aluminium brass, 70:30 Copper-Nickel,
Pitting
90:10 Copper-Nickel
Rust, weld
Water storage tank
316 stainless steel
corrosion
Water pipes
316 stainless steel weld
Pitting
Cooling towers
Galvanised steel
General corrosion
Pumps
Stainless steel
Crevice, pitting
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Relevant Microorganisms
Microorganisms that are known to cause corrosion can be grouped as shown in Table
24.3.
Table 24.3 Microorganisms involved in MIC
1.
Bacteria
Sulphate Reducing Bacteria (SRB)

Desulfovibrio
Sulphur Oxidising and acid producing bacteria.
Acidithiobacillus
Iron
Oxidising
Bacteria
(IOB)
and
metal
depositing bacteria
Gallionella, Crenothrix, Leptothrix
Metal reducing bacteria
Pseudomonas, Shewanella..
2.
Fungi
Cladosporium resinae
Aspergillus niger
Aspergillus fumigatus
Penicillium cyclospium
Paecilomyces varioti
3.
Algae
Blue green algae
4.
Microbial
Symbiotic activity among different groups of
consortia
microorganisms
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The sulphur cycle in nature is important to MIC. Sulphur and sulfide oxidising and
sulphate reducing bacteria (SRB) are involved in a number of biogenic redox
reactions leading to products such as H2S, metal sulphides and sulfoxy compounds.
All these microbially - intermediated processes participate in corrosion processes in
soils and aqueous environments.
For example, sulphate reducing bacteria like
Desulfovibrio reduce sulphate to sulphide and hydrogen sulphide, under reducing

conditions.
SO=4 + 4H2 S= + 4H2O
2H+ + S- - = H2S
Sulphur (sulphide) oxidizing and sulphate reducing bacteria (SRB) involved in the
biological sulphur cycle in natural environments are shown in Fig. 24.1.
Fig. 24.1 Biological sulphur cycle in nature
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Sulphur and ferrous iron-oxidising bacteria such as Acidithiobacillus thiooxidans and

Acidithiobacillus ferrooxidans are acidophilic and aerobic promoting oxidation of
sulfur and sulfides.
2H2S + 2O2 = H2S2O3 + H2O
5Na2S2O3 + 8O2 + H2O = 5Na2SO4 + H2SO4 + 4S
4S + 6O2 + 4H2O = 4H2SO4
Fe++ = Fe+++ + e
Acidithiobacillus bacteria can exist over a range of pH from acidic, to alkaline

conditions. For example, Thiobacillus thioparus could oxidise sulphur, sulphide and
thiosulphate at a pH of 6-10.
Microbiological features of some thio-bacteria
involved in MIC are illustrated in Table 24.4.
Morphological features of some bacteria implicated in MIC along with typical

growth curves are illustrated in Fig 24.2 to 24.11.
All these bacteria are implicated in microbial corrosion processes and their growth
characteristics and metabolic reactions are important in understanding corrosion
mechanisims.
No.of Cells / mL
10
10
10
20
30
40
50
60
70
80
Time (hours)
Fig 24.2 Bacillus
Cell number as a function of time

during growth of Bacillus subtilis
Fig. 24.3
subtilis
6x10
1.8
5x10
1.6
4x10
3x10
1x10
EESE
Sulphate
concentration
1.4
1.2
1.0
0.8
0.6
0
0
20
40
60
80
100
Time (min)
120
140
160
0
-50
-100
-150
-200
-250
EESE in mv

2x10
cell count
sulphate concentration(g/L)
Number of cells/ml
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Fig 24.5 Cell number, SO4 conc and ESCE as a

function of time during growth of Sulphate reducing
bacteria
4.0x10
2.3
450
2.2
2.1
Cell count
pH
2.0
ESCE
1.9
400
350
8
6
Fe3+
Fe2+
4
2
0
300
10
Time (hours)
40
50
2.1
1.8
8.0x10
24
20
pH
1.5
6.0x10
pH
1.2
16
Sulphate conc.
4.0x10
0.9
2.0x10
0.6
0.0
50
100
150
200
250
300
Time (Hours)
Fig. 24.10 Cell number as a function of

time during growth of At. thiooxidans
0
0
50
100
150
200
250
Time (Hours)
Fig. 24.11 pH & SO4 conc. as a

function of time during growth
of At. thiooxidans
9
12
8
0.3
Fig. 24.9 Acidithiobacillus

thiooxidans
70
28
Cell count
1.0x10
60
Fig 24.8 Ferrous and ferric concentration

as a function of time during growth of
At.ferrooxidans
1.2x10
Number of cells / mL
30
10 20 30 40 50 60 70
Fig 24.7 Cell number, pH, ESCE as a

function of time during growth of
Acidithiobacllus sp
Fig. 24.6
Acidithiobacillus Sp
20
Time (hours)
250
Sulphate concentration (g / L)
500
3+
8.0x10
2.4
and Fe conc (g / L)
1.2x10
550
2+
1.6x10
10
2.5
Fe
ESCE in mV
2.0x10
pH
No.of cells / mL
Fig 24.4 Sulphate reducing bacteria
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Fig. 24.12 to Fig. 24.14, illustrate typical morphological features of fungi such as
Cladosporium and Aspergillus besides those of an iron and manganese oxidizing
bacteria.
Fig. 24. 12 Cladosporium
resinae
Fig. 24.13
Aspergillus spp
Fig 24.14
Gallionella spp
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Morphological features of Aspergillus,SRB and Acidithiobacllus are more

revealingly illustrated in Fig. 24.15.
Fig. 24.15 Morphological features of Aspergillus fungal network, SRB with flagellum, Acidithiobacillus and SRB
colonizing a steel surface.
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Table 24.4 Microbiological features of some thio-bacteria
Organism
Environment
Activity
Desulfovibrio desulfuricans
Mud, sewage oil wells,
Anerobic, sulphate
(Sulphate reducing)
subsoil
reduction, pH 6-7.5,
Temp. 25-300C (some
moderate thermophiles)
Acidithiobacillus thiooxidans
Sulphur and iron
Anerobic, pH2 4,
Acidithiobacillus ferrooxidans
bearing minerals, soils
28 35oC, oxidizes
and water
sulphur, sulphides
producing sulphuric acid,
Ferrous to ferric
oxidation.
Thiobacillus Thioparus
Water, mud, sludge,
Aerobic pH 6-8,
sulphidic soils
30-350C, oxidises
thiosulphate and sulphur
to sp.
From the sulfur-bacteria cycle, bacterial oxidation and reduction cycles involving
sulfur species are evident.
Both these redox concepts are important in MIC
mechanisms.
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Lecture 25: MIC Electrochemical Aspects and General Mechanisms
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Lecture 25
MIC Electrochemical Aspects and General Mechanisms
Keywords: Electrochemical Aspects, Direct Mechanism, Indirect Mechanism.
Eh and pH are the important environmental parameters controlling the growth and
activity of various aerobic and anaerobic organisms. The stability regions of various
types of microorganisms corresponding to optimum activity can be defined through
Eh pH diagrams. Eh-pH diagram for sulphur water oxygen system wherein the
stability and growth regions of various types of microorganisms are represented will
be useful in the understanding of MIC.
Iron and sulphur-oxidising acidophilic
bacteria such as Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans

grow under higher oxidising potentials and acid pH levels. Sulphur and thiosulphate
oxidising autotrophs such as Thiobacillus thioparus have optimum activity at near
neutral pH ranges and relatively higher oxidising potentials.
Sulphate reducing
bacteria (SRB) grow under reducing and neutral pH environments. Iron oxidising
heterotrophs are stable and active at neutral pH and higher oxidising conditions.
Stability regions for some acidophilic chemolithotrophs and anaerobic heterotrophs

such as SRB are shown in a S-H2O O2 diagram in Fig. 25.1. Ferric-ferrous ratios at
high acidic pH levels determine the potential limits for Acidithiobacllus ferrooxidans
where as sulfate formation from sulphide oxidation at acidic pH dictates the stability
limits for Acidithiobacillus thiooxidans. Sulfate reducing bacteria are anaerobes
having optimum growth at neutral pH ranges. Stability region for SRB corresponds
to reducing potentials at neutral to mildly alkaline pH.
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Fig.25.1 Stability regions for Acidithiobacllus and SRB in a S-H2O-O2 diagram.
Eh-pH corrosion diagrams can be readily constructed for various metal-wateroxygen systems in the presence of micro-organisms to predict the regions of MIC,
immunity and passivation. Common Eh-pH diagrams cannot represent the corrosion
behavior of metals and alloys in the presence of micro-organisms. Superimposition
of bacterial stability regions on these diagrams may bring about significant changes
in the regions of corrosion, immunity and passivation. There are instances where
electrochemical prediction of corrosion went astray when microbial activities at the
respective Eh and pH conditions were also considered. Due to microbial growth and
biofilm formation, corrosion and protection regions in such diagrams can shift.
Principal slime forming bacteria such as Bacillus subtilis, Bacillus cereus and
species of Flavobacterium, Aerobacters and Pseudomonas are present in soil
environments. Pseudomonas can grow in systems containing hydrocarbon sources
such as oils and emulsions using hydrocarbons as energy source.
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Algae range from single cell plants to multicellular species of diverse forms and
shapes.
They contain coloured pigments, the most important of which is the
chlorophyll. Algae generally grow on moist surfaces such as cooling towers, screens
and distribution systems. Some common algae groups are blue-green algae, the green
algae and the diatoms. Owing to their ability to produce corrosive organic acids,
oxygen and metabolites corrosion can be promoted.
Fungi are similar to algae but do not contain chlorophyll.
Mould fungi are
filamentous in form but most of yeast fungi are unicellular. Some corrosion-causing
fungi are Aspergillus niger, Aspergillus fumigatus, Penicilium cyclospium and
Cladosporium resinae. Production of various types of organic acids such as oxalic
acid, citric acid and gluconic acid by fungal metabolism create corrosive
environment.
Direct and indirect mechanisms
Reactions involved in MIC are based on electrochemical reactions similar to general

corrosion principles.
Anodic:
M = M++ + 2e
Cathodic:
O2 +4H+ + 4e = 2H2O (aerated, acidic)

O2 + 2H2O + 4e = 4OH- (aerated, neutral and alkaline)
2H+ + 2e = H2 (in the absence of oxygen in acid solutions)
Microorganisms, very often contribute towards corrosion without being solely and
directly responsible for the failure.
Both direct and indirect mechanisms are
involved. Microorganisms can play both direct and indirect roles. In direct attack
mechanisms, the organisms interlinks an electrode reaction (anodic or cathodic)
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through metabolism, while indirect mechanisms involves indirect microbial

contribution to corrosion through creation of corrosive environments, such as
differential aeration cells, acidic reaction products and other metal solubilising
bioreagents
.
General mechanisms can therefore be seen in different perspectives:
Changes in dissolved oxygen levels through microbial growth leading to

formation of concentration cells.
Biodegradation of additive reagents present in lubricants and emulsions.
Biogeneration of corrosive products and hydrogen consumption.
Microbiological breakdown or disruption of organic paint coatings, plastic
fittings and linings, protective films and inhibitors.
Typical examples of some of the corrosive metabolic products are illustrated below:
Both organic and inorganic acids can be produced by microbial metabolism.
Oxidation of inorganic sulphur compounds by Acidithiobacillus group of bacteria

to produce sulfuric acid.
Oxidation of iron sulphides by Acidithiobacillus ferrooxidans to produce acidic
ferric sulfate.
In the presence of organic carbon such as sucrose, fungi such as Aspergillus
generate oxalic, citric and gluconic acids.
Exopolysaccharides and bioproteins secreted by Bacillus species.
Several bacterial enzymes are electrocatalysts.
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At environmental pH, the following bacterial mechanisms are relevant.
Corrosion by cathodic depolarization attributable to Sulfate Reducing Bacteria

(SRB) which contain the enzyme, hydrogenase.
Corrosion by differential aeration cells due to deposits and biofilms formed by
iron bacteria and other slime bacteria.
Corrosive products such as organic sulphides, mercaptides, amines, ammonia,
phosphorous compounds and surfactants.
Organic corrosion inhibitors such as diamines and aliphatics are used as nutrients by
bacteria. For example, Nitrosomonas and Nitrobacter oxidise ammonia and amines
to nitrite and nitrate, destroying the inhibition properties of several inhibitors. Ferric
oxide coatings are degraded by Pseudomonas, exposing the base metal for corrosion.
Iron sulphide films are broken down by Sulphate Reducing Bacteria. Protective
aluminium oxide layers (passive film) on aluminium and its alloys could be
destroyed by the fungus, C. resinae.
Bacterial attachment and Biofilms.
Under environmental conditions, submicroscopic bacterial cells can be considered as

living colloids. Bacterial suspensions as in water and soil exhibit colloidal behavior.
At natural pH, bacterial surfaces are negatively charged. Bacterial cell walls contain
many types of cationic, anionic and nonionic polymeric substances such as
polysaccharides, phospholipids and proteins.
Cell surface hydrophobicity and
hydrophilicity depends on cell wall architecture. Surface chemical characteristics

of microorganisms are important since they govern their adhesion behavior to solid
substrates. Bacterial adhesion and biofilm formation on metals and alloys are initial
events in ultimate metallic corrosion. Forces of bacterial adhesion (attachment) need
to be understood to get an insight into biofilm formation mechanisms. A fully
developed microbial biofilm may consist of both micro and macro- organisms
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along with their metabolic products and chemical reaction products. It should be
understood that initial stages in biofilm formation invariably involves only bacterial
attachment. Attached and colorized bacterial cells prepare the foundation on which
macroorganisms subsequently attach and grow. Under the circumstances, it becomes
imperative to understand forces and mechanisms of bacterial attachment to metals
and alloys in different environments (water, air and soil).
Attachment of Acidithiobacillus organisms on (A) aluminium (B) mild steel and (C)
stainless steel are illustrated in Fig. 25.2.
Fig. 25.2. Scanning electron micrographs illustrating attachment of Acidithiobacllus sp on (A) aluminium, (B) mild
steel and (C) stainless steel surfaces.
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Attachment
of
sulfate
reducing
bacteria
such
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as
Desulfovibrio
and
Desulfotomaculum on titanium surfaces is illustrated in Fig 25.3
Fig. 25.3 Scanning electron micrographs showing SRB attachment and biofilm formation on titanium surfaces
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Lecture 26: MIC Bacterial Transport, Attachment and Affected Materials
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Lecture 26
MIC-Bacterial Transport, Attachment and Affected
Materials
Keywords: Bacterial Adhesion, Biofilms, Structural Materials.
Bacterial transport to metal surface involve:
Fluid dynamic forces (currents in water bodies and eddy diffusion in

turbulent flow systems).
Flocculation or sedimentation.
Chemotactic response due to energy gradients.
Brownian motion (colloids).
Surface properties such as charge, free energy and roughness influence bacterial
adhesion. There can be reversible and irreversible adhesion. Many forces such as
electrostatic, chemical and hydrophobic forces may be involved in bacterial adhesion
mechanisms. The following stages can be visualised to understand a fully developed
biofilm on a metal surface.
Transport of organics from bulk.

