Unit 3 Corrosion
Unit 3 Corrosion
Unit 3 Corrosion
1. INTRODUCTION
Industrialized nations depend on metals which are used in structures like bridges, in automobiles,
ships, in pipelines, cars, trains and storage tanks. Metals also find use in various electronic
applications such as printed circuit, computer discs, connectors and switches. In addition, metals
also are used in coins, in jewelry, in historical monuments, and in objects of arts. Metals are used in
the human body in the form of replacements, as stents, surgical plates, screws and wires. Irrespective
of their use all metals tend to react with their environment to different extents and at different rates.
Thus, Corrosion is a natural phenomenon that causes a deterioration of the properties of the metal
due to the destructive attack of a metal by its environment.
Corrosion can be defined as spontaneous destruction or deterioration of a metal or alloys by
the surrounding environment because of chemical or electrochemical interaction. Free metals, as
such are unstable and whenever favorable situation arises they combine with other elements like
oxygen and form the compounds of minimum energy and maximum stability. Hence figure 3.1
shows that corrosion can be viewed as the reverse process of extractive metallurgy.
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Figure 3.1 Corrosion as reversal of metallurgy
Iron + oxygen Iron oxide (rust)
4Fe(s) + 3O2 (g) 2Fe2O3(s)
Iron ore + carbon monoxide Iron + carbon dioxide Fe2O3 (s) + 3 CO 2Fe(s) + 3 CO2 (g)
Three most common examples of corrosion include rusting of iron objects forming reddish brown
scale, tarnishing of silver in contact with traces of H2S or SO2 in the atmosphere or eggs rich in
sulfur compounds and formation of green scales on copper vessels. The process and the products
formed in these reactions are described in the following equations.
Rusting of iron 4Fe(s) + 3O2(g) 2Fe2O3.H2O(s)
Tarnishing of silver 4Ag(s) +2 H2S(g) + O2(g) 2Ag2S(s) + 2H2O(l)
Scales on copper 2Cu(s) + H2O(l) + O2(g) + CO2(g) Cu2(OH)2CO3(s)
Corrosion science aims to understand corrosion mechanisms.by gaining basic scientific knowledge
while Corrosion engineering involves the use of scientific knowledge to corrosion protection and
prevention. Corrosion science and corrosion engineering complement and reinforce each other.
Understanding of corrosion mechanisms can help develop new corrosion resistant alloys,
improved surface treatments, and better corrosion control methods.
Oxidation corrosion occurs when metals are attacked by dry oxygen (absence of moisture) at
extreme conditions like low or high temperature leading to oxidation type of corrosion. The direct
oxidation of metals takes place according to the following reaction scheme:
2M 2Mn+ + ne
nO2 + 2ne 2nO2
2M + nO2 2Mn+ + 2nO2
When the metal undergoes oxidation, a thin layer of oxide formed on the metal surface, and the
nature of this film decides the further action. If a stable film is formed, it behaves as protective
coating in nature, thereby shielding the metal surface. Consequently, further oxidation of metal is
prevented. eg: Al, Sn, Pb, Cu and Pt. Unstable metal film decomposes back into the metal and
oxygen. Hence oxidation corrosion is not possible in such cases: e.g. Ag, Au, and Pt. In some
cases, volatile film layer volatilizes as soon as it is formed, thereby accelerating the corrosion. e.g:
MoO3.
Corrosion by other gases like SO2, Cl2, CO2, and H2S, depends mainly on the chemical affinity
between the metal and the gas involved. For example, dry Cl 2 attacks silver metal and forms
AgCl as a thin protective and non-porous layer on the metal. As a result of this protective layer on
the metal surface, the intensity of corrosion decreases.
Liquid metal corrosion occurs when a molten liquid is continuously passed on a solid metal surface
or on alloy. This behavior may be either due to the dissolution of the molten liquid or due to
penetration of the molten liquid into the metal phase.
2.2 Wet or Electrochemical Corrosion
Wet corrosion occurs due to the existence of separate anodic and catholic areas, between which
current flows through the conducting solution. It involves flow of electron current between the
anodic and cathodic areas through electronic conductor. When a metal is in contact with an acid
solution or dissimilar metals are dipped partially in a corrosive environment this type of corrosion
can be observed.
2.2.2 Mechanism of rusting: Rusting is the name more commonly referred for the corrosion of
iron. When iron is exposed to atmosphere, in the presence of moisture, it undergoes corrosion.
Depending upon the concentration of oxygen present in the environment different types of
corrosion products are produced. Figure 3.3 illustrates the rusting process of iron.
