What is Corrosion?

  Corrosion is a process of formation of the compound of pure metal by the chemical

reaction between metallic surface and its environment. 

 It is an oxidation process. It causes loss of characteristic metallic properties 
 Hence, disintegration of a metal by its surrounding chemicals through a chemical
reaction on the surface of the metal is called corrosion.
 Deterioration of metallic articles by physical or mechanical means is not called
corrosion, rather it is described as erosion

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 Example
 Formation of rust on the surface of iron, formation of green film on the surface of copper
 Rusting of iron is the most common example of corrosion. Rust is formed on the surface of iron in the presence
of air and moisture. Rust does not have any metallic properties, so the rusted iron becomes weak.

When iron corrodes, it forms a red-brown hydrated metal oxide

(Fe2O3.xH2O), which is rust. The rust continually flakes off to
expose a fresh metal surface vulnerable to reaction with oxygen
and water. Because both oxygen and water are required for rust to
form, an iron nail immersed in deoxygenated water will not rust—
even over a period of several weeks. Similarly, a nail immersed in
an organic solvent such as kerosene or mineral oil will not rust
because of the absence of water even if the solvent is saturated
with oxygen.
3
steel deck support topside rusted steel pipe hanger (Naval ship)
brackets for topside electrical conduit
vertical ladder (Naval clamps
ship)

Railing of a bridge Cast iron pump impeller

 Example
 Copper exposed to moist air containing CO2 forms a green layer on its surface.
 This green layer is often found on the statue made of brass(Cu+Zn alloy). This green layer is
composed of CuCO3 + Cu(OH)2 popularly known as patina.

Why Statue of Liberty is Green?

Coal, which was often high in sulfur, was burned extensively in the early part of the last century. As
a result, sulfur trioxide, carbon dioxide, and water all reacted with the CuO

5
 Example

Figure 1. (a) The Statue of Liberty is covered with a copper skin, and was originally brown, as shown in this painting.
(b) Exposure to the elements has resulted in the formation of the blue-green patina seen today. 6
 Reason for Corrosion Study

 Economic (due to material loss)

 Safety (to prevent catastrophic consequences resulting from operation failure
of equipment).
 Conservation (to conserve metal resources, which are limited).

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 Types of Corrosion

Generally eight types of corrosion:

 Uniform corrosion
 Pitting corrosion
 Transgranular and Intergranular (Intercrystalline ) corrosion
 Exfoliate corrosion
 Stress corrosion
 Crevice corrosion
 Galvanic corrosion
 Erosion
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 Uniform Corrosion
 Uniform (or general) corrosion refers to the relatively uniform reduction of thickness
over the surface of a corroding material. It is relatively easy to measure, predict and
design against this type of corrosion damage.
 This type of corrosion develops as pits of very small diameter, in the order of a
micrometer, and results in a uniform and continuous decrease in thickness over the
entire surface area of the metal. 
 It is a very common form found in ferrous metals and alloys that are not protected by
surface coating or inhibitor
 The rate of uniform corrosion can be easily determined by measuring the mass loss, or the
quantity of released hydrogen
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 Uniform Corrosion
 In conventional applications this form of corrosion can usually be recognized on steels, copper alloys
and silver jewelry
 Uniform corrosion results in a homogeneous deterioration of the entire metal surface, that is exposed
to the corrosive environment. This initially causes a change in the visual appearance of the surface, at
which point the impact on the mechanical properties of the material are negligible.
 If the corrosion process is allowed to continue, then it leads to gradual loss of weight and decrease in
dimensions. As it occurs uniformly in a given environment, the lifetime of a material can be estimated
by carrying out corrosion tests in order to measure the rate of corrosion. For that purpose, the
corrosion test has to be carried out in conditions similar to the real application environment. 
 In the case of steels in outdoor conditions with regular exposure to moisture and oxygen, uniform
corrosion is caused by randomly distributed anodic and cathodic areas on the surface, that migrate as
the process takes place 10
Uniform Corrosion

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 Pitting Corrosion
Pitting is initiated by:
  Localized chemical or mechanical damage to the protective oxide film; water chemistry factors which
can cause breakdown of a passive film are acidity, low dissolved oxygen concentrations (which tend to
render a protective oxide film less stable) and high concentrations of chloride (as in seawater) 
 Localized damage to, or poor application of, a protective coating 
 The presence of non-uniformities in the metal structure of the component, e.g. nonmetallic
inclusions.