Attachment and colonisation by bacteria.
Incorporation of higher organisms (fungi, algae, protozoa).
Build up of biofilms in thickness.
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Besides its contribution towards MIC, biofilms can pose several other engineering
problems such as:
Reduction in heat transfer leading to energy loss (condenser tubes).
Reduction in mass and fluid transfer (water, oil, gas pipelines).
Structural failures (buildings, bridges, platforms and construction
materials)
Increased fuel and operating costs (ships and engines).
Several mechanisms and models have been proposed to understand biofilm

formation.
Aerobe-Anaerobe mutualism: Growth of aerobic bacteria such as Acidithiobacillus

and iron oxidizers utilizing oxygen and nutrients at the metal-solution interface
creating an anaerobic environment in the vicinity.
Sulfate and other oxidised
metabolic products formed in the biofilm due to activity of such aerobes serve as
nutrients and energy source for anaerobic bacteria such as SRB which subsequently
proliferate in the anaerobic environment. Bacterial mutualism leads to the formation
and growth of a heterogeneous biofilm (often patchy and incoherent). Oxygen
concentration cells would be formed under such conditions as illustrated below in
Fig 26.1.
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Fig. 26.1 Model for bacterial film formation on metals involving aerobic and anaerobic bacteria
Schematic representation of biofilm formation and consequent development of

differential aeration cells are shown in Fig. 26.2.
Fig. 26.2 Formation of differential aeration cells on metal surfaces due to biofilm growth.
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Tubercles (massive bio chemical deposits) can result with time. Extensive pitting
and cracks become visible under the biofilm.
Anodic and cathodic reactions
pertaining to MIC of steels in marine or soil environments are illustrated in Fig. 26.3
and Fig. 26.4.
Fig. 26.3 Model for biocorrosion of ferrous alloys due to biofilm formation.
Fig. 26.4 Anodic and cathodic reactions in differential aeration cells formed on metal surfaces.
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MIC of important structural materials
There are no known metals or alloys which can completely resist biofilm formation
and subsequent microbially-influenced corrosion. Behavior of various commonly
used metals and alloys in relation to microbially-influenced corrosion is outlined
below:
Copper and copper alloys. Commonly used in heat exchangers, pumps, valves and
condensers.
90-10 and 70-30 copper-nickel, brasses, aluminium bronzes and
admiralty brasses are used in marine environments. SRBs present in marine

environments contribute to localised corrosion of the above alloys.
They are
susceptible to microbially-influenced corrosion of different kinds. Extra-cellular

polymers secreted by microorganisms can induce corrosion of copper-base alloys
through differential aeration, selective dissolution and cathodic depolarization.
Pitting, plug / dealloying and ammonia cracking of brasses and bronzes can occur.
Sulphate-reducing bacteria generate tubercles through formation of sulphide-rich
scales on copper alloys.
In spite of copper toxicity, copper and copper alloys are not free from biological
corrosion. Acidithiobacillus group of bacteria develop higher tolerance to copper
ions and dissolve the metal. Slime forming bacteria together with iron were isolated
from the corrosion products of copper-nickel alloy and monel tubes used in a nuclear
power plant. Sulphate reducing bacteria can corrode underground copper tubes and
pipes. Biologically generated ammonia is responsible for stress corrosion cracking
of several copper alloys. Corrosion of brass in heat exchanger tubes by ammonia
produced by bacteria is reported.
Steels. Tubercle formation with pitting underneath is encountered in steel pipes and
tubes, resulting in hampered flow and plugging problems. Carbon steels are used for
water, oil and gas transport under sub-soil and marine environments.
Aerobic
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bacteria such as Gallionella, Leptothrix and Acidithiobacillus contribute to MIC

resulting from differential aeration cells. These organisms oxidize ferrous to ferric
resulting in the deposition of ferric oxyhydroxides. Anaerobic bacteria such as
Sulfate Reducing Bacteria inhabit the tubercles.
Aerobic bacteria can bring about MIC through formation of slimes, oxidation of iron
and sulphides and generation of acidic metabolites. Hydrated slimes coat the metal
surfaces, creating differential aeration cells. Iron oxidising bacteria listed in Table
26.1, oxidise ferrous ions to less soluble ferric ions, leading to the formation of
insoluble tubercles, which consist of hydrated ferric oxides and biological slimes.
Steel water pipes are prone to such attack. Massive tubercle formation inside steel
pipes, hinders fluid flow, and creates severe corrosion problems, such as extensive
pitting, fissures and crevices.
Table 26.1 Role of slime forming bacteria in metallic corrosion
Organism
Action
Gallionella Sp
Aerobic,
Iron & Steels, Tubercle
formation
Sphaerotilus Sp
Aerobic,
Iron & Steels, Ferrous oxidation
and tubercle.
Pseudomonas Sp
Aerobic,
Iron & Steels, (Some iron
reducing)
P.aeroginosa
Aerobic,
Aluminium alloys (pitting)
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Stainless steels. Stainless steels are used in nuclear power plants in sea water
environments. Iron oxidising and depositing bacteria induce MIC of stainless steels
characterized by pitting, usually adjacent to weldments. SRB can attack stainless
steels, super stainless steels such as duplex steels and molybdenum steels. Slimes
formed by bacteria can create sites for initiation of pits in stainless steels in sea water
or fresh water. Destruction of passive films in stainless steels is observed through
reducing environments created by SRBs.
Nickel-based alloys. Monels and inconels are susceptible to MIC. Nickel-based
alloys used in nuclear power plants corrode due to microbial attack under marine
environments.
Aluminium and its alloys. Protective oxide (passive) films present on aluminium
and its alloys could be disrupted and destroyed through biological attack.
Aluminium and 2024, 7075 alloys used in aircraft and fuel storage tanks are
susceptible to MIC in the presence of hydrocarbons (fuels). The generation of watersoluble organic/inorganic acids by bacteria and fungi lead to corrosion of aluminium
and alloys (pitting and intergranular corrosion).
Aluminium-magnesium (5000
series) alloys used in marine applications are susceptible to pitting, intergranular

corrosion, exfoliation and stress corrosion through microbial interaction.
Aircraft fuel tanks and sea water components of aluminium and its alloys are
corroded by organisms such as Pseudomonas, Leptothrix, Sulphate Reducing
Bacteria and fungi. The fungus, Cladosporium resinae can proliferate on kerosene
or paraffins as sole carbon sources, developing pinkish brown colonies. Fuel tanks
of especially ground aircrafts are affected by fungal growth.
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The following microorganisms had been observed in an aircraft tank sludge.

Pseudomonas aeruginosa.
Aerobacter aerogenes.
Clostridium,
Bacillus,
Desulfovibrio,
Fusarium,
Aspergillus,
Cladosporium and
Penicillium.
Titanium. Titanium is susceptible to biofouling. SRBs and acid-producing bacteria
may generate differential aeration cells leading to destruction of passive films.
Titanium and its alloys used in marine environments are susceptible to biofilm
formation involving manganese and iron oxidising bacteria as well as sulfate
reducing halophiles. Surface passive films on titanium could be disrupted in the
presence of anaerobes, leading to ennoblement and pitting.
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Lecture 27:MIC Role of Aerobic and Anaerobic Microorganisms
NPTEL Web Course
Lecture 27
MIC Role of Aerobic and Anaerobic Microorganisms
Keywords: Aerobic, Anaerobic, Sulfate-Reducing-Bacteria
Corrosion initiated and accelerated by microorganisms (metals and alloys)

MIC is also referred to as Biocorrosion
Microbial corrosion
Microbially-induced corrosion
Biofouling all types of biological attachment and growth on metal and nonmetal
surfaces in contact with natural waters (fresh or sea water).
Micro and macro-fouling refer to deposits through the growth of microbes and other
higher organisms.
Biodeterioration generally refers to deterioration of nonmetallic materials or
degradation brought about by microbes.
Microorganisms associated with MIC are generally characterized by a number of

features such as:
Small size (few micrometers)
Ubiquitous and omnipotent
Sessile or motile (active or sedentary)
Ability to attach to substrates and grow colonies.
Extremophiles (tolerant to wide range of metal concentrations, acidity,
temperature, pressure, oxygen and lack of oxygen)
Existence of consortia and mutualism
Rapid reproduction.
Generate organic and inorganic acids, alkalis, chelating agents and
extracellular polymeric substances such as proteins and polysaccharides.
Can oxidize or reduce metals and ions.
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Most of the microorganisms involved in MIC are chemolithotrophs and can be

aerobic anaerobic, mesophilic-thermophilic, autotrophs- heterotrophs, acidophilicneutrophilic and many are slime formers.
Chemotrophs get energy from chemical sources unlike photosynthetic organisms.
Microorganisms involved in MIC can be generally classified as

a) Sulfur-sulfide oxidizing bacteria.
b) Manganese oxidizers / reducers
c) Iron-oxidizing /reducing bacteria.
d) Sulfate-reducing bacteria (SRB).
e) Bacteria secreting exopolymers / slime and organic acids.
Sulfate-reducing bacteria (SRB) are a group of diverse anaerobes which bring about
dissimilatory sulphate reduction to sulfides. Although they are considered as strict
anaerobes, some genera can tolerate oxygen, hydrogen serving as electron donor.
Oil, gas and shipping industries are seriously affected by SRB activities (soil and
water) due to H2S generation. Common SRB include Desulfovibrio, Desulfobacter
and Desulfotomaculum. SRB are capable of growing in soil, fresh water and seawater environments and also in stagnant areas.
They oxidize organic substances to organic acids or CO 2, by reduction of sulfate to
sulfide through anaerobic respiration.
Tolerate pH ranges 5-9.5.
Black deposits of precipitated sulfides and odour of H2S emanation are characteristic
of SRB growth
Environmental growth conditions and metabolic features of some corrosion
causing bacteria are illustrated in Table 27.1.
Growth conditions and corrosion aspects of some heterotrophs are illustrated in
Table 27.2.
Characteristics of some sulfate reducing bacteria relevant to MIC are given in Table
27.3.
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Table 27.1 Environmental and metabolic aspects of MIC causing bacteria
Bacteria
Desulfovibrio
D. desulfuricans
pH
Temp
(0C)
Oxygen
Corrosion
Characteristics
4-8
10-40
Anaerobic
Iron and
steel,
stainless
steels,
aluminum
zinc, copper
alloys
Utilize hydrogen in
reducing SO4-- to S-and H2S promote
formation of sulfide
films.
Desulfotomaculum
D .nignificans
6-8
10-40
Anaerobic
Iron and
steel
stainless
steels
Reduce SO4-- to S-and H2S (spore

formers).
Desulfomonas
..
10-40
Anaerobic
Iron and
steel
Reduce SO4-- to S-and H2S.
Acidithiobacillus
thiooxidans
0.5-8 25-40
Aerobic
Iron and
steel copper
alloys,
concrete
Oxidizes sulfur and

sulfides to form
H2SO4, damages
protective coatings.
Acidithiobacillus
ferrooxidans
1-7
Aerobic
Iron and
steel
Oxidizes ferrous to
ferric
25-40
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Table 27.2 MIC causing heterotrophs
pH
Temp 0C
Oxygen
Gallionella
7-10
20-40
Aerobic
Iron and
steel
Oxidizes ferrous
and manganoustubercle
formation
Sphaerotilus.
7-10
20-40
Aerobic
Iron and
steel
Oxidizes ferrous
and manganous tubercle
formation
S.natans
..
..
..
Pseudomonas.
4-9
20-40
Aerobic
Iron and
steel
P.aeruginosa
4-3
20-40
Aerobic
Aluminium
alloys
Cladosparium resinae
(fungi)
3-7
10-45
Aerobic
Aluminium
alloys
Organism
Affected
metals
Action
Aluminium
alloys
Some strains can

reduce Fe+++ to
Fe++
Produces organic
acids.
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Table27.3 Important characteristics of some sulfate reducing bacteria
Desulfovibrio
Single flagellum. Do not form spores. Hydrogenase present.
Dv. desulfuricans
Dv. vulgaris
Dv. Salexigens
Curved rods (vibrios); sometimes spirilloid, occasionally straight.

Typical size 3-5 m / 0.5-1 m single flagellum.
Dv. Gigas
Large curved rods or spirilla, 5-10 m / 1.2 1.5 m.
Desulfotomaculum
Peritrichous flagella
Dt .nigrificans
Hydrogenase activity variable. Growth on pyruvate in sulphatefree media.
Dt. Orientis
Fat curved rods, 5 m x 1.5 m. Hydrogenase absent.
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Lecture 28: Mechanisms and Models for SRB Corrosion
NPTEL Web Course
Lecture 28
Mechanisms and Models for SRB Corrosion
Keywords: Anaerobic Corrosion, Hydrogenase, Biogenic Sulfides, Depolarization
Microbiological characteristics of several sulfate reducing bacteria were illustrated in

lecture 27.
Role of SRB in metallic corrosion can be understood by

a) H2S generation
b) Creation of oxygen concentration cells
c) Formation of insoluble metal sulfides
d) Cathodic depolarization
A well known mechanism involving SRB involves generation of several corrosion
cells by their attachment and subsequent interaction and metabolism. Many
hydrocarbons encountered in oil and gas exploration and mining sustain SRB
through nutrient supply.
Cathodic hydrogen (as a common corrosion reactant)
generated at metal surfaces (as in pipes) promote SRB growth. Hydrogenase-positive

SRB are implicated in hydrogen utilization which is used for bacterial reduction of
sulfate. The bacteria thus scavenge away cathodically-generated hydrogen leading to
cathodic depolarisation promoting anodic corrosion. A model for SRB attachment
on steel surfaces resulting in subsequent hydrogen depolarization is shown in Fig.
28.1.
Fig. 28.1 Model showing surface anchoring of SRB cells and cathodic depolarization.
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Proposed reactions include

Anode
Fe = Fe++ + 2e
Cathode
2H+ + 2e = H2
Depolarization
SO4-- + 8H = S-- + 4 H2O
Interaction with iron Fe++ + S-- = FeS

Fe++ + 2OH- = Fe (OH)2
Overall reaction can be stated as
4 Fe + SO4-- + 4H2O = 3 Fe (OH)2 + FeS + 2OHThe following aspects need be stressed to explain promotion of metallic corrosion in
the presence of SRB.
a) Necessity of hydrogenase enzyme as a catalyst in hydrogen utilization.
b) Bacterial generation of H2S (HS-) and formation of FeS (MeS) as a reaction
product.
c) Depolarization through cathodic hydrogen removal.
d) Role of iron (and or metallic) sulfide.
Possibility of galvanic cell formation between steel (Fe) and the iron sulfide which
serves as cathode indeed promotes corrosion. The presence of bacteria can be seen as
a biocatalyst promoting the electrochemical reactions as illustrated in Fig. 28.2.
Fig. 28.2 Model showing galvanic interaction between Fe and FeS in the presence of SRB cells.
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Metal corrosion rate is proportional to iron sulfide content in the environment.
Many other factors can also influence metallic corrosion in the presence of SRB.
a) Anodic depolarization.
b) Formation of volatile phosphorus compound.
c) Presence of iron-binding biopolymers.
d) Sulfide-induced stress corrosion cracking.
e) H2 induced stress corrosion and cracking.
The basic idea of cathodic depolarization theory is the removal of hydrogen from the
cathodic regions by the bacterial hydrogenase, coupled with sulfate reduction to
sulfide. Severe corrosion of steels in water-logged clay soils can be attributed to this
type of MIC. Ferrous sulfide and hydroxides are corrosion products. In fact, SRB
uses the adsorbed hydrogen in sulfate reduction, increasing the anodic corrosion rate
by allowing the cathodic reaction to proceed faster. Such a microbial reaction
bypasses the recombination of adsorbed hydrogen atoms, which requires higher
activation energy.
Another suggestion regarding cathodic polarization in the
presence of SRB is attributed to bacterially generated H2S.
Cathodic reaction such as
H2S + e = HS- +
H2 can occur.
Effect of precipitated iron sulfide need also be stressed. The depolarizing effect of
ferrous sulfide on hydrogen evolution was also confirmed.
In metals and alloys exhibiting active-passive behavior, breakdown of passivity by
the metabolic products of SRB can occur promoting pitting corrosion.
(Eg:-
Stainless steels).
Properties of biogenic sulfides generated by SRB and chemical sulfides need be
compared. SRB metabolites containing thiosulfates and polythionates are corrosive
to steel. Added presence of chlorides as in sea water would further aggravate the
corrosion process.
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MIC in anoxic environments in the presence of SRB need thus be understood in the
light of various combinations of parameters such as:
a) Biogenic sulfides nature of protective film on metal surface.
b) Depending on pH, poorly protective sulfide films could form.
c) Breaking down of passivity by SRB metabolites.
d) Cathodic
depolarization
hydrogenase
activity or
iron
sulfide
precipitation.
SRB influenced corrosion of steel is seen to be significantly influenced by the
nature and structure of the sulfide films.
Metal-biofilm-solution interface and
parameters such as pH, ionic concentration, oxygen levels and exopolymeric

substances control the surface corrosion products. Corrosion or protective nature of
such product films may vary depending on the environment. Presence of aggressive
anions such as chlorides could impact the corrosion rate.
SRB has been most troublesome among all organisms involved in MIC, especially in
environments related to oil, gas and shipping industries. Considerable work has been
focussed on the influence of SRB on mild steel and other iron-based alloys. Serious
problems in petroleum industries include increased refining costs due to bacterial
H2S generation (oil souring). SRB growth in sea water injection systems leads to
equipment damage besides contamination of oil and gas with viable cells and their
reaction products. They are termed obligate anaerobes obtaining energy from
oxidation of organics, using sulfate as external electron acceptor. Corrosion of steels
is generally realized as a localized attack as pitting.
Many strains are capable of respiring oxygen with hydrogen serving as electron
donor. General pH range of activity is from 5 to 10 within temperatures 50C to 500C.
In industrial environments, SRB exhibit strong affinity for adhesion to available
surfaces to develop often patchy biofilms.
Such sessile SRB biofilm initiates
localized pitting corrosion. Extracellular polymeric substances (EPS), entrapped

particles, precipitates, adsorbed ions and organic molecules are present in SRB
biofilms which are heterogeneous with thickness ranging from microns to
centimeters.
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Biofilm formation involves steps such as:

