Corrosion and its Control

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Introduction
• Corrosion is an oxidation process.
• Most metals exist in nature in combined form as their oxides, carbonates, hydroxy, sulphides,
chlorides, and silicates.
• These are reduced to their metallic states from their ores during their extraction processes.
• Hence, corrosion is exactly opposite process of metallurgy (extraction of metals).
• Corrosion is a spontaneous process.
• When metals are exposed to the environment of dry gas, moisture, liquids etc. they will begin to
decay by the conversion into the more stable metal compounds.
• Any process of deterioration or destruction and consequent loss of a solid metallic material
through an unwanted and unintentional chemical or electrochemical attack by its environment
starting at its surface is called corrosion.
• The most familiar example of corrosion is rusting of iron when exposed to atmospheric conditions
it forms reddish scale and powder of iron oxide Fe304 and iron becomes weak.
• Another common example is the formation of green film of basic carbonate and hydroxide on the
surface of copper when exposed to moist air containing carbon dioxide.
• The process of corrosion is slow and causes damages of machines, equipment and other metallic
products and care must be taken to prevent the corrosion.

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Types of corrosion

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Dry or chemical corrosion
• This type of corrosion occurs mainly through the direct chemical action of environment such as
oxygen, carbon dioxide, halogen, hydrogen sulphide, sulphur dioxide, nitrogen and anhydrous
inorganic liquid with metal surface in immediate proximity.

a) Oxidation corrosion
• This is due to the direct action of oxygen at low or high temperature on metals usually in the
absence of moisture.
• At ordinary temperatures metals in general are very slightly attacked. But alkali metals and
alkaline earth metals even rapidly oxidised at low temperatures.
• At high temperature almost all the metals are oxidised except silver, gold and platinum.

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• When oxidation starts a thin layer of oxide is formed on the metal surface and the nature of this
film decides the further action there are 4 types of films: Stable film, unstable film, volatile film,
porous film.

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• Stable film behaves as a protective coating in nature, thereby shielding the metal surface. Oxide
films on Al, Sn, Pb, Cu, Pt etc. are stable, tightly-adhering and impervious (water proof) in nature
and further oxidation corrosion is prevented.
• Unstable film decomposes back into the metal and oxygen. Consequently, the oxidation corrosion
is not possible in such a case. Thus, Ag, Au and Pt do not undergo oxidation corrosion.

Metal Oxide → Metal + Oxide

• Volatile film volatilizes as soon as it is formed, thereby leaving underlying metal surface exposed
for the further attack which causes rapid and continuous corrosion leading to excessive
corrosion. Film on Molybdenum oxide (MoO3) is an example of volatile film.

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• Porous film has cracks or pores through which, the atmospheric oxygen has access to the
underlying surface of metals by which corrosion continues unobstructed till the entire metal
completely decays.

Pilling-Bedworth rule
• According to this rule, “an oxide is a protective or non-porous, if the volume of the oxide is at-
least as great as the volume of the metal from which it is formed”. On the other hand, “if the
volume of the oxide is less than the volume of the metal, the oxide layer is porous (non-
continuous) and hence, non-protective because it can’t prevent the access of oxygen to the
fresh metal surface below”.
• Alkali and alkaline-earth metals such as Li, Na, K, Mg etc. forms the porous oxides due to which
they face stress and strain and develop the cracks and pores in the structure by permitting free
access of oxygen and corrosion continues non-stop.
• Metals like Al forms non-porous oxides which are tightly-adhering and due to which, the absence
of pores or cracks in the oxide film, the rate of oxidation rapidly decreases to zero.

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b) Corrosion by gases
• This is caused by gases like SO2, CO2, Cl2, H2S, F2 etc. and the corrosive effect depends on mainly
the interaction between metal and gas involved and the degree of attack depends on the porous
or non-porous oxide film formation on the metal surface.
• If the film formed is non-porous the intensity of attack decreases such as AgCl film formed by
chlorine gas on Ag.
• If the film formed is porous the surface of whole metal is gradually destroyed such as chlorine
gas attack on Sn forming volatile SnCl4 which volatilizes immediately leaving the surface of metal
open for further attack. Similarly, H2S attack at high temperature on steel forms FeS scale which
is porous in petroleum industries is another example of porous oxide film.

c) Liquid metal corrosion

• This is caused due to the chemical action of flowing liquid metal at high temperatures on solid
metal or alloy.
• This type of corrosion occurs in the devices used for the nuclear reactors for the power
generation.
• which involves either dissolution of a solid metal by a liquid metal or internal penetration of the
liquid metal into the solid metal and both the pathways cause the weakening of the solid metal.