Apart from the localized loss of thickness, corrosion pits can also be harmful by acting as stress risers.
Fatigue and stress corrosion cracking may initiate at the base of corrosion pits. One pit in a large system
can be enough to produce the catastrophic failure of that system. An extreme example of such
catastrophic failure happened in Mexico, where a single pit in a gasoline line running over a sewer line
was enough to create great devastation to a city, killing 215 people in Guadalajara.  12
 Pitting Corrosion
 Pitting corrosion is a localized form of corrosion by which cavities or "holes" are produced in the
material. Pitting is considered to be more dangerous than uniform corrosion damage because it is
more difficult to detect, predict and design against.
 This localized form of corrosion is characterized by the formation of irregularly shaped cavities on the
surface of the metal. Their diameter and depth depend on several parameters related to the metal,
the medium and service conditions.

  A small, narrow pit with minimal overall metal loss can lead to
the failure of an entire engineering system.
 Unlike uniform corrosion, the intensity and rate of pitting
corrosion can be assessed neither by determining the mass
loss nor by measuring released hydrogen.
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 Pitting Corrosion
  Pit growth. In presence of chloride ions pits are growing by autocatalytic mechanism. Pitting corrosion
of a stainless steel is illustrated in the figure:
  Anodic reactions inside the pit:
 The electrons given up by the anode flow to the cathode (passivated
surface) where they are discharged in the cathodic reaction:

 As a result of these reactions the electrolyte enclosed in the pit gains

positive electrical charge in contrast to the electrolyte surrounding the pit,
which becomes negatively charged. The positively charged pit attracts
negative ions of chlorine Cl- increasing acidity of the electrolyte according to
the reaction:
pH of the electrolyte inside the pit decreases (acidity increases) from 6 to 2-3, which causes further
acceleration of corrosion process. High electron demand by the large cathode is put on the small
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anode, the result is intense pitting corrosion.
 Intergranular Corrosion
 Intergranular corrosion (IGC), also known as intergranular attack (IGA), is a
form of corrosion where the boundaries of crystallites (grains) of the material
are more susceptible to corrosion than their insides
 The microstructure of metals and alloys is made up of grains, separated by
grain boundaries. Intergranular corrosion is localized attack along the grain
boundaries, or immediately adjacent to grain bondaries, while the bulk of the
grains remain largely unaffected. This form of corrosion is usually associated
with chemical segregation effects (impurities have a tendency to be enriched
at grain boundaries) or specific phases precipitated on the grain boundaries.
Such precipitation can produce zones of reduced corrosion resistance in the
immediate vicinity.
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 Intergranular Corrosion
 The attack is usually related to the segregation of specific elements or the formation of a compound in
the boundary. Corrosion then occurs by preferential attack on the grain-boundary phase, or in a zone
adjacent to it that has lost an element necessary for adequate corrosion resistance - thus making the
grain boundary zone anodic relative to the remainder of the surface. The attack usually progresses
along a narrow path along the grain boundary and, in a severe case of grain-boundary corrosion, entire
grains may be dislodged due to complete deterioration of their boundaries.
 Causes of this corrosion:
• Segregation of the impurities at the grain boundary, e.g. Fe in Al alloy
• Enrichment of one of the alloying elements or depletion of one of these elements in the grain
boundary areas

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 Intergranular Corrosion
Figure: Chromium depletion at the grain boundary of stainless steel

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 Exfoliation Corrosion
Exfoliation corrosion is a type of selective corrosion that propagates along a large number of planes
running parallel to the direction of rolling or extrusion. In metallurgy, exfoliation corrosion (also called
lamellar corrosion) is a severe type of intergranular corrosion that raises surface grains from metal by
forming corrosion products at grain boundaries under the surface. It is frequently found on extruded
sections where grain thickness is not as thick as the rolled grain. It can affect aircraft structures, marine
vessels, heaters and other objects. Between these planes are very thin sheets of sound metal that are not
attacked, but gradually pushed away by the swelling of corrosion products, peeling off like pages in a book;
hence the term exfoliation corrosion.