Transport of organic matter to metal surface.
Transport of planktonic cells to surface to become sessile cells.
Attachment and growth of cells within biofilm.
A pictorial representation showing stages in the attachment of SRB cells on metal

surfaces is given in Fig. 28.3.
Fig. 28.3 Stages in metal surface attachment of SRB cells
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Hydrogenase and depolarization activity of some SRB are given below:
Fresh water isolates

Desulfovibrio vulgaris
++
Desulfotomaculum orientis
Depolarization
No depolarization
Depolarization
Depolarization
Desulfovibrio spp
No depolarization
Thermophiles
Desulfotomaculum nigrificans
Halophiles
Activity of SRB in soils and waters should be reflected in the measured rest
potentials.
For example.
Eh
Corrosivity
< 100 mV
Severe
100 200 mV
Moderate
200 400 mV
Low
>400 mV
Insignificant
Aggressive and nonaggressive soil sites can be classified in relation to soil

resistivity, redox potentials, pH, water content and SRB cell counts. Similarly, soil
types such as clayey, chalky, sandy and loamy can have a bearing on metallic
corrosion.
Water samples from fresh water and salty water environments can
similarly be analyzed for the various parameters for corrosivity.
Recording of redox potentials of liquid samples can be useful to establish the

presence and growth conditions for SRB. Any contamination of the system by SRB
can be monitored through physicochemical and biochemical tests. Accumulation of
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black iron sulfides and the emanation of H2S smell will invariably suggest SRB
presence. SRB can be detected in solid and liquid samples using Starkey medium (in
water or in presence of NaCl)
Dipotassium hydrogen phosphate
0.5 g/L
Ammonium chloride
1.0 g/L
Sodium sulfate
1.0 g/L
Calcium Chloride
0.1 g/L
Magnesium sulfate
2 g/L
Sodium lactate (70%)
5 g/L
Addition of iron sulfate into the inoculated culture would result in black precipitate
and evolution of H2S.
SRB can usually be found in

a) Stagnant regions in flow lines.
b) Under sludge or in mud at bottom of pits.
c) Under the scales in low velocity flow lines, crude oil storages and water
tanks.
d) Sand and gravel filters- sewerage lines.
e) Injection wells, oil-fields, oil-water interface
f) Buried pipe lines.
Hydrocarbon degrading SRB proliferates in oil and gas reservoirs.

Anaerobic bacteria such as SRB can be found even in oxygenated environment and
the existence of oxygen-resistant proteins in some species has been observed.
Possible use of oxygen as terminal electron acceptor by SRB is also mentioned.
Oxygen gradients in biofilm include anoxic zones rich in SRB.
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Lecture 29: MIC and Biofilms
NPTEL Web Course
Lecture 29
MIC and Biofilms
Keywords: Biofilms, Potential Ennoblement, Indirect Role.
Microbially-influenced corrosion (MIC) in natural marine environments involves

two biomediated consequences:
a) Corrosion potential ennoblement.
b) Sulfate reduction-biogenic sulfide formation.
High stainless alloys (Ni-Cr-Mo), titanium alloys, platinum and gold (noble
metals) are capable of sustaining ennobled corrosion potential without enhanced
susceptibility to crevice corrosion.
Common stainless steels also exhibit corrosion potential ennoblement But
highly amenable to localised crevice corrosion.
Irrespective of cuprous ion toxicity, copper alloys are not immune to biofouling.
Microorganisms having high copper tolerance can attach and colonise on copper
base alloys. Some copper alloys exhibit potential ennoblement. Invariably, MIC
of copper alloys is caused by biogenic sulfides due to presence of SRB.
For selection of alloys for marine applications, susceptibility for crevice corrosion is
often the limiting factor. For most of the passive alloys, formation of biofilms
results in corrosion potential ennoblement, in sea water and brackish waters.
Microbially-deposited manganic and ferric oxides could well be the reason behind
such ennoblement followed by localised corrosion.
Proposed mechanisms for ennoblement in marine environments can be based on

three aspects, namely, thermodynamic, kinetic and changes in the nature of the
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reduction reaction. pH changes in the metal-film interface or an increase in partial

pressure of oxygen can influence the potential of the oxygen reaction leading to
ennoblement in corrosion potential. Shifts in the exchange current density for the
oxygen reduction also would result in shift in the potential. Pitting potentials would
also be affected under the conditions of ennoblement. Kinetic interpretation of
ennoblement implies changes in oxygen reduction kinetics due to increase in
exchange current densities. Cathodic oxygen reduction rates could be enhanced due
to increase in exchange currents and biopolymers in the biofilm could further
catalyze the cathodic reaction. Bio-enzymes are known to be excellent catalysts for
several electrochemical reactions.
Another viewpoint is the role of bacterial siderophores that possess excellent

corrosion inhibition properties. The model for predicting SRB-mediated corrosion is
based on the possibility of the metal interacting with biogenic sulfides. Reducing
environment generated by bacterial sulfate reduction in the biofilms can destabilize
the surface oxide (passive) layer, leading to metal dissolution. Thermodynamic
feasibility for the conversion of metal oxide to sulfide need be ascertained.
Corrosion and Ennoblement through biogenic manganese and iron oxide

deposition
Microbial colonization of metals and alloys can influence the mechanisms and rate
of electrochemical reactions. For example, ennoblement of passive metals such as
stainless steels and titanium can occur due to positive shifts in their open circuit
potentials in the presence of microbial colonies. An increase in cathodic current
density during cathodic polarization is often associated with enhancement of open
circuit potentials.
Biofilm formation on stainless steels changed their
electrochemical behavior through significant positive shifts in open circuit potentials

and increase in cathodic currents. Similar behavior could be observed on titanium as
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Microbial colonization responsible for such ennoblement results in
biogeneration of extracellular substances, organo metallic complexes and metal

specific enzymes. Microbially-modified acidification at metal-solution interfaces
and generation of oxidants such as H2O2 can also cause ennoblement. Microbial
production of passivating siderophores is yet another possibility.
Microbial
deposition of iron and manganese oxides / hydroxides can lead to ennoblement of

passive metals. Iron and manganese oxidizing bacteria inhabiting fresh and sea
waters as well as soils can attach and colonise on metal surfaces and precipitate
manganic and iron oxyhydroxides.
Mn+2 + 2H2O = MnO2 + 4H+ + 2e
MnOOH + OH- = MnO2 + H2O + e
Depending on the pH of water, the above reactions can influence the measured open
circuit potentials to deviate in a nobler direction.
Electrochemical oxidation/reduction of manganese and iron is part of the natural

manganese and iron cycles in natural environments.
Both manganese and iron
oxidizing and reducing microorganisms take part in the cycle involving biochemical
and electrochemical pathways.
Microbially produced MnO2 can also corrode active metals such as mild steel
Fe + MnO2 + 4H+ = Fe++ + Mn++ + 2H2O
Manganese oxidizing organisms can corrode stainless steel welds.
Mn-oxidizing microbes have been implicated in the microbial corrosion of stainless
steel welds. Formation of MnO2 ennobles its potential in natural environments. Due
to ennoblement, potentials shift above repassivation potential to the pitting potential.
Mn++ + O2
MnO2
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Indirect role of Microorganisms in MIC

Role of SRB in cathodic depolarization through consumption of hydrogen iron has
been discussed as a direct attack mechanism.
Bacterial and fungal metabolites such as organic acids may decrease anodic
polarization. Many biogenic organic acids such as citric and oxalic acids can form
soluble metal ion complexes, promoting anodic oxidation. Similarly mineral acids
such as sulfuric acid and nitric acids can be produced by microbes promoting metal
dissolution. Microbially-generated phosphorus compounds and H2O2 produced in
biofilms are aggressive corrosive agents.
In many industrial water systems bacterial colonization of metal surfaces lead to
slime formation containing extracellular polysaccharides. Slime-coated organisms
provide conducive environment of further microbial growth. A slime (or capsuble)
surrounding attached bacterium protects them from biocides and corrosion inhibitors.
Developments of concentration cells under the biofilms (oxygen and ion
concentration gradients) trigger formation of anodic and cathodic areas, promoting
corrosion.
Identification and enumeration of slime-forming microorganisms are
important tools to predict MIC in cooling water systems. Many iron and manganese
oxidizing bacteria contribute to formation of oxide scales on metal surfaces.
Presences of chloride ions aggravate corrosion since they destroy oxides and
passivity.
Disruption of passive films and oxide layers from metal surfaces through biofilm
formation and SRB metabolites has been discussed. Incorporation of extracellular
polymeric substances into the copper oxide film is suggested to be one of the reasons
for microbial corrosion of copper. 316 stainless steel interacted with and colonized
with of Citrobacter freundii was found to be subjected to local chromium depletion
under the passive layer. Similarly, depletion of iron with enrichment of sulfides
could be observed in steels subjected to SRB interaction. Many industrial failures
brought about by localised pitting in stainless steel condensers were identified as due
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to MIC. Sulfoxy anions such as thiosulfates, and tetrathionates (SRB metabolites)

present in circulating water could reduce the pitting potential of stainless steels.
Continued activity of SRB would inhibit repassivation, when chloride ions are also
present.
Stress corrosion cracking of metals and alloys can be accelerated by microbial
processes. For example, Stresses can be induced by biologically generated sulfide
and hydrogen at neutral pH.
Similarly, corrosion fatigue can be biocatalyzed.
Microbial activity can influence cathodic hydrogen generation and its entry into the
metal matrix. Hydrogen embrittlement of steels can thus be contributed by microbial
activity. Further, biogenic sulfides such as H2S and thiosulfates can act as poisons
for the hydrogen recombination reaction and promote diffusion of atomic hydrogen
into steel matrix. Under cathodic protection conditions, especially in the presence of
SRB, hydrogen-induced stress cracking of steels could occur.
Other stress-inducing biogenic products include CO2. Biological degradation of
protective coatings can also occur.
Souring of petroleum products due to H2S
presence (due to SRB activity) is a serious problem.

Degradation of
Corrosion inhibitors
Coatings and paints
Lubricants and emulsions and
Cathodic protection systems.
are influenced by microbial activity. Microorganisms can grow in inhibitor-added
electrolytes utilizing the carbon and hydrogen present in the organic chemical.
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Microorganisms are involved in corrosion in metal machining and processing

operation.
Destruction of
Anticorrosive agents in coolants.
Emulsions used in hydraulic fluids.
Oil emulsions at alkaline pH favours bacterial growth.
The microbes grow in
aqueous phase and metabolize on nutrients available (carbon,
nitrogen,
phosphorous). Due to microbial activity, degradation of emulsifiers takes place and

such an emulsion turns corrosive. Degradation of anticorrosive agents occurs in
coolants used in several engineering operations. Recirulated lubricants are prone to
bacterial infection.
Protective coatings are provided for buried structures and interior surfaces of tanks
and pipings. Microbial attacks can occur in chemical and polymer coatings.
Biodegradation of adhesives is yet another problem. Biodegradation of coatings on
pipe lines subjected to cathodic protection is of serious concern since it could
enhance current requirements for protection all of a sudden.
Experimental
observations have recorded increasing protection current requirements for pipe lines
under sub-soil conditions infested with SRB.
[Ref B.J. Little, J. S. Lee and R. I. Ray, The influence of marine biofilms on
corrosion, A concise Review, Electrochim. Acta; 54 (2008), 2-7].
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Lecture 30: MIC Case Studies and Mechanisms
NPTEL Web Course
Lecture 30
MIC Case Studies and Mechanisms
Keywords: Aircraft Fuel Tanks, Steel Corrosion, Tubercles.
To illustrate typical MIC case studies, specific engineering systems prone to

microbial attack are discussed.
Aircraft fuel systems

Microbial corrosion in aircraft systems was unknown till the1950s. Fungi and
bacteria were identified as responsible for corrosion of structural alloys used in fuel
tanks. Aviation fuel contains several types of hydrocarbons and can be contaminated
with several types of heterotrophs. Spores of fungi and bacteria can survive for
longer periods in fuel.
Aliphatic hydrocarbons present in aviation fuels can be
biodegraded. The ability of the fuel to serve as a carbon source for microbial
metabolism is a key factor in fuel microbiology.
Pseudomonads are frequently
isolated from aqueous phases associated with aircraft fuel systems. The predominant
organism present in aircraft fuel tanks has been observed to be a fungus,
Cladosporium resinae which have been isolated from corrosion pits in integral tanks.
Growth of Sulfate Reducing Bacteria (SRB) in ground storage fuel tanks has been
reported.
Aviation kerosenes may contain upto 100mg/L of water, and can promote active
growth of the above heterotrophs.
Water presence in integral tanks can occur
through condensation. Cladosporium resinae are capable of spore formation in the

kerosene layer and rapid build-up of high spore concentrations can occur.
Ambient temperature determines their growth in ground aircraft and installations.
Periods spent on ground therefore may be a factor that decides the amenability and
severity of fuel tank corrosion.
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Fungi and bacteria produce a variety of water-soluble organic acids. Drained water
from contaminated tanks record a pH of 3-4. Acid corrosion of structural metals and
alloys can thus occur. Aluminium alloys are extensively used in aircraft parts and
structures. Oxygen concentration gradients can also occur due to microbial colonies
which can induce formation of corrosion cells on aluminium alloy surfaces.
Fuel cleanliness and use of fuel biocides could mitigate the problem to certain extent.
Microbe related problems in fuel systems are illustrated in Table 30.1.
Table 30.1 Microbial Problems in fuel systems.
Type of Problem
Organisms
Clogging of pipes, valves and filters
Fungi, polymer-generating bacteria
Sludge accumulation
Various microorganisms
Reagent generation and oil / water emulsification.
Fungi and aerobic bacteria
Biocorrosion of storage tanks
Fungi and anaerobes
Suspended solids in the oil
Various microorganisms
Hydrocarbon biodegradation
Fungi and aerobic bacteria
Injectors biofouling
Aerobic bacteria and fungi
Sulfur accumulation
SRB
Engine parts breakage
Bacterial corrosion
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Aerobic bacteria and steel corrosion

From a corrosion view-point, aerobic bacteria can bring about several consequences
such as:
Slime formation
Sulfur and sulfide oxidation
Iron oxidation
Acid containing metabolites.
Slime formation is a major problem in paper mills. There are several examples of
slime formers such as filamentous fungi, algae, protozoa, diatoms and bacteria.
Hydrated biofouling slimes coat the metal surface creating favorable conditions for
initiation of concentration cells and also for the subsequent growth of anaerobic
organisms.
Sulfuric acid and reduced sulfur constituents generated by chemolithotrophs are
corrosive.
Iron oxidizers such as Gallionella, Sphaerotilus and Pseudomonas, oxidize ferrous to
ferric ions. Insoluble tubercles consisting of hydrated ferric oxides and excreted
slimes grow on the corroded steel surfaces. Fig. 30.1 shows advanced tuberculation
inside water pipelines due to bacterial iron oxidation.
Fig. 30.1 Tubercle formation inside water pipeline
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Pipelines carrying water, oil and gas are susceptible to such tuberculation. Massive
tubercles can hamper mass and heat flow. Differential aeration cells can be formed
beneath such deposits. Oxygen-rich regions serve as cathodes
O2 + 2H2O + 4e = 4OH-
Fig. 30.2 Formation of differential oxygen cells in steel pipes due to tubercle formation.
and oxygen-depleted areas act as anodes, promoting steel corrosion.