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Wet or electrochemical corrosion
• This type of corrosion occurs in two situations:
o where a conducting liquid is in contact with metal
o when two dissimilar metals or alloys are either immersed or dipped partially in a solution
• This is caused by the formation of anode and cathode on the surface of metal where oxidation
and reduction take place and due to this anodic metal is destroyed by either dissolving or
assuming combined state such as an oxide formation.
• Thus, corrosion always occurs at anodic areas of metal.

• On the other hand, at cathodic areas, reduction takes place where the cathode is not affected by
the reaction since metals are already in the reduced form and can’t be further reduced.
• So, at cathodic part, dissolved constituents in the conducting medium accepts the electrons to
form some ions like hydroxide, oxide etc.
• By this way, metallic ions at anodic part and non-metallic ions at cathodic part diffuse towards
each other through conducting medium and form a corrosion product somewhere between anode
and cathode.
• Thus, electrochemical corrosion involves
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 o the formation of anodic and cathodic areas
o presence of conducting medium
o corrosion of anodic areas only
o formation of corrosion product somewhere between anodic and cathodic area
M → Mn+ + e- (Oxidation of metal at anode)
• On cathode reaction consumes electrons with either (a) evolution of hydrogen gas or (b)
absorption of oxygen gas depending on the nature of environment.

a) Evolution of hydrogen gas

• This corrosion occurs usually in acidic environment.
• Considering metal like Fe, the anodic reaction is dissolution of ferrous ions with the liberation of
electrons, which flow through the metal form anode to cathode where H+ ions are eliminated as
hydrogen gas.
Fe → Fe2+ + 2e- (Oxidation)
2H+ + 2e- → H2 ↑ (Reduction)
Fe + 2H+ → Fe2+ + H2 ↑ (Overall reaction)
• This type of corrosion causes displacement of hydrogen ion from acidic solution by metal ions.
• consequently, all metals above hydrogen in the electrochemical series have a tendency to get
dissolved in acidic solution with simultaneous evolution of hydrogen.
• In this type of corrosion, the anodes have usually very large areas whereas cathodes have small
areas.
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b) Absorption of oxygen gas
• Rusting of iron in neutral aqueous solution of electrolytes like any NaCl solution in the presence
of atmospheric oxygen is a common example of this type of corrosion.
• The surface of iron is usually coated with a thin film of iron oxide, however if this iron oxide film
develops some cracks, anodic areas are created on the surface; while the well-metal parts act as
cathode
• In this type of corrosion, the cathodes have usually very large areas whereas anodes have small
areas.
• At the anodic areas of the metal dissolves as ferrous ions with the liberation of electrons.
• These electrons flow form anode to cathode through iron metal, where electrons are intercepted
by the dissolved oxygen.
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• Ferrous ion at anode and hydroxide ion at cathode diffuse and when they meet ferrous hydroxide
is precipitated.
• If enough oxygen is present ferrous hydroxide is easily oxidised to ferric oxide.
• This product is called yellow rust which actually corresponds to Fe203.H2O.
• If supply of oxygen is limited the corrosion product may be even black and hydrous magnetite
Fe304.H2O.
Fe → Fe2+ + 2e- (Oxidation)
1/2O2 + H2O + 2e- → 2OH- (Reduction)
Fe + 2OH- → Fe(OH)2 ↓
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3
• Note that Fe2+ and OH- originate from the anode and cathode respectively but they combine near
cathode because the smaller size of Fe2+ diffuses more rapidly than the larger OH- and hence the
corrosion occurs at the anode but rust is deposited near the cathode.
• There are two effects observed due to the increase in oxygen:
o It forces the cathodic reaction to the right, producing more OH- ions.
o It removes more electrons and therefor accelerate the corrosion at anode.
• Both the effects supply more reactants for the rust formation.