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Exfoliation Corrosion

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 Stress Corrosion
 It is the cracking induced from the combined influence of tensile stress and
a corrosive environment.
 Stress-corrosion occurs when a material exists in a relatively inert
environment but corrodes due to an applied stress
 This form of corrosion is particularly dangerous because it may not occur
under a particular set of conditions until there is an applied stress. The
corrosion is not clearly visible prior to fracture and can result in
catastrophic failure  
 Many alloys can experience stress corrosion, and the applied stress may
also be due to a residual stress in the material. An example of a residual
stress could be a stress remaining in a material after forming, or a stress
due to welding. 20
Stress Corrosion

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 Crevice Corrosion
 Crevice corrosion refers to corrosion occurring in confined spaces to which the
access of the working fluid from the environment is limited. These spaces are
generally called crevices. Examples of crevices are gaps and contact areas
between parts, under gaskets or seals, inside cracks and seams, spaces filled with
deposits and under sludge piles. 
 Crevice corrosion is an electrochemical oxidation-reduction (redox) process,
which occurs within localized volumes of stagnant solution trapped in pockets,
corners or beneath a shield (seal, deposit of sand, gasket, fastener, etc.).
 Crevice corrosion is highly accelerated if chloride, sulphate or bromide ions are
present in the electrolyte solution.
 Stainless steels, Aluminum alloys and other metals forming a passive oxide layers
on their surfaces in electrolytes and atmosphere are sensitive to crevice corrosion 23
 Crevice Corrosion
 Mechanism of crevice corrosion is similar to that of Pitting corrosion: dissolution of the passivating
film and gradual acidification of the electrolyte caused by its insufficient aeration (Oxygen
penetration).
 Typically, the electrolyte won’t pose a problem at first. However, as it remains in the crevice, oxygen
levels will deplete. This then triggers a surplus of positive metal ions within the crevice, turning the
interior of the crevice into an anodic node. 
 The surrounding solution will then attempt to balance this situation by sending negative ions into the
crevice (often in the form of chloride ions) further enhancing acid creation and attacking the metal.

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Crevice Corrosion

25
 Crevice Corrosion
 Consider bolted metal plates exposed to seawater as shown in the figure. The small crevice (A) inside
the assembly forms the anode and the outside area, the cathode.
 At the anodic areas, as usual oxidation would occur inside the crevices which form the anodes. 

 The oxygen inside the crevice is depleted due to the consumption in the cathodic reaction. The
phenomenon inside the crevice makes the surface area inside the crevice a small anode compared to
the outside of a crevice. This is virtually the formation of a differential aeration cell. The formation of
differential aeration cell accelerates the metal dissolution inside the crevice. At the cathodic areas,
reduction of oxygen takes place:

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 Crevice Corrosion
 The amount of oxygen inside the crevice is depleted due to its consumption in the cathodic reactions
such as the reaction utilizing the Cl- ions from the electrolyte. The metal in the crevice, however,
continues to corrode and an excess of metal ions and Mz+ are accumulated. These positive ions attract
the negative Cl- ions and a metal chloride (MCl) is formed, which reacts with water for form a metal
hydroxide (MOH) which leaves a free acid (M+Cl-).

 The production of free acid causes metal dissolution and accelerates the anodic reaction. Each ion
which dissolves, releases an electron which flows through the metallic particle and combines with
oxygen to form hydroxide ions, outside the crevice. The outside of the crevice is protectd by the
cathodic protection and it does not corrode.
 As more and more anodic dissolute proceeds, more Cl- ions are attracted, more hydrolysis occurs and
crevice corrosion proceeds unchecked. 27
Crevice corrosion
 Chlorides concentrate inside the crevice (the anode), worsening the
situation.
 Ferrous ions form ferric chloride and attack the stainless steel
rapidly.
 The pH and the oxygen content are lower in the crevice than in the
bulk water solution, just as they are inside a pit.
 The pH inside the crevice may be as low as 2 in a neutral solution.
Once a crevice has formed, the propagation mechanism for crevice
corrosion is the same as for pitting corrosion.
Crevice corrosion
The major factors influencing crevice corrosion are:
 crevice type: metal-to-metal, metal-to-non-metal
 crevice geometry: gap size, depth, surface roughness
 material: alloy composition (e.g. Cr, Mo), structure
 environment: pH, temperature, halide ions, oxygen
 Galvanic Corrosion
 Galvanic corrosion is an electrochemical process in which one metal corrodes preferentially when in
electrical contact with a different type of metal and both metals are immersed in an electrolyte.
 When two metals having different electrode potentials are in contact with each other in the presence
of an electrolyte, one metal acts as a cathode whereas the other acts as an anode. This leads to an
electrochemical reaction as a result of which, the anode is dissolved into the electrolyte. This
electrochemical process is called galvanic corrosion of metals.
 This leads to the anodic metal corroding more quickly than it otherwise would; the corrosion of the
cathodic metal is retarded even to the point of stopping.
 The presence of electrolyte and a conducting path between the metals may cause corrosion where
otherwise neither metal alone would have corroded.