Fe = Fe++ + 2e
Tubercles can harbor different organisms including anaerobes such as SRB. Stages
in tubercle build up and generation of differential oxygen cells in steel pipes are
illustrated in Fig. 30.2.
Bio-slimes can also initiate pitting corrosion of stainless steels in sea water, fresh
water or sub-soil environments. Aerobically generated biofilms catalyse cathodic
oxygen reduction, enhancing corrosion potentials. Pitting and crevice corrosion
(especially in presence of chlorides) can thus be propagated.
Stainless steel
weldments are susceptible to MIC.
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Microorganisms influence the corrosion of active-passive metals and alloys such as

stainless steels and titanium through biofilm formation.
a) Ennoblement of corrosion potential and enhancement of cathodic reaction
rates.
b) Initiation of pitting.
The above electrochemical effects are due to biological interactions through
formation of microbial biofilms. Differences in the behavior of bare and biofilmformed metals confirm the above observation. The phenomenon of potential
ennoblement due to biofilms is often variable and variations from sample to samples
under different conditions could be observed. Percent surface coverage is shown to
play a role in the above behavior (Fig. 30.3). Mechanisms involved in ennoblements
are still inconclusive. Mixed potential theory can be applied to explain shift in
potentials in the noble direction.
Fig. 30.3 Potential ennoblement due to surface coverage.
For example, for oxygen reduction as a cathodic process for stainless steel,
ennoblement could be caused by noble shift in reversible potential for the oxygen
reduction or enhancement in its exchange current density. Tafel slopes for the
reaction would also be affected.
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Proposed mechanisms include:

a) Biocatalysis of oxygen reduction.
b) Change in pH under biofilm influencing the cathodic process or
c) Emergence of new cathodic reactions.
The role of biofilms in enhancing corrosion in the presence of microorganisms can
be quite complex involving several bio-and physico-chemical parameters. Biofilms
can act as a diffusion barrier for reactants such as oxygen and aggressive anions and
cations.
Detachment of biofilms from metal surfaces can lead to removal of
protective films. Inducement of corrosion cells such as differential oxygen and

differential concentration of reactive species can be a consequence of heterogeneous,
patchy biofilms. All the above factors can lead to generation of potential differences
at localized regions where corrosion current flow would be facilitated. Biofilms can
also influence the nature of oxidation reduction conditions at metal solution
interfaces. Redox conditions could thus differ in different regions of the biofilm.
Microbial consortia within the biofilm can influence redox conditions.
Consequences of biofilm formation can be summarized as follows:

a) Localised corrosion initiation, especially in active-passive alloys.
In marine environments, crevice corrosion can be initiated and propagated in
presence of biofilms.
Increase in probability for both crevice and pitting corrosion.
b) Galvanic corrosion as a consequence of enhancement of cathode kinetics.
For example, both the open circuit potential and cathodic kinetics for
stainless steel were seen to be increased in the presence of biofilms.
Similarly, in a galvanic couple involving an active-passive alloys (stainless
steel), corrosion currents for the couple with a biofilm was found to be higher
than that without a film.
c) Role of discrete bio - deposits on stainless alloys need also to be understood.
Examples are biocorrosion of stainless steels where,
(i)
Pitting occurs under a bacterial colony or tubercle.

6

(ii)
Corrosion in the vicinity of the weld and
(iii)
Crevice attack
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In saline waters containing chlorides, biofilms involving manganese and iron

oxidizing bacteria can initiate several complex reactions under discrete bio-deposits.
Presence of anaerobic bacteria such as SRB and an iron-manganese oxidizer such as
Gallionella can trigger formation of metallic sulfides and chlorides under discrete
bio-deposits.
Models to illustrate initiation of pitting corrosion due to biofilm formation on metal
surfaces and welded joints are given in Fig. 30.5.
Role of various bacterial species present in sea water in biofilm formation and
subsequent metal corrosion in the presence of different reaction products such as iron
sulphides, chlorides and reduced sulfur species is illustrated in Fig. 30.6.
Fig. 30.5 Biofilm and pitting on a metal and welded joint.
Fig. 30.6 Biofilm consisting of various bacteria and reaction products and generation of differential oxygen cells.
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Generally, biofilms have been implicated in increasing corrosion rates of metals.

This is especially true for patchy, heterogeneous bio-deposits which can initiate
formation of concentration cells as indicated earlier.
There are instances, where aerobic bacteria such as Bacillus spp can decrease
biocorrosion. Ten-fold decrease in corrosion of SIS 1146 steel has been observed
with cultures of Pseudomonas. Sp. Aerobic biofilms can decrease corrosion
compared to sterile controls However, it is possible that such aerobic biofilms may
ultimately enhance corrosion due to colonization of anaerobic SRB.
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Lecture 31: Biofouling of Titanium Biofilm Studies
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Lecture 31
Biofouling of Titanium Biofilm Studies
Keywords: Biofouling, Sea Water, Titanium.
Titanium has many attractive properties such as light weight, good mechanical
strength and above all excellent corrosion resistance even in sea water. It will then
be very useful to assess biofouling tendency of titanium in sea water environments in
order to understand its utility in several nuclear power generation plants.
Biofouling refers to undesirable accumulation of a biofilm deposit on an engineered

surface. An organic film composed of microorganisms embedded in a polymeric
matrix forms the basis for the attachment of various macro-organisms, inorganic and
corrosion products. Such formation of biofilms on material surfaces poses a threat to
the successful utilization of materials in industrial environments.
Energy losses reduced heat transfer efficiency resulting from insulating
biofilm
Increased capital costs.
Enhanced maintenance costs and replacements.
Shutdowns .
Stages in marine biofouling:
a) Successive coverage of a surface by growth of primary colonizing bacteria
and other organisms. Aerobic followed by anaerobic organisms colonise in
succession.
b) A transient stage where multilayers of cells become embedded in their own
polymer matrix.
c) The final stage of development of a mature biofilm with high density of
macrobial population (diatoms, protozoa etc).
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Biofilms initially formed can be easily removed by physical or chemical means.

However, those formed for extensive periods of time are difficult to be removed due
to incorporation of inorganic and organic products formed by the metabolic activities
of attached microorganisms. Biomineralization such as oxidized manganic and iron
oxides occur within biofilms.
Two fundamentally different forms of biomineralization are recognized. Biologically
induced mineralization in which organisms generate conditions suitable for
precipitation of extracellular mineral phases. The second one called boundary
organized biomineralization involves growth of inorganic particles within organic
biomatrix.
Titanium is used as the tube material for seawater-cooled condensers in nuclear
reactors and also, in plate-type heat exchangers of the auxiliary cooling water
system. Titanium is known to be prone to microbial attachment and biofouling.
Biofouling of heat exchanger surfaces may result in the deposition of biogenic MnO2
on the surfaces severely compromising efficiency.
Investigations were carried out to study mineralization of manganese on titanium

surfaces immersed in seawater due to the activities of marine bacteria. Microbial
fouling and formation of inorganic deposits on titanium grade-2, commonly used for
condenser tubes was established.
Bacterial isolation, culturing, growth and
attachment on titanium surfaces were studied. Total viable counts of culturable

marine bacteria on titanium surface were monitored as shown in Fig. 31.1.
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Viable counts / cm
Marine organisms
Manganese oxidizers
10
10
10
10
10
12
14
16
18
20
Exposure (Months)
Fig. 31.1 Viable counts of marine bacteria and manganese oxidizers on titanium exposed to sea water.
The percentage of Manganese oxidizing bacteria (MOB) in the total bacterial counts
showed an increase from an initial value of about 3040% to almost 100% at the end
of about 20 months.
Epifluorescence studies showed increased biofilm formation on titanium surface
exposed to seawater with exposure time. Throughout the study the biofilm was
always patchy and non-uniform. Epifluorescence and confocal images indicated
highly irregular biofilms (Fig. 31.2).
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Fig. 31.2 Epifluorescence micrographs of biofilm development on titanium.
Surface coverage of the biofilm considerably increased with time.

The EPS content, which is the other major component of the biofilm besides the
microbial constituents, was determined as a function of exposure time. The Protein
and carbohydrate constituents of the EPS were analyzed. Contribution of
carbohydrate was more than that of protein in the biofilm.
Confocal scanning laser microscope image of an year old biofilm showing mature
biofilm is illustrated in Fig. 31.3.
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Fig. 31.3 confocal image of an year old biofilm on titanium.
Protein levels in the biofilm however increased rapidly after a year of exposure and
almost equaled the carbohydrate levels.
The ability of the isolated bacteria to oxidize manganese was determined both in
liquid as well as solid media.
The formation of visible brown colonies on a solid agar plate containing 50 ppm of
Mn (II) was confirmation of bacterial manganese oxidation. Solid agar plates
inoculated with MOB and manganous ions are shown in Fig. 31.4. Bacterial
manganese oxidation is evident as growth of coloured colonies. Presence of
brownish colonies on filter membranes is a confirmatory test for the manganese
oxidation ability of marine bacteria isolated from biofilms formed on titanium.
Biomineralization of manganese by the isolated bacteria was further confirmed by
studying manganese oxidation in liquid media. Various manganese oxidizing
bacteria were categorized with respect to their ability to oxidize manganous ions at
different concentration levels. The isolates exhibiting highest manganese oxidation
rates were shortlisted for further detailed investigations.
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Fig. 31.4 Agar plates containing manganous ions and manganese oxidizing bacteria (MOB) showing growth of
coloured colonies.
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Optical micrographs of some manganese (II) oxidizing bacteria isolated from the
biofilms grown on titanium surfaces are illustrated in Fig. 31.5.
Pseudomonas
Vibrio
Bacillus
Micrococcus
Bacillus
Fig. 31.5 Predominant manganese oxidizing bacteria isolated from marine biofilms on titanium.
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8
Lecture 32: Biofouling of Titanium Biomineralization and Corrosion Aspects

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Lecture 32
Biofouling of Titanium Biomineralization and Corrosion
Aspects
Keywords: Biomineralization, Biofilms, Titanium Corrosion.
Pseudomonas spp. and Bacillus spp. dominated the consortia of manganese

oxidizers, isolated from marine biofilms on titanium. 21 strains belonging to the
genus Bacillus and 16 strains of Pseudomonas were isolated.
Manganese oxidizing bacteria colonizing the titanium surfaces exposed to seawater

were characterized by periodically retrieving the coupons over a period of two years.
About 20% of the initial colonizers were capable of oxidizing manganese, and the
dominant manganese oxidizing bacteria were those belonging to Gram - negative
Pseudomonas spp. Gram positive, Bacillus spp, were also observed, though in
smaller population. Almost 40-60% of the biofilm formers observed during 1 5
months were capable of oxidizing manganese. There was a gradual shift in biofilm
colonisers from Gram - negative to Gram - positive bacteria, with Gram positive
members increasing in numbers and diversity with time.
Sulphate reducing bacteria (SRB) capable of growth under anaerobic conditions
were also isolated from the biofilms even as early as two days of exposure to
seawater. Different species of marine SRBs belonging to the genus Desulfovibrio
and Desulfotomaculum were isolated.
The frequency of occurrence of various isolated bacterial species on titanium biofilm

is shown in Fig. 32.1. A percentage frequency of 100 indicates the presence of at
least one species from this genus of bacteria in all the titanium surfaces studied
during the entire period of study. Bacterial species belonging to the genera Bacillus
and Pseudomonas showed 100% frequency. Genus Vibrio, Arthrobacter,
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Micrococcus, Flavobacterium etc. showed frequencies of 25-35%. Members of the

genera Staphylococcus, Citrobacter and E.coli, showed only a frequency less than
10%.
The dominant bacterial species in the biofilms on titanium surfaces, capable of
oxidizing manganese (II) were Pseudomonas and Bacillus spp.
Fig 32.1 Frequency of occurrence of different bacteria in the biofilm on titanium
Manganese and iron contents in the biofilm on titanium surfaces were analyzed. The
maximum manganese content on a titanium specimen of approximately 220 cm2
surface area was about 250g. This is a significant increase when compared to
<6g/L dissolved Mn (II) present in the coastal waters.
Biofilm characterization over a prolonged exposure period substantiated the fact that
titanium surfaces were susceptible to fouling. Within 24h of exposure, bacterial
attachment and subsequent growth on titanium surfaces could be seen. Titanium is
prone to biofouling due to its inert and non-toxic nature. The slime or the EPS is the
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structural framework of the biofilm. EPS content of the biofilm increased with
increasing exposure time. Titanium surfaces with the nutritionally rich organic
biofilm are an attractive substrate for attachment and growth of marine bacteria.
Predominant
marine
bacteria
like
Pseudomonas,
Vibrio,
Micrococcus,
Flavobacterium and Bacillus were present in the biofilms.
Formation of biogenic manganese oxide on the condenser tube surfaces and resulting
decrease in heat transfer have been reported in power plants. Analysis of the fouled
tubes revealed that MnO2 was formed on the inner surface due to the activities of
Leptothrix spp. and Sphaerotilus spp. present in the condenser cooling water.
Similar biofouling tests were also performed on titanium heat exchanger plates.
Reddish brown colonies of manganese oxidizing bacteria could be seen deposited on
titanium plates.
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Scanning
electron
micrographs
depicting
biofilms
of
Sulfate
Reducing
Bacteria(SRB) of the genus Desulfovibrio and Desulfotomaculum on titanium

surfaces are illustrated in Fig. 32.2.
Fig 32.2 Scanning electron micrographs depicting SRB biofilms on titanium surfaces.
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Open circuit potentials (SCE) with titanium in contact with MnO 2 and in the
presence of biofilms of MOB and SRB measured in sea water are shown in Fig. 32.3.
Ennoblement of potentials in the presence of MnO2 and MOB biofilms could be
seen. In the presence of SRB biofilm, titanium potentials deviate in the negative
(more reducing) direction.
Fig 32.3 Variation of open circuit potentials of MnO 2 - and biofilm coated titanium in sea water.
The following observations with respect to the electrochemical (corrosion) behavior

of titanium in sea water are noteworthy:
An ennoblement of open circuit potential of titanium occurs in a culture of

manganese oxidizing bacteria in artificial seawater nutrient broth, where as
titanium surface shows active potential in an SRB culture.
Cyclic anodic polarization curves in MOB culture shows good passivity and
no breakdown up to a potential of 2V
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Cyclic anodic polarization curves in SRB culture shows active dissolution

prior to the passive region showing that titanium is almost film free under
open circuit conditions in SRB culture.
A very low value of charge transfer resistance in electrochemical impedance
studies of titanium at open circuit potential in SRB culture confirms that
passive film is not stable under this condition
The implications of the above results are that while manganese oxidizing
bacteria are harmless to titanium from a corrosion point of view, sulphate
reducing bacteria and associated reducing environment makes titanium prone
to local dissolution
REFERENCES
1. Judy Gopal, P. Muraleedharan, H. Sarvamangala, R. P. George, R. K. Dayal,
B.V.R. Tata, H.S. Khatak and K. A. Natarajan, 2008, Biomineralisation of
manganese on titanium surfaces exposed to seawater, Biofouling, 24 (2008)
pp 275 282.
2. H. Saravamangala, J. Gopal, P. Muraleedharan, R. P. George, R. K. Dayal
and K. A. Natarajan, 2008, Biomineralization of manganese by Bacillus spp
isolated from a marine biofilm. Minerals and Metallurgical Processing, 25,
pp 149 155.
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Lecture 33: MIC Failure Analysis
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Lecture 33
MIC Failure Analysis
Keywords: MIC Failures, Monitoring Programs, Biological Tools
It is essential to assess susceptibility of an engineering system for MIC. Generally,

any system exposed to water and nutrients can induce microbial growth. Microbial
corrosion failures often manifest as
Loss of efficiency in heat exchangers.
Pressure drop and / or impaired flow through piping.
Certain regions in piping such as spots where collection of water occur, dead-ends as
well as tank bottoms where water-hydrocarbon interface exists are more susceptible
to microbial fouling. MIC is prevalent in refineries, cooling water installations, oilfield water handling, sprinklers, oil, water and gas pipelines and pulp and paper
mills. Power generation installations (both thermal and nuclear) in coastal belts are
prone to different types of MIC.
Analyses of MIC failures need to take into consideration the environment to which
metals and alloys are exposed. For example, in soils, corrosion rates can be
correlated with Eh, pH, moisture content, type of soil and resistivity. Aerobic and
anaerobic soil environments attract growth of aerobic and anaerobic microorganisms.
Factors correlating with SRB-induced corrosion in soils can be identified for buried
steel pipes.
Bacterial density
103 108 cells / g
Total organic carbon in ground water
upto 1.2%
Soil resistivity
500 30,000 ohm.cm
Eh range
-300 to -390 mV
Sulfate content
upto 200 mg / g
Based on corrosion severity and its localised nature, potential MIC sites can be
identified.
Metallurgical damage, corrosion products, environmental and
microbiological factors need be analysed to confirm MIC. Morphology,

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directionalism and dimensions and distributions of pits need be metallurgically

assessed. Biological analyses enumerate viable cells of different aerobic, anaerobic
and acid producing bacteria. Chemical estimation of corrosion products also need to
be undertaken at the corroded and neighbouring surfaces. For examples, corroded
steel surfaces would yield yellowish brown or black ferric oxides and other iron
oxides such as goethite, magnetite etc. in the presence of aerobic organisms.
Corroded steel in the presence of SRB would reveal presence of blackish, amorphous
and finely divided iron sulfides. Standard methods are available for identification of
MIC corrosion products in different environmental and industrial conditions. (eg: oil
and gas, cooling water, buried pipelines etc).
For example, in cooling water systems, factors such as

Microorganisms byproducts
Microbially unique morphology
Corrosion products, and
Environmental conditions need be looked into.
With reference to steels, reported MIC trends based on failure analyses are:
Often associated with untreated, stagnant water in pipes low or intermittent
flow most damaging.
Weld damage in stainless steel pipes.
Pitting more prevalent in the bottom third of pipe.
Low pH / High chlorides enhance corrosion.
Design of monitoring programs in industrial systems is documented. Probes,

sampling coupons and other corrosion monitoring gadgets are available.
For
example, biofouling can be assessed by monitoring pressure drops across pipelines.