3 GALVANIC SERIES
The galvanic series is a listing of measured corrosion potentials of metals and alloys in natural sea
water in the order of their corrosion tendencies / corrosion resistence.
2. The electrochemical series does not account for corrosion behavior of alloys. The
electrochemical series lists Eo values of pure metals. But engineering applications involve many
alloys under various circumstances. Consequently, a more practical series called galvanic series
has been prepared by studying corrosion of metals and alloys in a given environment like sea
water.
3.2 Galvanic Series
Mg Active (more anodic)
Mg alloys
Zn
Al
Cd
Mild Steel Increasingly Active Increasingly Inert
Cast Iron
Stainless steel
Nickel
Ag
Ti
Graphite
Au
Pt Passive (more cathodic)
Similarities: In both, base metals are placed higher and noble metals lower in the series.
4. TYPES OF CORROSION
This form of corrosion occurs when two dissimilar metals are in physical contact in an aqueous
electrolyte. The less resistant metal acts as anode and the more resistant metal acts as cathode.
Figure 3.4 depicts galvanic corrosion.
Pitting corrosion is a localized attack that results in extreme cases holes in the metal. Surface
appears rough as pits are sometimes isolated or close together. Generally a pit may be described as a
cavity or hole with the surface diameter about the same length as or less than the depth. Pitting is
localized and intense form of corrosion and failure often occurs with extreme suddenness without
prior indication.
The important reasons for the pitting corrosion include
Surface roughness or non- uniform finish.
Whenever dust particles are deposited, owing to the different amount of oxygen in contact, with
metal, the small part beneath the impurity becomes the anodic areas and the surrounding large parts
become the cathodic areas. Intense corrosion starts just underneath the impurity. Examples: peeling
of tin coat on iron, deposition of dust, sand on the steel surface Pitting form of corrosion can be
represented as shown in Figure 3. 5
4.4 Stress Corrosion: Stress corrosion or cracking refers to cracking caused by the combined
effect of a tensile stress (residual, applied or thermal) and a specific corrosive environment. During
stress corrosion/ cracking, the metal or alloy is virtually un-attacked over most of its surface, while
fine cracks progress through it. The two classic cases of stress corrosion cracking are season
cracking of brass cartridges and caustic embrittlement of steel boilers. Figure3.9 indicates stress
corrosion cracking.
The metal atoms under stress are at higher energy levels compared to those free from stress. The
stressed part of the metal becomes more reactive than the stress free part. Corrosion cell are formed
withstressed part acting as anode and stress-free part acting as cathode. The stressed part undergoes
corrosion under specific corrosive environment, initiating the crack. Thus the stress corrosion is
characterized by three distinct steps of crack initiation, crack propagation and final failure.
The caustic embitterment is a typical example of stress corrosion. This is a dangerous form of
stress corrosion observed in boiler. Water fed into boilers may contain free alkali. Water softened by
lime soda process contains sodium carbonate. Under high temperature and pressure prevailing
within boilers sodium carbonate hydrolyses to sodium hydroxide and carbon dioxide.
Figure 3.10. Effect of temperature on corrosion rate of Ni in HCl and stainless steel in HNO3
Structures should be so designed that water does not collect at the top or in the crevices. Profile
should be so designed that water is drained completely and moisture retention should be as low as
possible.
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b) Avoid crevices: Crevices allow moisture and dirt to be trapped which result in increased
corrosion.If crevices are either present in a structural or cannot be avoided they should be filled
by welding or by using filler.
d) Avoid sharp corners and bends: These are the potential corrosion sites and these must be
replaced by round corners. Sharp corners result in thin coating at corners and are not protected
effectively rounding the corners resulting in an even coating. Sharp bends and other areas were the
fluid direction is changed rapidly can promote corrosion and should therefore be avoided.
Figure 3. 12. Mg being used as sacrificial anode for protecting iron article
Mg is more reactive metals than iron and hence it is usually used as anode. It becomes anodic
part in contact with iron. Following reaction take place when Mg is made to couple with Iron.
At Anode: 2Mg(s) 2Mg2+ (aq) + 4e
At Cathode: O2 (g) + 2H2O (l) + 4e 4OH(aq)
Net reaction: 2Mg (s) + O2 (g) + 2H2O (l) 2Mg(OH)2
Advantages: * No external power supply is necessary.
* Can be used in remote and difficult to reach areas.
* Low installation cost.
* Minimum maintenance cost.