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Galvanic Corrosion

31
Galvanic Corrosion

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 Galvanic Corrosion
 A common example of galvanic corrosion is the Statue of Liberty: galvanic corrosion of the iron armature
in contact with the copper skin.
 The results of galvanic corrosion on the statue were very serious rust, weakening of armature bars, etc.
 After considering all options to halt the corrosion process, it was decided to replace the iron armature
throughout the Statue; it was necessary to take into account corrosion resistance and mechanical
properties of any replacement material. Atmospheric exposure tests were conducted to determine a
suitable replacement armature material. Finally, the type 316L stainless steel was chosen to replace the
iron armature of the Statue not only because of its excellent corrosion resistance and compatibility with
copper, but also because of it strength, ductibility and ability to be fabricated

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 Erosion
 Erosion corrosion is a degradation of material surface due to mechanical action, often by impinging
liquid, abrasion by a slurry, particles suspended in fast flowing liquid or gas, bubbles or droplets,
cavitation, etc.
 This type of corrosion is related to the flow speed of the corrosive fluid.
 It leads to local thinning of the metal, which results in scratches, gullies, and undulations, which are
always oriented in the same direction, namely the flow direction.

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DIFFERENT THEORIES OF CORROSION

 Dry or chemical theory of corrosion and

 Wet or Galvanic or electrochemical theory
Dry corrosion: Corrosion by oxygen
Dry corrosion: Corrosion by oxygen
In oxidation corrosion, the nature of the oxide film plays an important role. It may be
Dry corrosion: Corrosion by oxygen
 Pilling-Bedworth Ratio
 The Pilling–Bedworth ratio (P–B ratio), in corrosion of metals, is the ratio of the volume of the
elementary cell of a metal oxide to the volume of the elementary cell of the corresponding metal (from
which the oxide is created).
 On the basis of the P–B ratio, it can be judged if the metal is likely to passivate in dry air by creation of a
protective oxide layer or not.

For MgO, n=1

For V2O5, n=2

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Pilling-Bedworth Ratio

40
Dry corrosion: Corrosion by oxygen
Dry corrosion: Corrosion by hydrogen
Dry corrosion: Corrosion by hydrogen
 Wet or Electrochemical Corrosion
Wet corrosion refers to the degradation and/or rust formation on a
metal surface that occurs due to the generation of a reactive
electrochemical cell.
i) A metal is exposed to two different concentrations of environment.
ii) Two different metals are in contact in a medium.
• At anode:- Oxidation (Corrosion) takes place, i. e.

• At cathode:- Reduction takes place, Where electrons are consumed.

• Corrosion of an anode is based on how electrons are consumed at
cathode.
• At cathode consumption of electron takes place either by-
a. Liberation/ evolution of hydrogen
b. Absorption of oxygen
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Wet corrosion: electrochemical corrosion
Wet corrosion: Oxygen absorption
 Corrosion Rate
 Corrosion rate is the speed at which any metal in a specific environment deteriorates. It also can be defined as the
amount of corrosion loss per year in thickness. The speed or rate of deterioration depends on the environmental
conditions and the type and condition of the metal under reference.
 Several pieces of data must be collected when calculating the corrosion rate of any given metal. Required data
includes:
Weight lost (the decrease in weight of the metal during the period of reference), density of the metal, total surface
area initially present, length of time taken.
 The rate of corrosion reaction is expressed in various units. The most commonly used units are:

• mdd (milligram weight loss per square decimeter per day)

• ipy (inch penetration per year
• gmd (gram weight loss per square meter per day
• mils (1 mil = 0.001 inch penetration per year  
47
 Factors Effecting Corrosion
 The rate of corrosion mainly depends on two factors:
1. Nature of the metal
2. Nature of the corroding Environment

Nature of the metal Nature of the corroding environment

Physical state Temperature
Purity of the metal Humidity of air
Position in galvanic series Presence of impurity in atmosphere
Over voltage Influence of pH
Nature of surface film Microbial corrosion
Passivity Concentration of dissolved oxygen
Concentration of dissolved salts

48
Factors affecting corrosion
Factors affecting corrosion
 Factors Effecting Corrosion
 Position in galvanic series:
When two different metals are in contact in presence of Medium, the more active metal (top in galvanic series)
undergoes Corrosion. The rate of corrosion depends on difference in their positions.