Heat exchanger efficiency can be assessed before and after fouling. Electrochemical
measurements to monitor biofilms development, bioporducts and corrosion are
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available.
Bioactivity
can
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be
detected
through
electrochemical
probes.
Measurements of corrosion potential, redox potential, linear polarization resistance,

impedance and resistance through electrochemical instrumentation have become
possible.
As indicated above, detection, diagnosis and monitoring are critical to minimize MIC
failures. Only through proper diagnosis, a corrective action plan for corrosion
mitigation can be undertaken. Assessment should take the background history into
consideration. Prior events, corrosion monitoring records, repairs undertaken, water
chemistry and treatment etc need be evaluated. Data with particular emphasis on
materials of construction, water and deposit analysis, microbial and metallurgical
analysis and treatment are essential to assess MIC failures.
Similarly, failure
analysis constitutes of several principal stages such as:

Collection of background information.
Visual, non-destructive, destructive and chemical examination.
Mechanical tests and analysis of failure causes.
Various instruments and kits for the above are readily available. For microbiological
analyses, standard procedures are available. Biological assays can be done on liquid
and solid samples in order to identify involved microbes, their metabolic activities
and concentrations of enzymes and other byproducts.
Modern biological tools and techniques for characterizing microbial populations and
their metabolic activities can be used.
For example, separation of DNA/RNA, PCR (Polymerase Chain Reaction) and

surface analytical tools such as mass spectrometry, AFM, SEM, TEM, etc.
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Some common analytical methods for biological evaluation are given below:
Cell numbers
Counting chamber
Specific organisms
Microscopy
Viable cell count
Serial dilution
Aerobe, anaerobe, others
MPN
Identity
Biochemical tests
DNA/RNA Probes
Reverse sample genome probing.
Biomass
Proteins, polysaccharides, nucleic acids
Metabolism
ATP
Enzyme activity
Hydrogenase assay, Radio-active labelling.
Sulfate reduction
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Lecture 34: MIC Prevention and Control
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Lecture 34
MIC Prevention and Control
Keywords: Control of MIC, Design Aspects, Biocides.
Prevention of MIC (Microbially- influenced corrosion) would be cheaper than its

control after manifestation.
Basic approach should be to keep microbial growth under control.
How to maintain sterile environment?
There are several factors to be considered.
Appropriate design:
Use correct materials
Avoid improper design
Environmental control
For example, for designing water-containing systems, many parameters such as pH,
source of water, salinity, hardness, oxygen levels, nature of impurities, rates of flow
and temperature need be considered. For buried pipe lines, soil corrosivity need be
assessed in terms of moisture content, pH, oxygen, availability of cations and anions,
presence or absence of stray currents and resistivity.
Pipelines are invariably coated for corrosion resistance and also to reduce cathodic
protection current requirements. Barrier coatings on pipelines can at times disbond
during service. In practice, cathodic protection is always used along with protective
coatings.
Cathodic protection can be applied to external surfaces of buried
underground structures or installations submerged in water and also at times to inside

of tanks, heat exchangers and clarifiers. Interrelationship between cathodic
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protection and MIC in marine and sub-soil environments needs to be understood.

Effect of applied current (or maintained potential) in attachment and growth behavior
of microorganisms, such as SRB needs to be ascertained.
In the presence of anaerobic bacteria, such as SRB, applied potentials for protection
must be more negative than that usually considered (in the absence of
microorganisms). Besides, effect of biofilms and bio-products on applied potential
or current needs to be assessed.
System design and operation are key factors in prevention and control of MIC.
Avoidance of water seepage, collection and stagnation need be avoided. Tanks and
fuel-storage vessels should be designed to drain of water at the bottom. For larger
engines, such as seagoing vessels, breaking emulsions and separating water from oils
can be done through recirculation. Prevention and timely removal of scales, debris
and deposits will be beneficial. Pipeline cleaning devices can be effectively used
frequently to remove deposits and tubercles.
Chemical treatment using biocides is also recommended to deter bacterial attachment
and growth. Chemical agents are designed as bio-stats and biocides and could also
scavenge oxygen, inhibit corrosion, control pH and deposit formation. Biocides are
generally added to chemical treatment packages to control biofouling and subsequent
corrosion. For different industrial environments, chosen biocides need be used, such
as:
Chlorine / ozone
Reactive aldehydes
Quaternary ammonium salts etc.
Screening tests and site-trials are essential in the choice of the most appropriate
biocide.
Biocides are classified into two families as oxidizing and non-oxidizing.
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Chlorine and bromine are oxidizers.

Cl2 + H2O = HOCl + HCl
HOCl = H+ + ClOStrict regulations exist concerning chlorine gas and its residuals in chlorinated water.
Chlorination may be continuously performed, preferably, in the range of 0.1 0.2
mg/L or intermittently as shock treatment in the range of 0.5 1.0 mg/L. Other
oxygenating biocides for bacterial growth control include:
Hypochlorites
Chlorine dioxide
Ozone
Chlorinated or brominated donor molecules
Biocides that inhibit bacterial metabolism include:
Methylene bisthiocyanate
Gluteraldehydes
Amines
Quaternary ammonium salts
All the above can be effectively used in cooling water treatment systems.
Thiocyanate compounds can be used to control algae, fungi and bacteria such as
SRB.
Today many types of newer instrumentation and analytical tools are available for
assessment and evaluation of MIC. Electrochemical, microbiological, optical and
other chemical methods could be effectively used not only in research laboratories,
but also in industrial situations.
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The following developments are noteworthy:

Chemical analysis within biofilms using micro-sensors to evaluate the
chemistry at the surface and within the biofilm.
Study of structure of biofilm using fiber-optic microprobe.
Electric field mapping using scanning vibrating microprobe.
Advanced microbial techniques such as DNA probes to investigate biofouling
and MIC-Molecular techniques involving bacterial DNA and RNA.
Environmental scanning electron microscope, confocal laser scanning
microscopy and Atomic force microscopy to observe biofilm development in
real time.
Microelectrodes for in-situ oxygen measurements.
Development of corrosion sensors and electrochemical measurement technology has
attracted particular attention. An electrochemical sensor for monitoring biofilms has
been recently developed, which provides an immediate indication of the biological
activity and can be used to optimise and control biocide treatment.
MIC affects the operation and maintenance costs of pipelines. About 40% of all
internal pipeline corrosion in the petroleum industry can be attributed to MIC. In oil
pipelines, hydrocarbon and water stratify at the bottom and cannot easily be drained
off.
Both aerobic and anaerobic bacteria besides various types of fungi may
participate in the corrosion process.
Presence of iron-and manganese-oxidizing
bacteria, acid producing bacteria and methanogens may also be involved in oil and
gas-pipelines. There are case studies of bacteria and fungi isolation from gas, oil and
water pipelines. Sessile organisms are the dominant forms in the biofilms.
Planktonic cells are not that numerous.
Many such organisms isolated from
pipelines may not grow in culture and thus there is a chance one may underestimate
the true population of a system.
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Bacterial enumeration and identification studies in diesel and naphtha pipelines

showed the occurrence of several bacterial species such as:
Bacillus subtilis
Bacillus cereus
Pseudomonas aeruginosa
Bacillus pumilus
Bacillus megaterium
Characterization of microbial populations in gas pipelines indicated the presence of
colonies consisting of:
Desulfovibrio vulgaris
Citrobacter freundii
Clostridium sporogenes
It becomes clear that the microorganisms inhabiting pipeline systems significantly
defer from place to place and system to system.
Corrosion management strategies may thus change from system to system. Various
management strategies need be adopted for a dedicated pipeline corrosion abatement
programme, which should include.
Corrosion modeling
Corrosion risk assessment.
Specific identification of corrosion types.
Review of performance indicators for abatement processes.
Biofouling is a severe problem in power plants.
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Microbial growth and its effects in fuel systems are listed in Table 30.1.
By proper corrosion management, about 50% of the damages of condenser tubes

could be prevented.
Biofouling and MIC are serious problems in sea-going vessels. Biofouling is a

serious problem in ships hull, propeller and rudder, and bottom parts. By
appropriate surface coating (painting) technology which incorporates pertinent
biocides, fouling of marine going vessels can be minimized.
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Lecture 34: Microorganisms In Biofouling And Biocorrosion
NPTEL Web Course
Lecture 34
Microorganisms In Biofouling And Biocorrosion
Keywords: Biocorrosion, Biofouling, Microorganisms
So for we have seen the beneficial aspects of microorganisms with relevance to biogenesis of
minerals, bioleaching and biobeneficiation.
Many types of microorganisms are also
responsible for metal degradation and corrosion. Role of microorganisms in biofouling

and metallic corrosion is discussed in lectures 34-37, with reference to biofilms,
biocorrosion, role of aerobic and anaerobic organisms, biomaterials and corrosion of
human implants [227-244].
Microbially-influenced corrosion (MIC) takes place in environments such as soil, fresh water
and sea water and is estimated to be responsible for more than 30 percent of all corrosion
damage. Microorganisms causing MIC are many such as sulfur-sulfide oxidizing, ironmanganese oxidizing, sulfate-reducing, acid producing, and ammonia and acetate producing
bacteria and fungi. Microbial growth under natural environmental conditions influences
electrochemical reactions directly or indirectly. Microbe-metal interactions lead to initial
adhesion and biofilm formation. [227-236]
The role of microorganisms in the deterioration and failure of materials can be categorized into
Biofouling, Biodeterioration and Microbiologically-influenced corrosion (MIC). Biofouling
refers to attachment of micro- and macro-organisms onto material surfaces in marine, fresh water
and soil environments leading to formation of fouled layers of biofilms. Deterioration of
nonmetallic materials like cement, wood, plastics and rubber due to microbial action is termed
biodeterioration. Corrosion of metals and alloys influenced by the activities of microorganisms is
defined as microbially-influenced corrosion (MIC).
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Microorganisms are omnipresent and grow at very rapid rates in soil, water and air. They exhibit
extreme tolerance to varying environmental conditions such as acidic and alkaline pH, low and
higher temperatures as well as metal toxicity.
The industrial significance and relevance of MIC can be seen from Table 34.1. The severity of
microbial corrosion processes is evident from the fact that many of the commercially used metals
and alloys such as stainless steels, nickel and aluminium-based alloys and materials such as
concrete, asphalt and polymers are readily degraded by microorganisms. Protective coatings,
inhibitors, oils and emulsions are also subject to microbial degradation.
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Table 34.1:Relevance of MIC in industrial environments
Thermal and nuclear power plants
Coolant tubes, sub-sea pipe lines, stainless

steel and carbon steel, copper and aluminiumalloys
Mining and metallurgical operations
Underground equipment and engineering

materials.
Chemical
Condensers, heat exchangers, pipings and

storage vessels.
Water treatment and mechanical
Heat exchangers, Breakdown of oils,
engineering
emulsions and lubricants
Piping (oil, gas and water)
Steels
Construction
Concrete structures in marine, fresh water and

sub-soil conditions, bridges, buildings
Oil exploration and petrochemicals
Aluminium alloys and steels
Aviation sector
Aluminium fuel tanks
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MIC in power plants can occur in the following operational metals and alloys
Heat exchanger tubing -
Aluminium brass, Copper-Nickel, alloys
Water storage tank -
stainless steels
Water pipes
stainless steel welds
Cooling towers
Pumps
Galvanized steels
Stainless steels
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MIC causing microorganisms

Microorganisms that are known to cause corrosion can be generally classified as follows:
Bacteria
Iron Oxidising Bacteria (IOB) and metal

depositing bacteria
Sulphate Reducing Bacteria (SRB)
(Desulfovibrio)
Sulphur Oxidising and acid producing
bacteria. (Acidithiobacillus)
Iron
oxidizing
bacteria.
and
metal
(Gallionella,
depositing
Crenothrix,
Leptothrix)
Metal reducing bacteria
(Pseudomonas, Shewanella)
Fungi
Aspergillus fumigatus
Cladosporium resinae
Paecilomyces varioti
Aspergillus niger
Penicillium cyclospium
Algae
Blue green algae
Microbial
Mutualism among different groups of
consortia
microorganisms
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The sulphur cycle in nature is relevant to MIC. Sulphur and sulfide oxidising and sulphate
reducing bacteria (SRB) are involved in a number of biogenic redox reactions leading to
products such as H2S, metal sulphides and sulfoxy compounds.
Microbially - mediated
processes result in corrosion in soils and aqueous environments. For example, sulphate reducing
bacteria such as Desulfovibrio reduce sulphate to sulphide and hydrogen sulphide, under
reducing conditions.
SO=4 + 4H2 = S= + 4H2O
2H+ + S- - = H2S
Both sulphur (sulphide) oxidizing and sulphate reducing bacteria (SRB) are involved in the
biological sulphur cycle in nature.
Sulphur and ferrous iron-oxidising bacteria such as Acidithiobacillus thiooxidans and
Acidithiobacillus ferrooxidans are aerobic acidophiles promoting oxidation of sulfur, sulfides as
well as ferrous ions.
2H2S + 2O2 = H2S2O3 + H2O

5Na2S2O3 + 8O2 + H2O = 5Na2SO4 + H2SO4 + 4S
4S + 6O2 + 4H2O = 4H2SO4
Fe++ = Fe+++ + e
Morphological features of some organisms relevant to MIC are given fig. 34.1:
All these bacteria are implicated in microbial corrosion processes and their growth characteristics
and metabolic reactions are important in understanding corrosion mechanisims.
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Bacillus
Acidithiobacillus Sp
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Sulphate reducing bacteria (SRB}
Acidithiobacillus thiooxidans
Aspergillus fungus
Desulfovibrio sp.
Fig. 34.1: Morphological features of bacteria and fungi relevant to microbial corrosion
Principal slime forming bacteria like Bacillus subtilis, Bacillus cereus, Flavobacterium,
Aerobacter and Pseudomonas are present in soils.
Pseudomonas proliferates in systems
containing hydrocarbon sources such as oils and emulsions using hydrocarbons as energy source.
Algae include single cell to multicellular species of diverse forms and shapes. They contain
coloured pigments, such as the chlorophyll, and grow on moist surfaces of cooling towers,
screens and distribution systems. Some common algae include blue-green algae, the green algae
and diatoms. They produce corrosive organic acids, and oxygen promoting metallic corrosion.
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Fungi are akin to algae but do not contain chlorophyll. Mould fungi are filamentous; but most of
yeast fungi are unicellular. Fungi implicated in MIC include Aspergillus niger, Aspergillus
fumigatus, Penicilium cyclospium and Cladosporium resinae. Fungal generation of various
organic acids such as oxalic acid, citric acid and gluconic acid create a corrosive environment.
General mechanisms
General electrochemical reaction mechanisms hold good in MIC also.
M = M++ + 2e (anodic)
O2 +4H+ + 4e = 2H2O (acid, aerated)
O2 + 2H2O + 4e = 4OH- (neutral, aerated)
2H+ + 2e = H2 (acid in the absence of oxygen)
Direct and indirect mechanisms are involved when microorganisms participate in a corrosion
process. Microbes directly interlink an electrode reaction through their metabolism in direct
mechanism while indirect mechanisms involves indirect microbial role of generation of corrosive
environments, such as differential aeration cells, acidic reaction products and other metal
chelating solvents.
.
General mechanisms can be classified as follows:
Changes in dissolved oxygen concentrations owing to microbial growth and formation of

concentration cells.
Biodegradation of inhibitors and additives in lubricants and emulsions.
Microbial hydrogen consumption.
Biological breakdown of paint coatings, plastics and, protective films.
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Microorganisms can generate both organic and inorganic acids.
Oxidation of reduced valence sulphur compounds by Acidithiobacillus to produce sulfuric

acid.
Oxidation of sulfide minerals by Acidithiobacillus ferrooxidans to generate ferric sulfate
containing sulfuric acid.
Heterotrophic bacteria and fungi such as Aspergillus generate oxalic, citric and acetic acids.
Other corrosion mechanisms include.
Corrosion by cathodic depolarization attributable to hydrogenase positive Sulfate Reducing

