Module-3a Factors Affecting Corrosion

FACTORS INFLUENCING CORROSION:

GALVANIC SERIES:
In electrochemical series (EMF Series)
→ Reduction electrode potential is tabulated increasing downward.
→ A metal high in the series is more anodic and undergoes corrosion faster than the
metal below it.
i) Li>Mg ii) Zn>Fe iii) Cu>Ag
Exceptions: (Tl, Al, Cr, Mg, Ni, Co)
 Tl (above Ag in EC series) is less reactive than Ag.
 Zn –Al couple Zn (below Al in EC series) is more active and corroded faster.
 Because Tl and Al develop strongly adhering oxide layers on their surfaces and
hence their effective electrode potential are more positive ( or less negative)
→ For the study of corrosion of metal and alloys → galvanic series is more useful
rather than EC series.
→ It gives real and useful information.
FACTORS INFLUENCEING CORROSION:
A) Nature of the metals
B) Nature of the corroding environment
A) Nature of the metals:
i) Position in galvanic series:
→ In an electrical contact in the presence of electrolyte, the more active metal ( or
higher up in the series) suffers corrosion.
→ Rate and severity of corrosion depends on the difference in their positions.
→ Faster is the corrosion of the anodic metal/alloy
ii) Overvoltage:
→ If Zn metal is placed in 1N H2SO4 it undergoes corrosion forming a film and
evolving hydrogen gas.
 The initial rate of reduction is quite slow due to high overvoltage (0.70V) of Zn
metal, because it reduces the effective electrode potential to a small value.
→ If a few drops of CuSO4 solution is added, corrosion rate of Zn will increase. Cu
gets deposited in the Zn-Metal forming minute cathode where the hydrogen
overvoltage is only 0.33V.
→ Corrosion rate gets accelerated.
iii) Relative areas of the anodic and cathodic parts:

→ when dissimilar metal or alloys are in contact, the corrosion of the anodic part is

directly proportional to the ratio of areas of the cathodic part and the anodic part.

→ Corrosion is more severe and rapid if the anodic area is small (e.g. a small steel

pipe fitted in a large Cu-tank).

 Current density on the anodic surface is more.

→ Larger cathodic part demands more number of electrons, and hence

→ Corrosion on the anodic part will be more and more faster.

iv) Purity of metal:

→ Impurity leads of heterogeneity → forming tiny/minute electrochemical cells (at the

exposed parts) → the anodic parts gets corroded.

Ex: Zn metal containing impurity (Pb or Fe)

→ the rate of corrosion α exposed area x extent of impurity.

 So, corrosion resistance of a metal is increased by improving purity.