 Passivity:
Metals like Ti, Al, Ca, and Mg are passive and they have high corrosion resistance. This is due to formation of
protective oxide film having salt-healing nature

51
 Factors Effecting Corrosion
 Humidity of air:
Rate of corrosion increases with increase in humidity and the relative humidity above which the rate of corrosion
increases sharply is called critical humidity.
 Temperature:
The rate of corrosion increases with increase in temperature.

52
 Factors Effecting Corrosion
 Corrosion is a chemical reaction. As with any chemical reaction, the hotter the chemical, the faster the reaction.
This is because as any molecule heats up it gets excited and vibrates at a higher frequency. This increases its
‘collision rate’ with other chemicals that it may react with, and in turn increases the chemical reaction rate.
 In fact, there’s a rule of thumb that the corrosion rate of a metal doubles for every 10°C increase in temperature.
So if for example, if the corrosion rate is 10 mpa (mils per anum) at 50°C, expect it to be 20 mpa at 60°C.
 Oxygen level is the main variable here. Oxygen is the active ingredient of corrosion, hence the term ‘oxidation ‘.
This is apparent when we compare open vent systems vs sealed systems.
 In an open vented system, the water rapidly reduces its ‘dissolved oxygen’ content as the system heats up above
80°c. The fact it’s open to the atmosphere means this oxygen can leave the system and so after this temperature
the corrosion rate begins to drop rapidly.
 In a sealed system however, the fact its slightly pressurised increases this oxygen saturation temperature and so
the oxygen stays within the water. The fact the system is sealed also gives nowhere for the oxygen to go, and so
the corrosion rate steadily increases.
53
 Factors Effecting Corrosion
 Presence of impurities in atmosphere:
Presences of gases like CO2, H2S and fumes of HCl increases acidity of liquid surrounding metals and increases
corrosion.
 Influence of pH:
Corrosion is more in acidic medium than neutral or alkaline medium.

54
 Factors Effecting Corrosion
 In the range of pH 4 to pH 10, the corrosion rate of iron is relatively independent of the pH of the
environment. In this pH range, the corrosion rate depends only on how rapidly the oxygen diffuses to the
metal surface. For pH values below 4.0, ferrous oxide (FeO) is soluble. Thus, the oxide dissolves as it is
formed rather than depositing on the metal surface to form a film. In the absence of the protective oxide
film, the metal surface is in direct contact with the acid solution, and the corrosion reaction proceeds at a
greater rate than it does at higher pH values.
 It is also observed that hydrogen is produced in acid solutions below a pH of 4, indicating that the corrosion
rate no longer depends entirely on oxygen diffusion, but on a combination of the two factors (hydrogen
evolution and oxygen diffusion). For pH values above about pH 10, the corrosion rate is observed to fall as
pH is increased. This is believed to be due to an increase in the rate of the reaction of oxygen with
Fe(OH)2 (hydrated FeO) in the oxide layer to form the more protective Fe2O3 (note that this effect is not
observed in deaerated water at high temperatures).

55
 Factors Effecting Corrosion
 Concentration of dissolved oxygen:

The rate of corrosion of the steel product depends on

the concentration of oxygen dissolved in the water at
the steel surface, as shown in Figure. At low
concentrations, the rate increases with increasing
dissolved oxygen concentration. At high concentrations,
the rate declines because of passivation

56
 Factors Effecting Corrosion
 Concentration of dissolved salt:
The decrease of corrosion rate at higher conc. of NaCl is
due to decreased dissolved oxygen with increased salt
conc., a phenomenon called salting out effect. The initial
rise of corrosion rate is due to the followings:
• With small increase in conc., conductivity of water
increases, which favors the electro-chemical
mechanisms of corrosion
• At small salt conc., there will be sufficient amount of
oxygen for the reaction to corrode metal surface
• As conductivity of water increases, the anode and
cathode can operate staying quite a part away from
each other. As a result, ions are form at far away from
57
each other and formation of Fe(OH)2 may not occur.
 Microbial Corrosion
 Microbial corrosion, also called microbiologically influenced corrosion (MIC), microbially induced corrosion (MIC) or
biocorrosion, is "corrosion affected by the presence or activity (or both) of microorganisms in biofilms on the
surface of the corroding material." This corroding material can be either a metal (such as steel or aluminum alloys)
or a nonmetal (such as concrete or glass).
 Some sulfate-reducing bacteria produce hydrogen sulfide, which can cause sulfide stress cracking. Acidithiobacillus
bacteria produce sulfuric acid; Acidothiobacillus thiooxidans frequently damages sewer pipes.
 Ferrobacillus ferrooxidans directly oxidizes iron to iron oxides and iron hydroxides; the rusticles forming on the RMS
Titanic wreck are caused by bacterial activity. Other bacteria produce various acids, both organic and mineral, or
ammonia.
 In presence of oxygen, aerobic bacteria like Acidithiobacillus thiooxidans, Thiobacillus thioparus, and Thiobacillus
concretivorus, all three widely present in the environment, are the common corrosion-causing factors resulting in
biogenic sulfide corrosion.