Bacteria (SRB).
Corrosion by differential aeration cells due to biofilms formed by iron oxidising and slime
forming bacteria.
Corrosive products such as organic sulphides, amines, ammonia and
phosphorous
compounds.
Organic corrosion inhibitors such as aminium compounds are used as nutrients by bacteria and
degraded. Bacteria such as Nitrosomonas and Nitrobacter oxidise amines to nitrite and nitrate.
Ferric oxide coatings are degraded by Pseudomonas. Iron sulphide films on steels are degraded
by Sulphate Reducing Bacteria. Protective passive oxide layers on aluminium and its alloys are
destroyed by the fungus, C. resinae.
Bacterial attachment and biofilm formation on metals and alloys are initial events in metallic
corrosion. Microbial biofilms consist of micro and macro- organisms together with their
metabolic and chemical reaction products. Initial stages in biofilm formation may involve only
bacterial attachment. Macroorganisms subsequently attach and grow.
Scanning electron micrographs showing SRB attachment and biofilm formation on titanium
surfaces are shown fig. 34.2.
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Fig. 34.2: Scanning electron micrographs showing SRB attachment and biofilm formation on titanium
surfaces
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Lecture 35: Implant Materials and Corrosivity of Human Body
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Lecture 35
Implant Materials And Corrosivity Of Human Body
Keywords: Human Body, Implants, Biocompatibility.
Recent innovations in the areas of biomedical engineering and biomaterials have

resulted in the development of different implants for implantation in the human
body.
Biomaterials engineering deals with scientific study of the structure and properties of
biomaterials in relation to their interaction with biological systems. Biomaterials
have to interface with human biological systems so as to evaluate, augment or
replace any organ, tissue or function of the body. Use of artificial metallic materials
to repair fractured and diseased tissues and organs has been practiced since centuries.
However, several developments have taken place in the use of advanced technology
for manufacture of corrosion resistant metallic and nonmetallic materials for
human body implants since the last two decades.
In lectures 35 and 36, developments in human implants with respect to corrosion
resistance are illustrated. A cross section of a human body with a few implant sites
such as dental cavity, hip joints and knee joints is shown in Fig. 35.1
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Fig. 35.1 Some human body implants
Human body environment presents a corrosive medium to various implant materials

- a highly oxygenated saline electrolyte at a pH of around 7.4 and temperature of
370C, containing water, dissolved oxygen, sodium, chloride, bicarbonate, calcium,
potassium, magnesium, phosphate, amino acids, proteins, plasma, lymph, saliva and
various organic compounds.
Various biological molecules influence the
electrochemical behavior of implant metals and alloys.
Anodic and cathodic
reactions are influenced by adsorption and interaction of such organic polymers. For
example, protein adsorption on implant materials can interfere with oxygen and
hydrogen redox reactions. Besides, bacteria present in the human body can also
influence the corrosion behavior of implant materials.
Infections can create
imbalance in the electrochemical equilibrium. Shifts in the physiological pH towards

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acidic and alkaline directions can occur. Release of metal ions from the implant can
change interfacial equilibrium and influence electrochemical kinetics.
Tolerable
corrosion rate for metallic implants is expected to be about 0.01 mils/year. Both
thermodynamic and kinetic factors influence the corrosion behavior of many implant
materials.
From a corrosion angle, chloride and oxygen contents as well as pH of body fluids
are very important.
Biological macromolecules interfere with anodic and cathodic reactions at the
implant biotissue interface. Proteins can bind to metal ions and transport them
across body upsetting double layer equilibrium, inducing enhanced metal
solubilisation. Stability regions for body fluids such as saliva, bile, urine, gastric
juice and intra - and intercellular fluids in terms of redox potentials and pH can be
represented in Eh pH diagrams.
In the human body, saliva, interstitial and
intracellular fluids occupy regions closer to oxygen line ( upper stability limit for
water) since they are oxygen saturated. On the other hand, stability limits for urine,
bile and gastric fluids are closer to the hydrogen line (reducing environment).
In vivo corrosion of implants need be analyzed in relation to effect on life span of the
device and levels of metal ion dissolution and transport. Since common methods of
corrosion control such as inhibition and changing environmental conditions will not
be suitable to human implants, the best solution would only be proper material
selection and design.
Corrosion forms such as galvanic corrosion, pitting, intergranular attack, uniform
corrosion, stress cracking, crevice and fatigue corrosion are prevalent in different
locations of the human body depending on the structural configuration and types of
metallic implants. Both in vivo and in vitro tests are carried out to assess corrosion
resistance of biomedical materials. In vivo tests are performed using animal
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candidates, while in vitro measurements are done using simulated body fluids. There
are ASTM standards for different tests and conditions, such as corrosion
performance of biomaterials, galvanic corrosion in electrolytes, crevice corrosion of
metallic surgical implant materials and for cyclic potentiodynamic polarization.
Effects of fretting and rupture on surface oxide films need also to be evaluated.
Surface oxide films formed on metals and alloys minimize release of metallic ions.
Tissue compatibility and regeneration of surface oxides is also important.
Regeneration periods of passive alloys differ depending on alloy composition
(stainless steels, titanium alloys, Co-Cr alloys etc.). Regeneration time is observed to
be longer for stainless steels, while shorter for Ti-6 Al-4V, an alloy widely used for
orthopedic implants. Surface coatings on implant materials reduce the corrosion
rate. Metal dissolution from implants contaminates human body systems and results
in undesirable consequences.
Important properties of (biomaterials) implants

Mechanical properties Enhanced risk of crack propagation and fatigue fracture.
Biocompatibility
A biocompatible (bio) material should not disrupt normal body function to any
significant level. Many factors such as size of implant, material properties and
surface-chemical characteristics influence biocompatibility.
Long-term stability of metal implants critical for patient health and survival.
- Stents
- Arthroplasty
- Fracture fixation
- Pacemakers
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Ideal implant materials should be

Inert
Nontoxic to body
Corrosion resistant
Inexpensive
Strong
Fatigue resistant
However, most synthetic materials once implanted in the body can induce foreignbody reaction. Presence of metal ions triggers enhanced foreign body response.
-
Osteolysis, implant loosening.
Blood clotting (thrombosis).
Corrosion and wear of implants produce changes in blood chemistry, such as

elevation in metal concentrations.
In case of stainless steel and chromium
containing alloy implants in Joints, dissolved chromium and nickel levels in serum
could occur. Metal dissolution can damage cells.
Approximate composition of some orthopedic implants is given in Table 35.1
Table. 35.1 Orthopaedic metallic implants
Alloy
Fe
Cr
Ni
Co
Ti
Al
Bal
5-6
3 4.5
Ti 6Al 4V
0.3
0.1
Co-cast
0.75
0.35
27-30 1.0
Bal
..
Co-forged
0.75
0.35
27-30 1.0
Bal
..
Co-wrought
3.0
0.05-0.15
19-21 9-11
Bal
..
Ti
0.5
0.1
Bal
..
316L
Bal
0.03
17-19 13-16
Synthetic biomaterials
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Metals Co-Cr alloys, Stainless steels, Gold, Titanium alloys, Vitallium,

Nitinol (shape memory alloys)
Uses orthopedics, fracture fixation, dental and facial reconstruction, stents.
Ceramics Alumina, Zirconia, Calcium phosphate, Pyrolytic carbon.
Uses orthopedics, heart valves, dental reconstruction.
Coatings Bioglasses, Hydroxyapatite, Diamond like Carbon, Polymers.
Uses orthopedics, contact lenses, catheters, in-growth.
Corrosion and erosion failures of implants can be categorized into:
Mechanical (overload, fatigue, wear, abrasive motion)
Electrochemical (different types of corrosion).
Biological (inflammation and infection, calcification, biodegradation).
There are also combined factors influencing corrosion, such as stress corrosion
failure, fretting and fatigue.
Biodegradation and bacterial interaction processes can lead to disastrous
consequences such as bone loss, structural deformity, and osteolysis.
Metal
accumulation in body fluids (nickel, cobalt and chromium) impart toxicity (metal
sensitization). Retrieval of wear particle remnants from the body fluids can help
with failure analysis and development of newer implant materials.
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The following are the most relevant corrosion types for different
implant materials:
Uniform corrosion: For a successful implant material, long term uniform corrosion
rate is expected to be less than one micrometer per year.
Galvanic corrosion: Dissimilar metal corrosion is common in orthopedic, dental and
other biomedical uses.
Examples:
Hip prosthesis with ball made of 316 stainless steel and a socket of Ti 6 Al
4V alloy.
Co Cr Mo femoral head in combination with Ti 6Al-4V femoral stem.
Gold crown in contact with amalgam in oral cavity.
Pitting and crevice corrosion:

Pitting is a common form of corrosion in 304 stainless steel implants. Addition of
molybdenum reduces pitting tendency.
Other treatments for enhancing pitting
resistance include nitrogen alloying and controlled cold working.
Titanium is
resistant to pitting.
Crevice corrosion
a) Micromotion between components results in fretting corrosion-lead to
initiation of crevice attack.
b) Passive oxide film for corrosion protection.
c) Repetitive motion-continuous breakdown and repassivation.
d) Crevice corrosion can be caused by localized oxygen depletion and metal ion
concentration gradients.
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Crevice corrosion is a problem in implants made of:

Mo containing stainless steels.
316 Stainless steels
Co Cr Mo alloys
Stress corrosion cracking is reported in cases of orthopedic implants made of
stainless steel.
Corrosion fatigue: Very uncommon if recommended specifications and processes
are adhered to.
Fretting corrosion is reported in orthopedic implants. Corrosion occurs at joints due
to motion. Prosthesis implant materials such as stainless steels, Co-alloys and Ti
alloys are amenable to fretting corrosion. Oxidized corrosion products aggravate this
type of corrosion.
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Lecture 35: Biofilms And General Mechanisms In Biocorrosion
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Lecture 35
Biofilms And General Mechanisms In Biocorrosion
Keywords: Biofilms, Structural Materials, Sulfate Reducing Bacteria
Biofilms on metals and alloys can cause several engineering problems. [227-235]
Heat transfer reduction leading to energy loss.
Reduction in mass and fluid transfer (water, oil, gas pipelines).
Structural breakdowns.
Enhanced fuel and operating costs.
Several mechanisms and models have been proposed to understand biofilm formation.
Growth of aerobic bacteria utilize oxygen at the metal-solution interface generating an anaerobic
environment.
Anaerobic bacteria such as SRB can subsequently grow in the anaerobic
environment. Bacterial synergy lead to the formation and growth of a heterogeneous biofilm
consisting of a mixture of aerobes and anaerobes.
MIC of some structural metals and alloys.

Copper and copper alloys: They are commonly used in heat exchangers, pumps, and
condensers. Copper-nickel alloys, brasses, aluminium bronzes and admiralty brasses are used in
sea water applications. SRBs in sea water environments can cause localised corrosion of these
alloys. Extra-cellular polymers and biofilms created by microorganisms can lead to corrosion of
copper-base alloys through differential aeration and selective dissolution. Pitting, dezincification
and ammonia cracking of brasses and bronzes can be caused by organisms. Sulphate-reducing
bacteria can generate tubercles (sulphide-rich scales) on copper alloys.
In spite of copper
toxicity, copper and copper alloys are not free from biofouling.
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Steels. Tubercle formation with pitting beneath the scales can occur in steel pipes and tubes, due
to microbial action. Aerobic bacteria such as Gallionella, Leptothrix and Acidithiobacillus can
oxidize iron, leading to deposition of ferric oxyhydroxides.
The above organisms can also cause corrosion through formation of slimes, oxidation of iron and
sulphides and generation of acidic metabolites. Iron oxidising bacteria oxidize ferrous ions to
less soluble ferric oxides, leading to the formation of insoluble tubercles. Steel water pipes are
amenable to such attack. Massive tubercle formation inside steel pipes, block fluid flow and can
cause extensive pitting, and crevices.
Stainless steels. Stainless steels find numerous applications in marine and other industrial
environments. Iron oxidising and depositing bacteria induce pitting corrosion of stainless steels
especially adjacent to weldments. SRB can bring about corrosion of stainless steels, duplex
steels and molybdenum steels. Slimes formed by bacteria can initiate pits in stainless steels in
marine environments. Destruction of passive films on stainless steels can be caused by reducing
environments created by anaerobic bacteria.
Nickel-based alloys. Monels and inconels are susceptible to microbial corrosion. Nickel-based
alloys used in power plants corrode due to microbial action in marine environments.
Aluminium and its alloys. Protective passive oxide films present on aluminium and its alloys
could be broken and destroyed by microbial action. Aluminium alloys used in aircraft and fuel
storage tanks are susceptible MIC in the presence of hydrocarbons. Production of organic and
inorganic acids by bacteria and fungi lead to pitting and intergranular corrosion of aluminium
and alloys. Aluminium-magnesium alloys used in marine applications are susceptible to pitting,
intergranular corrosion, exfoliation and stress corrosion in the presence of aerobic and anaerobic
microorganisms.
Aircraft fuel tanks and marine structures made of aluminium and its alloys are corroded by
microorganisms such as Pseudomonas, Leptothrix, Sulphate Reducing Bacteria and fungi. The
fungus, Cladosporium resinae grow and multiply using kerosene or paraffins as carbon sources.
MIC failure of aircraft fuel tanks is well established.
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The following microorganisms had been isolated from an aircraft tank sludge.
Bacillus,
Aerobacter aerogenes.
Pseudomonas aeruginosa.
Cladosporium
Aspergillus,
Clostridium,
Desulfovibrio,
Fusarium,
Penicillium.
Titanium.
Titanium is amenable to biofouling.
SRBs and acid-producing bacteria create
conditions that destabilize passive films. Titanium and its alloys used in marine environments
are susceptible to biofouling and biofilm formation in the presence of manganese and iron
oxidising bacteria and sulfate reducing halophiles. Surface passive films on titanium could be
disrupted in the presence of anaerobes, leading to potential ennoblement and susceptibility to
pitting.
MIC due to Sulphate Reducing Bacteria (SRB)

Microorganisms relevant to MIC possess the following general characteristics:
Extremophiles (tolerant to wide range of metal concentrations, acidity, temperature,
pressure, oxygen gradients)
Fast reproduction and growth.
Adhesion to metal substrates and colonisation.
Ubiquitous and omnipotent
Small size (few micrometers)
Sessile or motile
Existence of consortia and synergy
Production of organic and inorganic acids, alkalis, chelating agents and extracellular
polymeric substances such as proteins and polysaccharides.
Can oxidize or reduce metals and ions.
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Microorganisms relevant to MIC can be classified with respect to their functions.