* Replacement is much cheaper than replacing the tank/oil pipeline
b) Impressed Current Method
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Figure3. 13. Schematic diagram of impressed current method
In this method the metallic structure is made cathode with the use of impressed current by
connecting the negative terminal of the external DC power source to the metallic structure to be
protected and positive to an inert anode. The anode may be made up of steel, graphite and platinum
group metals. The anode may be consumed very slowly or may not be consumed at all depending
on the anode material. The anode is surrounded by back film consisting of coke breeze, gypsum to
improve electrical contact between the anode and the environment if it is a poor ionic conductor.
Schematic representation of impressed method to control corrosion is shown in the Figure 3.13.
Advantages:
* Applicable to large structures and long term operations.
* Uncoated parts can be protected.
Disadvantages:
* Larger installation cost.
* Higher maintenance cost.
* High energy consumption
* Localized corrosion may occur if the impressed current is not uniform on the
entire surface.
6.3 Anodic protection method
The principle of anodic protection method is that under certain ranges of potentials a metal (which
shows active to passive transition) or alloy becomes passive, resulting in the lowering or prevention
of corrosion. Anodic protection may be understood by means of potential current density diagram as
shown in Figure 3.14
a) Anodic Inhibitors: Substances used to stop anodic reaction are called anodic inhibitors. They
form insoluble compounds with the metal ions formed at the anodic part due to its initial
corrosion. These insoluble compounds form a protective film on the anode surface. This film
isolates the anode from the electrolyte medium and stops its corrosion. The anions such as
chromate, tungstate, molybdate and phosphate are used to arrest anodic processes. Anodic
inhibitors are found to be effective provided they are added above their critical concentrations. If
the added inhibitor is insufficient, it cannot plug all the anodic sites. This leads to severe pitting
corrosion.
b) Cathodic Inhibitors: Substances used to stop cathodic reaction are called cathodic inhibitors.
They form a protective film on cathodic surface and isolate it from the electrolyte medium.
Cathodic reaction stops as a result of this.
There are two major reactions taking place on cathodic surface depending on the nature of
corrosive environment. They are: 1) Hydrogen evolution type 2) Oxygen absorption type
1) Hydrogen evolution type inhibitors:- 2H+ (aq)+ 2e- -------->H2(g) (acid medium)
The evolution of hydrogen gas over the cathode can be prevented either by retarding the diffusion
of H+ ions to the cathode or by increasing the hydrogen overvoltage. The diffusion of H + to the
cathode is retarded by the addition of certain organic compounds which contain N or S. Urea,
thiourea, mercaptans and heterocyclic nitrogen compounds are widely used as cathodic
inhibitors. Such substances are adsorbed on the cathodic sites forming a protective film that
suppresses cathodic reaction. Even the use of insufficient concentration of these substances does not
have any adverse effect.The evolution of H2 at the cathode can also be prevented by increasing
overvoltage of hydrogen. This is achieved by the addition of oxides of Arsenic, Antimony or salts
like sodium meta-arsenite .They deposit as adherent metallic film on the cathode areas thereby
prevents the evolution of H2, since hydrogen overvoltage for those metals is quite high.
2) Oxygen absorption type inhibitors:- O2(g) + 2H2O (l) + 4e 4OH (aq) (in neutral or slightly
alkaline medium)This cathodic reaction can be easily controlled either by removing the oxygen from
the corrosive media or by decreasing the diffusion rate of oxygen to cathode. Reducing agents such
as N2H4 and Na2SO3 remove oxygen from the corroding environment by combining with it.
N2H4 + O2 N2 + 2H2O
Decreasing the diffusion rate of oxygen is achieved by adding salts such as ZnSO 4, MgSO4, NiSO4
to the aqueous environment. They undergo hydrolysis and form a deposit of their insoluble
hydroxide on the cathodic sites.
Zn2+ (aq) + 2OH (aq) Zn(OH)2.
The protective film being impermeable to oxygen prevents its further diffusion to cathodic sites
Applications:
ss
of containers for storing food
stuffs
7. SUMMARY
Metallic corrosion is one of the problems often encountered in our industrialized society, and
hence it has to be studied. The damage due to corrosion is observed in practically all industrial
and domestic fields, but predominantly in chemical and petrochemical plants, combustion
motors, vehicles, turbines, hydraulic power aggregates, nuclear reactors and many other
projects. The different types of corrosion include galvanic, pitting, inter-granular and stress
corrosion. Certain factors can tend to accelerate the action of a corrosion cell and these include
nature of the metal and their relative environment, cathode and anode areas, nature of corrosion
products, hydrogen overvoltage pH of the medium, temperature and polarization Various
measures are taken in almost all industries to control the corrosion rate. In this regard it becomes
essential to understand the different forms of corrosion and factors affecting it. Corrosion control
techniques include selection of materials and proper design, cathodic and anodic protection
methods, surface coating and the use of corrosion inhibitors.
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