58
 Microbial Corrosion
 Some sulfate reducing anaerobic bacteria also cause corrosion
 Layers of anaerobic bacteria can exist in the inner parts of the corrosion deposits, while the outer parts are
inhabited by aerobic bacteria.
 Some bacteria are able to utilize hydrogen formed during cathodic corrosion processes.
 Bacterial corrosion may appear in form of pitting corrosion, for example in pipelines of the oil and gas industry.
Anaerobic corrosion is evident as layers of metal sulfides and hydrogen sulfide smell. On cast iron, a graphitic
corrosion selective leaching may be the result, with iron being consumed by the bacteria, leaving graphite matrix
with low mechanical strength in place.

59
 Prevention of Corrosion
 Corrosion can be prevented by the following general methods:

• Modification of metals
• Modification of the environments
• Electro-chemical methods
• Applying protective coatings
• By proper designing

60
 Modification of Metals
 A metal can be modified by two ways:
i. By purifying it
ii. By making alloy
iii. By passive oxide film formation

• The first choice is to use noble metals such as gold and platinum.
• The next choice is to use purest possible metal.
• Thus, the next choice is the use of corrosion resistant alloys.
• Stainless steel containing chromium produce an exceptionally coherent oxide film which protects the steel from
further attack
• Cupro-nickel (70% Cu +30%Ni) alloys are now used for condenser tubes and for bubble trays used in fractionating
column in oil refineries.
• Highly stressed Nimonic alloys (Ni-Cr-Mo alloys) used in gas turbines are very resistant to hot gases. 61
 Modification of the Environments
 The corrosive nature of the environment can be reduced by two ways:
i. By removing harmful constituents from the environment
ii. By adding specific substances (inhibitors) to the environment

• In under water corrosion acidity, dissolved oxygen, dissolved salts etc. play important role on the rate of corrosion.
So, by removing these substances the rate of under water corrosion can be reduced to a large extent.
• Moisture content is an important factor for atmospheric corrosion. Reducing moisture content below the threshold
value decreases the atmospheric corrosion to a great extent.
• The pH of aq. Medium can be changed by adding small amount of metal carbonates, hydroxides etc.

62
 Modification of the Environments
Dissolved oxygen in water can be removed by the following ways:
 Spraying water in an evacuated chamber at a low temperature
 Allowing water to come in contact with scrap iron. The dissolved oxygen of water is removed by the oxidation of
scrap iron
 Applying heat with constant agitation
 Addition of some chemicals such as sodium sulfite, hydrazine etc.

2Na2SO3 + O2 2Na2SO4

H2N-NH2 + O2 N2 + 2H2O

 Freshly prepared ferrous hydroxide can be used for the removal of dissolved oxygen.

63
 Modification of the Environments
By using inhibitors:
Inhibitors are defined as the substances, which when added in small amount to the corrosive environment, decrease
the rate of reaction. These substances bring about certain chemical changes on the metal surface and thereby make
them inactive for the corrosion reaction. Several types of inhibitors:
 Anodic Inhibitors
 Cathodic Inhibitors
 Passivating inhibitors
 Non-passivating or vapor phase inhibitor

64
Prevention of Corrosion
Modification of environment: Anodic inhibitors
Inhibitors which retard the corrosion of metals by forming a
sparingly soluble compound with a newly produced metal cations.
This compound will then adsorb on the corroding metal surface
forming a passive film or barrier. Anodic inhibitors are used to
repair
a) the crack of the oxide film over the metal surface
b) the pitting corrosion
c) the porous oxide film formed on the metal surface.
Exemples: Chromate, phosphate, manganate, tungstate, nitrate,
silicate, molybdate etc.
Prevention of Corrosion
Modification of environment: Cathodic inhibitors
In an acidic solution: the main cathodic reaction is the liberation of hydrogen
gas, the corrosion can be controlled by slowing down the diffusion of H+ ions
through the cathode.