Iron-oxidizing /reducing bacteria.
Sulfur-sulfide oxidizing bacteria.
Bacteria secreting exopolymers / slime and organic acids.
Manganese oxidizers / reducers
Sulfate-reducing bacteria (SRB).
Sulfate-reducing bacteria (SRB) bring about dissimilatory sulphate reduction to sulfides. Oil,
gas and marine-based vessels and installations are seriously affected by SRB activities due to
H2S generation. Common SRB such as Desulfovibrio, Desulfobacter and Desulfotomaculum,
are capable of growing in soil, fresh water and sea-water environments and also in stagnant
marshy areas.
They oxidize organic substances to organic acids or CO2, by reduction of sulfate to sulfide
through anaerobic respiration.
Black deposits of precipitated sulfides and H2S smell are indicative of SRB growth.
Characteristics of some MIC-causing heterotrophs and Sulfate reducing bacteria relevant to MIC
are given in Tables 35.1 and 35.2.
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Table 35.1: Some MIC causing heterotrophs
pH
Temp 0C
Oxygen
Action
Gallionella
7-10
20-40
Aerobic
Oxidizes
ferrous and
manganoustubercle
formation
Iron and
steel
Sphaerotilus.
7-10
20-40
Aerobic
Oxidizes
ferrous and
manganous
- tubercle
formation
Iron and
steel
S.natans
..
..
..
Pseudomonas.
4-9
20-40
Aerobic
P.aeruginosa
4-3
20-40
Aerobic
Cladosparium resinae
(fungi)
3-7
10-45
Aerobic
Organism
Affected
metals
Aluminium
alloys
Some
Iron and
strains can
steel
reduce Fe+++
to Fe++
Aluminium
alloys
Produces
organic
acids.
Aluminium
alloys
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Table 35.2: Characteristics of some sulfate reducing bacteria
Desulfovibrio
Single flagellum. Do not form spores. Hydrogenase present, pH 48. 10-400C, anaerobic.
Dt .nigrificans
Hydrogenase activity variable. Growth even on pyruvate,

sulphate-free media, 10-400C, pH 6-8..
Desulfotomaculum
Peritrichous flagella, anaerobic, pH 6-8
Dt. Orientis
Fat curved rods, 5 m x 1.5 m, Hydrogenase absent, pH 6-8,

10-400C.
Dv. desulfuricans
Dv. vulgaris
Dv. Salexigens
Curved rods (vibrios); sometimes spirilloid,

Typical size 3-5 m pH 6-8, 10-400C,
Anaerobic
The manner in which SRB brings about microbial corrosion need be understood with respect to:
H2S and hydrosulfides
Oxygen concentration cells
Formation of insoluble metal sulfides (FeS)
Cathodic depolarization (Hydrogen reduction).
Metal adhesion of SRB results in generation of corrosion cells. Many hydrocarbons encountered
in oil and gas exploration harbour SRB through nutrient supply. Cathodic hydrogen generation
on metal surfaces promote SRB growth. Hydrogenase-positive SRB utilize hydrogen for
reduction of sulfate.
Bacterial scavenging of cathodically-generated hydrogen results in
cathodic depolarisation enhancing anodic corrosion. Effect of SRB attachment on steel surfaces
resulting in hydrogen depolarization is illustrated in Fig. 35.1.
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Fig. 35.1: Model showing surface anchoring of SRB cells and cathodic depolarization.
Electrochemical reations involved in microboal corrosion of steel are outlined below:

Fe = Fe++ + 2e (Anodic)
2H+ + 2e = H2 (Cathodic)
SO4-- + 8H = S-- + 4 H2O (Bacterial depolarization)
Fe++ + S-- = FeS (Reaction of iron with reduced sulfide)
Fe++ + 2OH- = Fe (OH)2 (Corrosion product)
Net corrosion reaction can be summarized as

4 Fe + SO4-- + 4H2O = 3 Fe (OH)2 + FeS + 2OH-
The following factors promote SRB corrosion of steels

Presence of hydrogenase enzyme as a catalyst for hydrogen utilization.
Bacterial generation of H2S and formation of FeS on metal surfaces as a reaction product.
Cathodic hydrogen removal leading to depolarization.
Role of iron sulfide galvanically promoting iron dissolution.
Possibility of galvanic couple formation involving steel (anode) and the iron sulfide (cathode)
promotes corrosion. The role of bacteria as a catalyst promoting the above electrochemical
reactions need be stressed.
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Other factors which influence MIC in the presence of SRB are.

Anodic depolarization (besides cathodic polarization).
Formation of volatile phosphorus compounds promoting steel dissolution.
Role of iron-binding biopolymers.
Stress corrosion cracking in the presence of sulfides and hydrogen induced cracking.
SRB corrosion of steel will also be influenced by the nature and structure of the sulfide films.
Metal-cells-solution interface and environmental variables such as pH, ionic concentration,
oxygen levels and nature of exopolymers will control the surface corrosion products. Presence of
aggressive anions such as chlorides would enhance the corrosion rate.
Serious corrosion problems due to SRB is reported in environments pertaining to oil, gas
exploration and shipping. Serious biocorrosion problems in petroleum industries result in
increased refining costs and oil souring. SRB growth in marine injection systems results in
material damage besides oil and gas contamination with viable cells and reaction products.
Level of SRB activity in soils and waters can be monitored through redox potential
measurements.
< 100 mV
Severe biocorrosion possibility
100 200 mV
Moderate
200 400 mV
Very low
>400 mV
Almost insignificant
Soil and water environments can be classified in terms of resistivity, redox potentials, pH, water
content and SRB cell counts. Similarly, soil types (clayey, chalky, sandy and loamy) will have a
bearing on SRB corrosion.
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Lecture 36:Biocorrosion And Biofouling Mechanisms, Failure Analysis And Control

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Lecture 36
Biocorrosion And Biofouling Mechanisms, Failure
Analysis And Control
Keywords: Biofilms, Ennoblement, Failure Analysis, MIC Control
Biofilms and MIC

Biofilm formation on passive metals and alloys can lead to ennoblement of corrosion
potential. [232-235]
Special stainless steels, titanium alloys and noble metals such as platinum and
gold are capable of maintaining ennobled corrosion potential.
Although common stainless steels also exhibit corrosion potential ennoblement
they are amenable to localised pitting and crevice corrosion.
Copper alloys are not free from biofouling. Microorganisms can develop copper
tolerance and attach and colonise on copper base alloys. Some copper alloys
exhibit potential ennoblement. Presence of biogenic sulfides in copper alloys
promote biocorrosion.
Microbially-deposited manganic and ferric oxides can also contribute to potential
ennoblement followed by localised corrosion of stainless steels.
Enoblement of passive metals such as stainless steels and titanium occur as positive
shifts in open circuit potentials in the presence of biofilms. An increase in cathodic
current density during cathodic polarization may result in enhancement of open
circuit potentials. Microbial colonization as in biofilms results in biogeneration of
extracellular substances, organo metallic complexes and metal specific enzymes.
Bio-acidification at metal-solution interfaces and production of oxidants such as
H2O2 and MnO2 can cause ennoblement. Passivating siderophores produced by
bacteria can lead to ennoblement. Deposition of biogenic iron and manganese oxides
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can lead to ennoblement of passive metals. Iron and manganese oxidizing bacteria
present in fresh and sea waters as well as soils can attach and colonise on metal
surfaces and deposit manganic and iron oxyhydroxides.
Mn+2 + 2H2O = MnO2 + 4H+ + 2e
MnOOH + OH- = MnO2 + H2O + e
Depending on the pH, these reactions can influence the measured open circuit
potentials.
Biogenic MnO2 can corrode active metals such as mild steel

Fe + MnO2 + 4H+ = Fe++ + Mn++ + 2H2O
Manganese oxidizing organisms can cause corrosion of stainless steel welds.
Formation of MnO2 ennobles stainless steel potential in natural environments, and
when the potentials shift above repassivation potential pitting potential is reached.
Indirect role of Microorganisms in MIC

Bacterial and fungal metabolic products such as organic acids may retard anodic
polarization. Biogenic acids such as citric and oxalic acids can form metal ion
complexes, promoting anodic oxidation rates. Similarly inorganic acids like sulfuric
acid and nitric acids produced by microbes enhance metal dissolution. Phosphorus
compounds and H2O2 produced by bacteria are aggressive corrosive agents.
In industrial water systems, bacterial colonization lead to slime formation which
contain extracellular polysaccharides. Slime (or capsuble) formation around attached
bacteria protects them from biocides and corrosion inhibitors. Developments of
oxygen and metal ion concentration cells under the biofilms generate anodic and
cathodic areas, promoting corrosion. Identification and estimation of slime-forming
bacteria in cooling water systems is essential.
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Disruption of passive films and oxide layers from metal surfaces through biofilm
formation and SRB metabolites has been well established. Presence of extracellular
polymeric substances (EPS) in the copper oxide film can lead to microbial corrosion
of copper. Stainless steel interacted with heterotrophs can lead to local chromium
depletion under the passive layer. Many industrial failures due to localised pitting in
stainless steel condensers are caused by MIC.
Stress corrosion cracking of many alloys can be accelerated by microbial interaction.
For example, stresses can be induced by biogenic sulfides and hydrogen. Corrosion
fatigue can be biocatalyzed. Hydrogen embrittlement of steels can thus be caused by
microbial activity.
Biological degradation of protective coatings is common. Souring of petroleum
products due to biogenic H2S is a serious problem.
Biodegradation of coatings, paints, inhibitors, lubricants and emulsions in industrial
systems need be analyzed to understand MIC.
Aircraft fuel systems
Microbial corrosion in aircraft systems was known only after the 1950s. Fungi and
bacteria were found to be responsible for corrosion of aluminium alloys used in fuel
tanks. Aviation fuel contains several hydrocarbons which are liable for bacterial
contamination.
Pseudomonads are isolated from aircraft fuel systems.
The
predominant organism growing in aircraft fuel tanks is a fungus, Cladosporium

resinae. Sulfate Reducing Bacteria (SRB) can readily grow in ground storage fuel
tanks.
Controlling moisture content of fuels and use of fuel biocides could minimise the
problem.
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Aerobic bacteria and steel corrosion

From a corrosion view-point, aerobic bacteria can initiate biocorrosion processes
through.
Slime formation
Sulfur and sulfide oxidation, generating acids
Iron oxidation and precipitation of oxyhydroxides
Filamentous fungi, algae, protozoa, diatoms and bacteria are slime formers. Slimes
deposit on metal surface creating favorable conditions for concentration cells.
Sulfuric acid and reduced sulfur compounds produced by chemolithotrophs are

corrosive.
Iron oxidizers like Gallionella, Sphaerotilus and Pseudomonas, oxidize ferrous to
ferric ions leading to formation of insoluble tubercles consisting of hydrated ferric
oxides and excreted slimes grow on the corroded steel surfaces.
Slime deposition can also initiate pitting corrosion of stainless steels in sea water,
fresh water or sub-soil environments.
Aerobically generated biofilms increase
corrosion potentials. Pitting and crevice corrosion are caused by microbial action..
Stainless steel weldments are susceptible to MIC.
Microorganisms promote corrosion of active-passive metals and alloys such as

stainless steels and titanium through biofouling and biofilm formation.
Ennoblement of corrosion potential and increasing cathodic reaction rates.
Pitting initiation.
Corrosion behavior of bare and biofilm-coated metals are differemt. Potential
ennoblement due to biofilms varies from sample to sample under different
conditions. Percent biofilm coverage influences potential ennoblement.
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Oxygen reduction on stainless steel, can occur by noble shift in reversible potential
for the oxygen reduction or enhancement in its exchange current density.
Role of biofilms in MIC can be seen with respect to the following:

Pitting corrosion initiation in active-passive alloys. In marine environments,
both crevice and pitting corrosion can be promoted.
Galvanic attack due to enhancement of cathode kinetics. Both the open
circuit potential and cathodic kinetics can be increased for stainless steels in
the presence of biofilms.
Role of discrete bio films on stainless alloys can be understood with respect
to pitting, weld decay and crevice attack.
Generally, biofilms have been implicated in increasing corrosion rates of metals.

This is especially true for patchy, heterogeneous bio-deposits which can initiate
formation of concentration cells as indicated earlier.
There are instances, where aerobic bacteria such as Bacillus spp can decrease
biocorrosion. Ten-fold decrease in corrosion of SIS 1146 steel has been observed
with cultures of Pseudomonas. Sp. Aerobic biofilms can decrease corrosion
compared to sterile controls However, it is possible that such aerobic biofilms may
ultimately enhance corrosion due to colonization of anaerobic SRB.
MIC Failure Analysis and Control:
It becomes mandatory to check susceptibility of an engineering system for MIC.

Any engineering component exposed to water and nutrients can promote microbial
growth and corrosion failures manifest as loss of efficiency in heat exchangers or as
pressure drops in piping.
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MIC is prevalent in refineries, cooling water installations, oil-field water handling,

sprinklers, oil, water and gas pipelines, pulp and paper mills and power generation
installations.
MIC failure analysis should take into consideration the environment such as soil,
water and corrosion rates can be correlated with Eh, pH, moisture content, type of
soil and resistivity. Aerobic and anaerobic soil environments need to be monitored.
Factors contributing to SRB-induced corrosion in soils can be identified for buried
steel pipes, with respect to bacterial population, sulfate and organics and redox
potentials.
Metallurgical damage, corrosion products, environmental and microbiological
factors need be assessed to confirm MIC.
Morphology, directionalism, dimensions and distributions of pits.

Biological analyses of viable cells of aerobic, anaerobic and acid producing
bacteria.
Chemical estimation of corrosion products.
Standard methods for identification of microbial corrosion products in different

environmental and industrial conditions are available.
MIC in steels are often associated with untreated, stagnant water in pipes, weld
damage in stainless steel and fitting at the bottom of pipe.
Monitoring programs in industrial systems can be designed. Biofouling can be

evaluated by monitoring pressure drops across pipelines. Heat exchanger efficiency
can be monitored before and after fouling.
Electrochemical measurements to
monitor biofilms development, bioporducts and corrosion are also available.

Detection, diagnosis and monitoring are critical to prevent costly MIC failures.
Background history should be taken into consideration. Prior events, corrosion
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related records, details of repairs undertaken, water chemistry and water treatment
need be critically analyzed.
Various instruments and kits for corrosion monitoring are now readily available. For
microbiological analyses, standard procedures are available. Biological assays can
be done on liquid and solid samples in order to identify growing microbes, their
activities and concentrations of metabolic products.
Some common instrumental and analytical tools for biological evaluation are:
Cell
population
of
specific Counting chamber/Microscopy
organisms
Viable
cell
count
(Aerobe, Serial dilution, MPN method
anaerobe, others)
Microbes identification
Biochemical tests, DNA/RNA Probes,

Reverse sample genome probing.
Indirect biomass estimation
Proteins, polysaccharides, nucleic acids
Bacterial metabolism
ATP
Enzyme activity, Sulfate
Hydrogenase assay, Radio-active labelling,
reduction and attachment
Epifluorescence microscopy.
Prevention of MIC would be cheaper than its control after failure has occured.
Appropriate design, use of correct materials and control of corrosive environment are
important parameters.
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For designing water-containing machinery, many factors such as pH, source of

water, salinity, hardness, dissolved oxygen, type of impurities, flow rate and
temperature need be considered. For buried pipe lines, corrosivity of soil can be
monitored with respect to moisture content, pH, oxygen, nature of cations and
anions, presence of stray currents and resistivity.
Pipelines need be effectively coated for corrosion resistance and to reduce cathodic
protection current requirements. In practice, cathodic protection is used only with
protective coatings. Cathodic protection can be applied to external surfaces of buried
structures and submerged in water installations and also to inside of tanks and heat
exchangers.
In the presence of anaerobic bacteria (SRB), applied potentials for protection need be
more negative than usual.
System design and operation are key factors. Water leaks, water collection and
stagnation should be avoided. Tanks and fuel-storage vessels should be so designed
as to drain water at the bottom. Prevention and frequent removal of scales, and
deposits will be beneficial. Pipeline cleaning devices can be frequently used to
remove deposits and tubercles.
Use of biocides is practiced to minimize bacterial attachment and growth. Biocides

are added to chemical treatment packages to control biofouling.
For different
industrial environments, appropriate biocides need be used, such as ozone, chlorine,

amines and ammonium compounds. Strict regulations exist concerning chlorine use
and its residual concentrations in chlorinated water.
Many recent developments in monitoring biofilms and MIC would be attractive.
Chemical analysis within biofilms with micro-sensors.

Fiber-optic microprobe for analysis of biofilm structure.
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Scanning vibrating microprobe for electric field mapping.