v) Physical state of metal:
→ Grain size, orientation of crystals and stress.
 Grain size: Smaller size → greater solubility and hence greater corrosion.
 Stress: Areas under stress (even in the pure metal) tends to be anodic and
corrosion will be at these areas.
vi) Nature of surface film:
 Specific volume ratio (SVR): volume of metal oxide/volume of pure metal
 Greater SVR → lower oxidation corrosion rate
→ SVR of Ni, Cr, and W are 1.6, 2.0 and 3.6 respectively
→ Oxidation rate of W is least even at elevated temperature.
vii) Passive character of metal:
→ metal like Tl, Al, Cr, Mg, NI and Co are more passive towards corrosion
→ highly protective very thin film of oxide on the metal or alloy surface
→ self healing in nature.
viii) Solubility of corrosion products:
→ In EC series, if corrosion products are soluble in the corroding medium, rate high.
ix) Volatility of corrosion products:
→ Excessive corrosion. MoO3 → volatile.
B. NATURE OF THE CORRODING ENVIRONMENT :
i) Temperature
ii) Humidity of air
iii) Presence of impurities in atmosphere
iv) Presence of suspended particles in atmosphere
v) Influence of pH
vi) Nature of Ions present
vii) Conductance of the corroding medium
viii) Formation of oxygen concentration cell
ix) Flow velocity of process stream
x) Polarization of electrodes
B) NATURE OF THE CORRODING ENVIRONMENT:
(i) Temperature.
→ Temperature increases → reaction rate and diffusion rate increase and hence
→ Corrosion rate also increases
(ii) Humidity of air:
→ it is the deciding factor in atmospheric corrosion
 Critical Humidity:
 Relative humidity above which the atmospheric corrosion rate of metal increases
sharply.
 Gases (like CO2, O2 etc.,) and vapours carry water to the electrolyte for setting up
an electrochemical corrosion cell.
 The oxide coating being a solid body possesses moisture absorbing capacity
needed for the occurrence of electrochemical type corrosion.
→ Corrosion rate is enhanced.
 Nature of moisture source:
 Rain water supply moisture as well as wash away a good part of oxide film from
the metal surface.
→ corrosion increases (Except : Oxide film of Cr and Al)
(iii) Presence of impurities in atmosphere:
→ Corrosive gases like CO2, H2S etc., and fume of HCl and H2SO4 increase the
acidity adjacent to the surface and its electrical conductivity.
→ Increases corrosion current flow in the local electrochemical cells on the exposed
metal surface
→ In the marine atmosphere the presence of sodium and other metal chlorides of
sea water causes increased conductivity of the liquid layer in contact with the
metal surface
→ Hence corrosion increases.
(IV) Presence of suspended particles in atmosphere:
In case of atmospheric corrosion
 If the suspended particles are chemically active like NaCl and (NH4)2SO4 and they
can absorb moisture and behave as strong electrolytes → increased corrosion.
 For chemically inactive nature i.e, charcoal
→ absorption of both sulphur gases as well moisture causing slowly enhanced
corrosion rate.
(V) Influence of pH:
Acid medium facilitates corrosion than neutral and basic media as a general rule
 Acidic medial (<pH 7) more corrosive than alkaline and neutral medium
 Amphoteric metals like Al, Zn and Pb etc dissolve in alkaline solution as complex
ions
 Corrosion of Fe in oxygen free water (<pH 5) is slow.
 Zn attacked by weakly acidic carbonic acid, but above pH >11 → no corrosion or
minimum corrosion.
 The corrosion rate of Fe in oxygen free water is very slow up to pH 5.0 but in the
presence of oxygen, the corrosion at pH 5.0 enhances greatly.
 At pH 4.0, the corrosion rate of Fe is very high since Fe2+ gets oxidized to Fe3+ .
 Zinc corrodes rapidly in acidic solutions but the rate of corrosion is low in alkaline
medium (pH 11.0).
 Aluminium corrodes less at pH 5.5 but the rate of corrosion is very high in pH 8.5.
vi) Nature of ions present:
 Anions like silicates form insoluble salts in the medium and inhibit further
corrosion.
 But, Cl- present in the atmosphere destroy the protective oxide film and
enhance rate of corrosion.
vii) Conductance of the corroding environment:
• In corrosion of underground and submerged structures, the conductance of the medium plays
a critical role in corrosion.

• Sandy soils have lower conductance than clayey and mineralized soils.
• Conductance due to stray currents through the soil will promote the corrosion.
viii) Formation of oxygen concentration cell:
• If one part of the metal is exposed to higher levels of oxygen, it becomes cathode and the
other part which is exposed to lesser levels of oxygen will become anode.
• This is called oxygen concentration cell which promotes corrosion by anodic
oxidation/dissolution.
• 2 H2O + O2 + 4e- 4 OH- (Cathodic reaction-higher O2)
• This OH- will move to the cathode where Fe2+ reacts to form Fe(OH)2 which later converts into
rust (Fe2O3.3H2O).
• Buried pipelines, cables etc., experience this kind of electrochemical corrosion.
ix) Flow velocity of process stream
 When a metal under diffusion control and is not passivating, an increase in flow
velocity of the medium enhances diffusion rate and also increase corrosion rate.
 For passive metal, it is difficult to predict this type of corrosion.