Examples: amines, mercaptans, thiourea, reductible salts of As, Sb etc.

In neutral solution: In a neutral solution, the cathodic reaction is the
adsorption of oxygen or formation of hydroxyl ions. eliminating oxygen from
the corroding medium or by retarding its diffusion to the cathodic area.

Example: hydrazine,Na2SO3, H2O2, salts of Mg, Zn or Ni.

Salts of metals react with hydroxide ion to form corresponding hydroxides,
which get deposited on the cathode forming impermeable barriers.
Prevention of Corrosion
Modification of environment: Passivators
 Passivators are the substances which contain ions those are oxidizing
agents. Example: Chromates, Nitrites, Molybdates etc. The inhibitors
normally get in contact with the metal and thereby react to produce thin
film on metal surface.
 Some substances do not have inhibiting capacity alone. They indirectly
enhance the passivation of iron and some other metals by providing
favorable condition for the absorption of oxygen. Example: NaOH, Na3PO4,
Na2B4O7 etc. These are non-oxidizing and require dissolved oxygen in
order to act as inhibitor.
 Some other non-oxidizing compounds such as sodium benzoate, sodium
cinnamate, sodium polyphosphate etc. passivate iron in the near neutral
range by the absorption of dissolved oxygen.
Prevention of Corrosion
Modification of environment: Vapor phase inhibitors
 These are organic inhibitors which are readily vaporised and form a
protective layer on the metal surface.
 These are conveniently used to prevent corrosion in closed spaces, storage
containers, packing materials, sophisticated equipments etc.
 Examples are Dicyclohexylammonium nitrate, dicyclohexyl ammonium
chromate, benzotriazole, phenylthiourea etc.
Prevention of Corrosion
Electrochemical Method:
 Cathodic Control
 Anodic Control
Corrosion control: Cathodic protection
Sacrificial anodic protection (Galvanic protection)
 An electrochemically more active metal is placed in contact with the
metal structure which is to be protected. Therefore, the whole
corrosion reaction is concentrated to the more active metal
(sacrificial anode) saving the metal structure in interest from the
corrosion.
 Commonly used sacrificial anodes are Zn, Mg, Al etc.
 Protection as buried pipelines, underground cables from soil
corrosion.
 Insertion of magnesium sheets into the domestic water boilers to
prevent the formation of rust.
 Calcium metal is employed to minimize engine corrosion.
Corrosion control: Cathodic protection
Sacrificial anodic protection (Galvanic
protection)
Corrosion control: Cathodic protection
Impressed current corrosion
 An impressed current is applied in opposite direction to nullify
the corrosion current and convert the corroding metal from
anode to cathode.
 Impressed current cathodic protection has been applied to open
water box coolers, water tanks, buried oil or water pipes,
condensers, transmission line towers, marine piers, laid up
ships etc.
Problems and Limitations of Cathodic
Control

Please see the attached scan copy on corrosion.

Corrosion control: Anodic protection
 Current is applied in a direction that renders the metal more anodic
and thereby passivates itself. In this case, there is the formation of a
protective film on metal by externally applied anodic current.
 Anodic protection is used for carbon steel storage tanks containing
extreme pH environments including concentrated sulfuric acid and 50
percent caustic soda where cathodic protection is not suitable due to
very high current requirements.
 In anodic protection potentiostat is used to maintain a metal at
constant potential with respect to reference electrode. Out of three
terminals of potentiostat one is connected to tank to be protected.
Another to an auxiliary cathode(platinum). Third to reference
electrode. Thus potentiostat maintains a constant potential between
tank and reference electrode.
Corrosion control: Anodic protection
 Anodic Protection
Advantages and limitations of anodic protection:

Please see the attached copy.

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 Applying Coating Materials
These coatings act as a physical barrier between the coated metal surface and the environment. This is the most
common and widely used method. Depending on the nature protective coatings are mainly classified into three
different classes.