DNA probes to investigate biofouling.
Environmental scanning electron microscope, Confocal laser scanning
microscopy and Atomic force microscopy to monitor biofilm growth.
In-situ oxygen measurements using microelectrodes.
9
Lecture 37: Microbially Induced Concrete Corrosion
NPTEL Web Course
Lecture 37
Microbially Induced Concrete Corrosion
Keywords: Concrete, Biocorrosion, Models, Prevention.
Corrosion of reinforcing steel in concrete structures is one of the most expensive

corrosion problems. Structural integrity of many bridges, buildings, terrestrial and
ocean structures has been affected by microbial processes. Cement and concrete can
be biodegraded and deteriorated through the action of various microorganisms.
Compounds such as calcium carbonate, silicates and aluminates slowly react with
water and bacterial metabolic products. Internal biocorrosion of reinforcing steel
reduces the life of concrete structures. Biocorrosion products having larger space
volume than the initial metal content initiate significant internal stresses leading to
fracture. Microbial weathering of cement and concrete increases porosity enhancing
water and corrodant penetration. Calcite precipitation and dissolution can be brought
about by indigenous microorganisms. A beneficial aspect in this regard would be
formation of calcium oxide (hydroxide) scales which can confer passive layer and
also selectively plug up the pores. Biogenic cement and concrete can thus confer
corrosion protection as well! This observation is of practical significance in curing of
cements and concretes. Microbial precipitation of calcium carbonate and calcium
hydroxide can lead to closure of pores, further increasing the corrosion resistance of
reinforcing steel.
Microbially induced concrete corrosion (MICC) has been known since 1900s.
Concrete sewer pipes were observed to be degenerated into a pasty mass. Sulfur
oxidizing bacteria could be identified and isolated from sewer pipes and channels.
Bacterial sulfur cycle involving both sulfur-oxidizing and sulfate-reducing bacteria is
relevant to MICC. SRB reduces sulfate present in sewage and soil materials to
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sulfides leading to generation of gaseous H2S, dissolved H2S as well as reduced

sulfur compounds such as hydrosulfides and polythionates. All the above sulfurbased reagents are corrosives to steel in cement and concrete structures. Bacterial
oxidation of sulfur and sulfides lead to biogeneration of sulfuric acid which can
corrode reinforcement steels and also dissolve cementaceous materials. Besides the
above sulfur-oxidizing and sulfate-reducing bacteria, other neutrophilic heterotrophs
of the genus, Bacillus and Pseudomonas present in sewer and soil environments
generate organic acids, polysaccharides and proteins that can also corrode many
metals and alloys. MICC can occur in different types of concrete systems such as
Waste water treatment.
Swimming pools and tanks.
Cooling towers.
Hydraulic structures, bridges and buildings.
Rapid deterioration occurs in areas with elevated H2S and acid concentrations. A
pictorial representation of microbial corrosion in sewage collection systems is
illustrated in Fig. 37.1.
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Fig. 37.1 Microbial corrosion of concrete pipes
Reaction sequences:
a) H2S generated by SRB in biofilms and sewerage-converted to various
reduced-valence sulfur compounds.
b) In presence of O2, water and S-bacteria, sulfuric acid is produced.
c) Acids and S-compounds react with binder in concrete-disintegration,
porosity, structural damage and reinforced steel corrosion.
Bio-and physico-chemical variables such as biomass (cell number), pH, Eh and
concrete ingredients change with time during the above mentioned process
sequences.
acidification.
The initial pH being neutral is rendered acidic through bacterial

Biological succession and pH reduction lead to deterioration of
concrete and corrosion of reinforced steel.
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Colonization of concrete is an excellent example of bacterial succession. Concrete is

generally alkaline with a pH of 11-13.
Environmental reagents such as CO2, H2S, HS- etc can reduce the concrete pH to 9.
Due to the availability of nutrients, bacterial attachment, growth and colonization on
concrete surfaces take place. Neutrophilic Acidithiobacllus spp, such as T.thioparus
can proliferate and the pH can drop to about 4-5 when other acidophiles take over.
In concrete corrosion, the following Acidithiobacllus species were found to take part
(Table 37.1).
Table 37.1 Acidithiobacllus bacteria involved in concrete corrosion
Bacteria
pH range
Substrate
T. thioparus
4-10
S2O3, H2S
T.novellus
5-9
S2O3
T. neapolitanus
4-9
H2S, S,
S2O3
T. intermedius
1.5-9
S2O3
At. Thiooxidans
0.5-9
S2O3, S
Besides bacteria, acidophilic and neutrophilic fungi can also grow on concrete
surfaces, reducing pH levels to highly acidic values (pH 2 and lower). Reaction of
biogenic sulfuric acid with the cementatious materials in concrete lead to structural
failure. Corroding layers consist of gypsum and moisture. Ettringite (3CaO . Al2O3 .
CaSO4 . 12H2O) produced due to bacterial action can induce internal stresses leading
to cracking, pits and fissures, which facilitates further acid penetration. Corrosion
rates up to 4-5 mm/year can be realized under the above conditions.
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A model for concrete biocorrosion is shown in Fig. 37.2
Fig. 37.2 Biocorrosion of concrete
Corrosion potential of steel in reinforced concrete is measured relative to a reference

electrode (Cu CuSO4) in contact with concrete surfaces using high impedance
voltmeters as shown in Fig. 37.3.
Fig. 37.3 Potential measurements in reinforced concrete
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Models have been proposed to predict microbial corrosion of concrete taking into
consideration the following parameters.
a) Sulfide generation.
b) Sulfide flux to the pipe wall.
c) Rate of acid reaction with concrete.
Prevention strategies
Corrosion effects of H2S and H2SO4 can be reduced by creating conditions that
prevent or minimize their generation. This may not be that easy always. Proper
treatment of sewer or modification of concrete could be useful. Concrete protection
methods include modification of concrete mix and design, coatings or paintings on
concrete surfaces or use of appropriate impermeable liners.
Increasing and maintaining alkalinity could prevent acid corrosion.
In sanitary
constructions, appropriate specifications of cement need be used.
Control of
concrete sewer corrosion by the crown spray process has been reported. A high pH
mixture is sprayed into the crown area of sewer. Deactivation and sterilization of
acid generating bacteria along with acid neutralization is aimed at. Activity of sulfate
reducing and sulfide-oxidizing bacteria in the environment and formation of biofilms
need be curbed. Magnesium hydroxide slurries of pH about 11 can be used to
neutralize acid.
Control of dissolved oxygen levels, sulfate concentrations and
organic levels in the sewer environment could deactivate the corrosion-causing

microbial load.
Modification of concrete materials used in structures is another strategy. Closure of
leakages and pores in the pipe lines through socket-seals would prove effective.
Microbial concrete is a novel strategy to restore damaged structures through
biomineralization of calcium carbonate using microbes such as Bacillus sp.
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Microbiologically induced calcite precipitation can generate highly impermeable

calcite layer over the surface of already existing concrete layers. Bacterial
concrete can be made by embedding bacteria that are capable of calcite
precipitation in the concrete. Bacteria such as Bacillus subtilis and Bacillus pasteurii
can induce calcite deposition. The use of microbial concrete enhances durability of
cement materials, sealing of decayed concrete structures and improves corrosion
resistance of buildings and structures.
Reduction in permeability through
bioprecipitation of calcite in situ can prevent penetration of corrosion reactants.
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References and recommended reading

(Lectures 24 37)
1. J.D.A Miller, Microbial Aspects of Metallurgy, Medical & Tech. Pub. Co,
Lancaster (1971).
2. S.W.Borenstein, Microbiologically influenced corrosion handbook, Wood head
Pub. Ltd., Cambridge (1994).
3. C.C. Gaylarde and H.A. Videla, (Eds), Bioextraction and Biodeteriortion of
metals, Cambridge Univ. Press, Cambridge (1995).
4. M.G. Fontana, Corrosion engineering, Mc Graw Hall, New York (1987).
5. D.A Jones, Principles and Prevention of Corrosion Prentice Hall Inc, New York
(1996).
6. H. A. Videla and L. K. Herrera, Microbiologically influenced corrosion: looking
to the future. Research Review. International Microbiology Vol.8, pp 169-180
(2005).
7. T.R. Jack, Biological corrosion failures.
8. I.B Beech, C.C. Gaylarde, Recent advances in the study of biocorrosion an
overview, Rev. Microbiol 30, pp 1-22 (1999).
9. K.A. Natarajan, Microbially influenced corrosion, chapter 3, in CORROSION
SCIENCE AND TECHNOLOGY, (Eds) U. K. Mudali and Baldev Raj. Narosa,
New Delhi (2008).
10. K.A. Natarajan, Microbes, Minerals and Environment, Geological survey of
India, Bangalore (1998).
11. G.Manivasagam, D.Dhimasekharan and A.Rajamanickam, Biomedical Implants:
Corrosion and its prevention. A Review, Recent patents on corrosion science, 2,
40-54 (2010).
12. D.C. Hansen, Metal Corrosion in the human body. The ultimate biocorrosion
scenario. The Electrochemical society interface, pp 31 -34 ( 2008).
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13. D.J Roberts, D. Nica, G. Zuo, J. L. Davis, Quantifying microbially induced

deterioration of concrete: initial studies. International Biodeterioration and
Biodegradation, 49, 227 234 (2002).
14. A.K. Parande, P.L. Ramasamy, S.Ethirajan, C.R.K Rao and N. Palanisamy,
Deterioration of reinforced concrete in sewer environments, Proc. Inst of civil
engg. Mucipal Engineer, 159, pp 11-20, (2006).
15. V.Achal, A.Mukherjee and M.S.Reddy, Microbial concrete: A way to enhance
durability of building structures, Int. conf. sustainable construction materials and
Technologies,. Ancona, Italy June (2010).
16. N.Eliaz, Biomaterials and corrosion, chapter 12, in CORROSION SCIENCE
AND TECHNOLOGY. (Eds, U. K. Mudali and Baldev Raj, Narosa, New Delhi
(2008).
17. U. K. Mudali, T. M. Sridhar and Baldev Raj, Corrosion of bio implants, Sadhana,
28, pp 601 637 (2003).
9
Worked-out Problems
1. 24 g of zinc are solubilized in 1M acid solution. Using Faradays law, calculate coulombs
(Q) produced in the anodic oxidation process.
F = 96500 Coulombs
n=2
for Zn = Zn++ + 2e
24g per 65.4 g/mole of Zinc

Q = 96500 x 2 x
= 70,325 coulombs
2. With respect to EMF series, indicate the easiness with which the following metals can be
cathodically reduced?
Cu++ / Cu, Pb++ / Pb, Fe++ / Fe, Co++ / Co
Answer: Cu (E0 = + 0.34V) easiest to reduce, followed by
Pb (E0 = -0.126V), Co (E0 = - 0.28V) and Fe (E0 = - 0.44V)
3. Which among the following metals is easily oxidized in solution? Ag, Au, Mg, Fe, Zn
Answer: Mg (E0 = - 2.38 V), Zn (E0 = - 0.76 V), Fe (E0 = - 0.44V),
Ag (E0 = + 0.8V), Au (E0 = + 1.68 V)
4. Potential measured for a metal in a solution with reference to hydrogen electrode is 1.0
V. What would be the potential Vs Ag/AgCl and Cu/CuSO4?
Answer: 1.0 0.2 = 0.84 V (Ag / AgCl)
1.0 0.34 = 0.66 V (Cu / CuSO4)
5. A luggin capillary is commonly used in potential measurements and polarization studies.

Comment on its advantages.
Answer: To Facilitate potential measurement is close proximity to the working electrode.
Eliminate liquid junction potentials.
6. How one can verify existence of concentration polarization for an electrochemical

reaction in a stagnant dilute solution?
Concentration polarization is affected by solution agitation (Stirring). If the polarization
disappears on agitation, one can confirm that it was indeed concentration polarization.
7. Calculate the cell potential
Ag | Ag+ (1.0M) || Cu++ (1.0M) | Cu0
As written, anode is Ag = Ag+ + e
E0 = + 0.8 V
cathode is Cu++ + 2e = Cu
E0 = + 0.34 V
Ecell = 0.34 ( + 0.8) = - 0.46 V

The cell is not spontaneous
If the electrodes are reversed in position, the Ecell becomes +0.46 V (spontaneous)
8. Using Faradays law, calculate time required to plate out 50 g of nickel from its sulfate
using a current of 4.0 amperes?
50 / 58.7 = g / mole = 0.85 mole of nickel
Ni++ + 2e = Ni
0.85 x 2 = 1.70 mol required
1.70 x 96500 = 1, 64050 coulombs / mol
1,64,050 x 4 = 656200 Seconds
Convert into minutes / hours
9. What is the difference between activation and concentration polarization?

Find answer from a book.
10. Simplify ln
to room temperature condition?
at 250 c
11. Calculate the reversible potential for zinc in contact with ZnCl2 at 10-3 M.
EZn = - 0.76 +
log [10-3]
= - 0.85 V
12. What is the potential of O2 electrode in a solution at pH = 10.
O2 + 2H2O + 4e = 2H2O
Eh = 1.23 0.059 pH
1.23 0.059 x 10 V
= 0.64 V
13. For the reaction Fe++ + Sn = Sn++ + Fe
Ecell = - 0.44 ( - 0.140) = - 0.301 V
This reaction is non-spontaneous
Cell reverses polarity at Ecell = 0
0.301 = 2.303
log
3
Log
= 6.4 x 10-11
14. Corrosion rate of iron in mpy for an equivalent corrosion current density of 1A / cm2
Atomic wt
0.129
= 0.46 mpy
Density
15. Penetration rate current density relationship for alloys require the determination of
equivalent weight.
Neq =
Where fi = mass fraction
ni = electrons involved
ai = atomic wt
Equivalent wt =
For an alloy with Fe = 72%
Cr = 18%
Ni = 10%
Neq =
= 0.04
Equivalent wt of alloy =
= 25
Refer Table 3.1 in reference, D. A. Jones to get the mpy for 1A / cm2 current density
and equivalent wt.
Similarly corrosion penetration rates for other alloys can be arrived at.
16.
Polarization resistance from the curve is

Rp = 1.5 x 102 ohm cm2
Icorr =
Determine
and
from the linear polarization plots. Suppose the value of
and
are 90 mV / decade.
icorr =
17.
The potential of a platinum electrode on which hydrogen evolved is 1.0 V (NHE) at pH

3.0. What is the hydrogen overpotential?
Eh = 0.059 pH
Eh = -0.18 V at pH 3
Over potential is E - Erev
-1.0 ( - 0.18) = -0.82 V
18. The fundamental concept in cathodic protection is that the protected structure (metal) is
polarized to the open circuit anode potential of local action cells for complete protection.
Theoretical calculations for minimum potential for cathodic protection can easily be
made.
For Fe, assume activity of Fe++ in equilibrium.
Calculate [Fe++] from solubility product of Fe (OH)2
log [Fe++]
Eh = - 0.44 +
[Fe++] =
Fe++ + 2 OH- = Fe (OH)2

Ksp = 1.8 x 10-15
Eh works out to be 0.60 V (NHE)
Similarly, minimum potentials for cathodic protection can be calculated for Cu, Zn, Pb
etc..
See the table below:
Metal
E0(V)
Ksp for M (OH)2
Calculated Eh (V)
Fe
- 0.440
1.8 x 10-15
- 0.60
Cu
+ 0. 34
1.6 x 10-19
+ 0.16
Zn
- 0.76
4.5 x 10-17
- 0.93
Pb
- 0.126
4.2 x 10-15
- 0.27

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Lecture 2: Electrochemical Cells Definitions and Principles

NPTEL Web Course

Definitions and types of electrochemical cells.

electrochemical cell contains two electrodes (anode and cathode); a liquid-liquid

Anode is the electrode where oxidation occurs.

Ion Ion (redox)

Metal insoluble salt

Liquid Junction: Serves as galvanic contact between electrodes (can be a salt

Lecture 2: Electrochemical Cells Definitions and Principles

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Fig.2.1 Electrochemical cell with salt bridge

IUPAC sign convention for electrode potentials

Lecture 2: Electrochemical Cells Definitions and Principles

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E0 is independent of number of moles of reactant or product.

Chemical energy to electrical energy

Electrical to chemical energy

Non spontaneous/Kinetic cell /

AG0 <O, E0cell >O

AG0 > O, E0cell < O

Eg: Dry cell

Lecture 2: Electrochemical Cells Definitions and Principles

NPTEL Web Course

Definition of electrochemical cell

Driving force for

electrochemical reaction is the potential difference between the electrodes, Ecell.

Where E0 is the standard electrode potential,

is the ratio between activities of

oxidized and reduced species.

Lecture 2: Electrochemical Cells Definitions and Principles

NPTEL Web Course

Fig.2.2 Diagrammatic representation of Daniel cell

(-)Zn | Zn++ (1M) || Cu++ (1M) | Cu(+)

Lecture 2: Electrochemical Cells Definitions and Principles

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For the reaction, Fe++ = Fe+++ + e

| Fe++ , Fe+++ || H+, H2 | Pt (+)

For the reaction 2H+ + 2e = H2

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

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Electrode potentials can be measured using a reference electrode in any desired

Fig. 3.1 Measurement of electrode potential with reference to standard electrode.

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

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Brief description of a few generally used reference electrodes given below:

Fig. 3.2 Hydrogen reference electrode

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

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Fig. 3.3 Saturated calomel electrode (SCE)

Hg2Cl2 + 2e = 2Hg + 2ClStandard potential = + 0.244V

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

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Silver / Silver chloride Electrode

Fig. 3.4 Ag/AgCl reference electrode

Copper / Copper sulfate electrode

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

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Types of galvanic cells

Lecture 3: Potential Measurements Galvanic Cells, Concentration Cells

NPTEL Web Course

See the model for rusting of iron given in Fig. 1.1.

Fig.3.5 Oxygen Concentration cell

Similarly, metal ion concentration gradients at metal-solution interfaces can create a