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a) Concentration cell corrosion
• This type of corrosion is observed due to the electrochemical attack on the metal surface exposed
to an electrolyte of varying concentrations varying aeration; due to the formation of concentration
cell, there will be difference in potential between differently aerated areas.
• This may be the result of local difference in metal-ion concentrations, due to the local
temperature difference or inadequate agitation or slow diffusion of metal ions produced by the
corrosion.
• Differential aeration corrosion is the most common type of concentration cell corrosion, occurs
when a metal part is exposed to different air concentrations from the other part.
• Poor oxygenated part will be the anode and more oxygenated part will be cathode.
• Waterline corrosion may be called as one type of concentration cell corrosion.
• If Zn strip is immersed in as solution of NaCl, the part above the waterline will act as cathode
and part immersed to greater depth, which has less access of oxygen will act as anode.
• So, a difference of potential is created which causes a flow of current between the two differently
aerated areas of the same metal.
• Zinc will dissolve at anodic area and oxygen will take up the electrons at cathodic area to form
hydroxide ions.
• The electrical circuit is completed by the migration of ions, through the electrolyte, and flow of
electrons, through the metal from anode to cathode.

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b) Galvanic cell (Bimetallic) corrosion
• When two dissimilar metals (e.g. zinc and copper) are electrically connected and exposed to an
electrolyte the metal higher in electrochemical series undergoes corrosion.
• This type of corrosion is called galvanic corrosion due to the formation of galvanic cell.
• Here, the zinc metal forms an anode and it is attacked and gets dissolved; while copper acts as
cathode as per the electrochemical series more noble metal will be protected.
• In acidic medium, corrosion occurs by the hydrogen evolution process while in neutral or slightly
alkaline medium oxygen absorption process occurs.
• The electron current flows from anodic metal zinc to cathodic metal copper.
• Thus, it is an evident that, the corrosion occurs at the anodic metal while cathodic metal is
protected from the attack.
• For e.g. Steel screws in a brass in marine hardware, Lead-Antimony solder around copper wire,
a steel propeller shaft bronze bearing, steel pipe connected to copper plumbing.
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c) Waterline corrosion
• When water is stored in a steel tank, it is generally found that the maximum amount of corrosion
takes place along a line just beneath (under) the level of the water meniscus.
• The area above the waterline (highly oxygenated) acts is the catholic and is completely unaffected
by corrosion.
• However, if the water is relatively free from acidity little corrosion takes place.
• This corrosion is the major concerns for the marine engineers.
• In ships, this kind of corrosion is often accelerated by marine plants attaching themselves to the
sides of ships.
• The use of special anti-fouling paints prevents this to some extent.

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d) Stress corrosion
• In a metallic structure, if there is a portion under stress, it will act as anode and rest part of the
structure will act as cathode.
• It is now a galvanic system and hence anodic part which is small in area will corrode more.
• For stress corrosion to occur, i) presence of tensile stress and ii) a specific corrosive environment
are necessary factors.
• The corrosive agents are highly specific and selective such are: A) caustic alkalis and strong
nitrate solution for mild steel, B) traces of ammonia for brass C) acid chloride solution for
stainless steel.
• This type of corrosion is observed in fabricated articles of certain alloys like zinc-brass and nickel-
brass alloys due to the presence of stresses caused by heavy working like rolling, drawing or
insufficient annealing (tempering).
• Pure metals are relatively immune to the stress corrosion.
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 • Season cracking and caustic embrittlement are the examples of stress corrosion.

e) Pitting corrosion
• Pitting corrosion is localised accelerated attack, resulting in the formation of cavities around
which the metal is relatively unattached.
• Hence, pitting corrosion results in the formation of pinholes, pits and cavities in the metals.
• Pitting is usually, the result of the breakdown or cracking of the protective film on a metal at
specific points; due to i) surface roughness or non-uniform finish, ii) scratches or cut edges, iii)
local straining of metal due to non-uniform stresses, iv) alternating stresses, v) sliding under
load, vi) impingement attack (caused by the turbulent flow of a solution over a metal surface),
vii) chemical attack etc.
• This process gives rise to the formation of small anodic and large cathodic areas.
• The crack portion acts as anode and rest of the metal surface acts as cathode.
• It is the anodic area which will be corroded and the formation of a pit is observed.