x) Polarization of electrodes
 Although the potential difference between the anode and the cathode is the
driving force for EC corrosion, the current flowing in the circuit controls the
corrosion rate.
 Addition of inorganic and organic substances (i.e., inhibitors) to the corroding
electrolyte species gets accumulated at the anode and depleted at the ccathode.
 The inhibitors causes certain irreversible changes around the electrodes and
opposes the flow of corrosion current direction.
 So, polarization at the electrodes due to
 Concentration changes at the electrodes
 Overvoltage
 Presence of surface film on the electrode.
Since diffusion controls polarization, the rate of corrosion will be slow at
 Stagnant situation
 Low concentration of the electrolyte species
 Low temperature
Delaysed diffusion →more polarization of electrode → less corrosion current
and corrosion rate.
CORROSION POTENTIAL (Ecorr) and CORROSION CURRENT (Icorr) :
Icorr depends on
 The current densities at the anode and cathode
 Potential difference between the electrodes
 Relative areas of the anode and cathode
 Polarisation characteristics of the electrodes
 Temperature
Icorr = Anodic current density (Ia) – Cathodic current density (Ic)
 If the cathodic area greater than the anodic areas → more corrosion of
anodic materials
 Higher polarization→ lower corrosion rate
 Corrosion rate is lower at lower temperature since diffusion rate is retarded.
 Evans Polarization diagrams:
 Electrochemical Series (EC) Series
SNo Metal ion Std Red Pot (in volts) Ref
1 Li+ -3.05 Anode
2 K+ -2.93
3 Ca2+ -2.90
4 Na+ -2.71
5 Mg2+ -2.37
6 Al3+ -1.66
7 Zn2+ -0.76
8 Cr3+ -0.74
9 Fe2+ -0.44
10 Ni2+ -0.23
11 Sn2+ -0.14
12 Pb2+ -0.13
13 Fe3+ -0.04
14 H+ 00 Reference
15 Cu2+ +0.34
16 Ag+ +0.80
17 Pt4+ +0.86
18 Au+ +1.69
19 ½F2 +2.87 Cathode
 Galvanic Series
SNo Metal ion Active/anodic
1 Mg
2 Mg alloys
3 Zn
4 Al
5 Cd
6 Al alloys
7 Mild steel
8 Cast iron
9 High Ni cast iron
10 Pb-Sn solder
11 Pb
12 Sn
13 Iconel
14 Ni-Mo-Fe alloys
15 Brasses
16 Monel
(Ni=7,Cu=30, Fe=rest)
17 Silver solder
18 Cu
19 Ni
SNo Metal ion
20 Cr stainless steel
21 18-8 stainless steel
22 18-8 Mo stainless
steel
23 Ag
24 Ti
25 Graphite
26 Au
27 Pt Noble/Cathodic
 EC series Galvanic series

1) Electrode potentials are measured by dipping 1) By studying corrosion of metals and

pure metals in their salt solution (1M alloys in unpolluted sea-water, without
Concn.) without any oxide film on them. their oxide films, if any, removed.

2) Position of a metal is fixed. 2) Position may shift.

3) No information regarding positions of alloys 3) Corrosion of alloys can be studied from

this series

4) Position is permanently fixed in EC series 4) The positions of a metal are different for
its pure form and alloys

5) It deals with only metals and non-metals 5) It deals with metals and alloys

6) It predicts the relative displacement 6) It predicts relative corrosion tendencies

tendencies.
 Tin coatings on steel structures
 Noble character and higher corrosion resistance nature of Sn w.r.t Fe.

Anodic coating Cathodic coating

1) Sacrificial type
2) Ep of anodic metal is
lower
3) If pores, breaks and
discontinuities occur, no
corrosion of base metal
4) Coating of Zn on Fe
1) Noble character and
more corrosion resistance
nature
2) Higher
3) Corrsion of base metal
will be at higher rate
4) Coating of Sn on Fe

iii) Metal cladding:

The process by which a dense homogeneous layer of coating metal is bonded firmly
and permanently to the base metal on one side or both sides
 Alloys like stainless steel, Ni alloys, Cu alloys, Pb alloys etc. and metals like Ni,
Cu, Pb, Ag, Pt, etc. → on mild steel, Al, Cu, Ni, and their alloys.