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 • Presence of external impurities such as sand, dust, scale embedded on the surface of metals lead
to pitting.
• For example, stainless steel and aluminium show pitting in chloride solution.

f) Intergranular corrosion
• This type of corrosion occurs along grain boundaries and only where the material is sensitive to
corrosive attack exist and liquid possesses a selective character of attacking only at the grain
boundaries but leaving the grain interiors untouched or slightly attacks.
• This is because of grain boundaries contain material; which shows electrode potential more
anodic than that of the grain centre in a particular corroding medium.
• This is also due to the precipitation of certain compounds at the grain boundaries, thereby
leaving the solid metal solution just adjacent to the grain boundary depleted in one constituent.
• The depleted part will act as an anode with respect to the grain centres as well as to the
precipitated compound so that it will be attacked preferentially by the corrosive environment.

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• This type of corrosion is generally found in alloys. For e.g., during the welding of stainless steel
(alloy of Fe, C and Cr) chromium chloride is precipitated at the grain boundaries, thereby the
region just adjacent to grain boundaries becomes depleted in chromium composition and is more
anodic with respect to the solid solution within the grain which is richer in chromium. For the
same reason, it is also anodic to the particles of the chromium carbide so precipitated.
• This corrosion occurs at microscopic level without any sign of intensive attack.
• This can cause sudden failure of material occurs i.e., can be broken suddenly without any prior
sing of corrosion due to the loss of cohesion between the grains.
• The remedy is proper heat-treatment followed by rapid quenching to avoid heterogenous
precipitation that, usually, occurs due to slow cooling.
• Usually, paint is applied to the welded part to prevent the corrosion.

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g) Passivity
• Passivity or passivation is the phenomenon in which a metal or an alloy exhibits a much higher
corrosion-resistance than expected from its position in the electrochemical series.
• Passivity is the result of the formation of a highly protective, but very thin (~0.0004mm) and
quite invisible film on the surface of metal or an alloy, which makes it more noble.
• This film is insoluble, non-porous and such a self-healing nature, that when broken, it will repair
itself on re-exposure to the oxidising conditions.
• Example of passive metals and alloys are: Ti, Al, Cr, Stell alloys containing Cr etc.
• These exhibit outstanding corrosion resistance in oxidising environments, but in reducing
environments, they become chemically active.
• Based on experimental results, in aerated 0.5M NaCl solution, the passivity of certain metals
falls in the following order:
Tl→Al→Cr→Be→Mo→Mg→Ni→Co→Fe→Mn→Zn→Cd→Sn→Pb→Cu
• Passivity is not a constant state, but exists only in certain environment condition, which tends
to maintain thin protective oxide films on their surfaces.
• In the presence of oxygen, the oxide film is automatically repaired when damages occurs, but in
the absence of oxygen passive metal and alloys become chemically active and are rapidly
corroded.
• For e.g., stainless steel is quite good resistant to the action of aerated dilute H2SO4, but shows
low resistance in air-free acid.
• The action of conc. HNO3 on Fe and Al produces a thin protective oxide film and makes it passive.
• They are not attacked further by conc. HNO3.

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 • On the other hand, dil. HNO3 on Fe, stimulates the cathodic reactions rapidly and corrosion of
Fe occurs without even hydrogen gas evolution.
• In the case of Stainless steel and Ti, the protective oxide film is maintained, even in dil. HNO 3,
so that these exhibits high corrosion resistance in HNO3 solution over wide range of
concentrations.

Differentiate between dry corrosion and wet corrosion

Dry corrosion Wet corrosion
• Corrosion occurs in the absence of moisture. • Corrosion occurs in presence of conducting
• It involves direct attack of chemicals on the medium.
metal surface. • It involves formation of electrochemical cells.
• The process is slow. • It is a rapid process.
• Corrosion products are produced at the site • Corrosion occurs at anode but rust is
of corrosion. deposited near cathode.
• The process of corrosion is uniform. • It depends on the size of the anodic part
of metal.

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Factors affecting the corrosion
• Nature of metal
• Anodic and cathodic area
• Purity of metal
• Passive character of metal
• Physical state of metal
• Nature of oxide film
• Volatility of corrosion products
• Solubility of corrosion products
• Temperature
• Humidity in air
• Presence of impurities in atmosphere
• Change in pH
• Nature of ions present in solution
• Formation of concentration cell
• Conductance of corroding medium

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Corrosion control (Protection or prevention against corrosion
• Proper designing
• Using pure metal
• Cathodic protection (Sacrificial protection)
• Painting the metal surface
• Changing the environment
• Using inhibitors
• Applying protective coating
• Galvanizing
• Tinning

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