 Inorganic metallic coating

 Inorganic non-metallic coating
 Organic coating
Organic coatings are again classified into four classes-
• Paint
• Varnish
• Enamels
• Lacquers

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 Applying Coating Materials
Metallic Coating:
Most often used metallic coatings are of Zn, Sn, Ni, Cu, Cr, Al and Pb.
Methods of applying metallic coatings are:
 Hot-dip process
 Electro-plating
 Metal spraying
 Cementation
 Metal cladding
 Cathode sputtering

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Applying Coating Materials: Hot-Dip Process
Hot-dip galvanizing process:
This method is usually used for applying coatings of metals whose melting points are considerably lower (Zn, Sn, Pb
etc.) than those of the base materials (Fe, Cu, steel etc.). The process in immersing the base metal in a bath of the
molten coating metal, covered by a molten flux layer (usually ZnCl2).

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 Applying Coating Materials: Electroplating
Electroplating is a general name for processes that create a metal coating on a solid substrate through the reduction
of cations of that metal by means of a direct electric current. The part to be coated acts as the cathode (negative
electrode) of an electrolytic cell; the electrolyte is a solution of a salt of the metal to be coated; and the anode
(positive electrode) is usually either a block of that metal, or of some inert conductive material. The current is
provided by an external power supply.

Electroplating is widely used in industry and decorative arts to improve the surface qualities of objects—
such as resistance to abrasion and corrosion, lubricity, reflectivity, electrical conductivity, or appearance. It
may also be used to build up thickness on undersized or worn-out parts, or to manufacture metal plates
with complex shape, a process called electroforming. It is also used to purify metals such as copper.

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 Applying Coating Materials

Simplified diagram for electroplating copper (orange) on a conductive object (the cathode, "Me",
gray). The electrolyte is a solution of copper sulfate, CuSO4. A copper anode is used to replenish the
electrolyte with copper cations Cu2+ as they are plated out at the cathode.
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Applying Coating Materials: Metal Spraying
This method is widely used for applying Al, brass, Zn, Cu, Pb and various other metals. This method consists of
three steps:
 Melting of the coating metal
 Atomizing the molten metal
 Depositing the atomic metal on the surface of the metal to be coated

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 Applying Coating Materials: Cementation
 This type of coating is obtained by heating the base metal in a revolving drum containing a powder of
coating metal.
 The process is suitable for coating small articles of uneven surfaces & intricate shapes like bolts, screws,
threded parts, vaives etc.

a) Sherardizing (Zn powder is used as coating metal)

b) Colorizing (Al powder is used as coating metal)
C) Chromizing (Cr powder is used as coating
metal)Melting of the coating metal

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Applying Coating Materials: Metal Cladding
 Base metal is covered with thin sheets of noble metals like gold, Pt etc.
 The principal cladding techniques includes hot-roll bonding, cold-roll bonding, explosive bonding and weld
cladding, although centrifugal casting, adhesive bonding, extrusion and hot isostatic pressing have also
been used to produce clad metals.
 Clad metals can be provided in plate, sheet, tube, rod and wire forms. Most engineering metals and alloys
can be clad.
 Applications include pressure vessels, reactors, heat exchangers and storage tanks.

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Applying Coating Materials: Cathode Sputtering
 Very similar to that of cathode ray’s experiment
 the destruction of the negative electrode (cathode) in a gas discharge as a result of the impact of positive 
ions. In a broader sense it is the destruction of a solid through bombardment by charged or neutral particles.
 This technique is specially useful for depositing thin metallic films on materials those are electrically
nonconductors e.g., fabrics, phonographic recording waxes etc.

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Applying Coating Materials: Non-metallic Coating
Among various inorganic non-metallic coatings the followings are important: 
 Anodized oxide coatings
 Vitreous or porcelain enamel
 Surface conversion or chemical-dip coatings.

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Applying Coating Materials: Anodized Oxide Film
 Al readily oxidizes and form oxide film, which can act as preventive layer
 By making Al as an anode in an electrolyte bath containing chromic acid or oxalic acid or sulfuric acid, a
thicker and stronger aluminium oxide film can be produced which can function as a protective layer.
 The properly prepared, anodized oxide coating provides high protection to the underlying metal and
possesses good resistance and abrasion.

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Applying Coating Materials: Vitreous Enamel
 Vitreous or porcelain enamel is a glassy material whose basic components are very similar to glass.
 Powdered glass applied on metal surface and heated in furnace
 Susceptible to mechanical damage or cracking by thermal shock
 These are chemically inert and is not attacked by most of the corrosive agents present in different
environments
 Because of the inertness, these are widely used in many industries such as in pharmaceuticals, dairy, food,
beverage industries etc.
 Vitreous enamel coated steel structural articles such as tabletops, kitchen utensils, bathtub, sanitary wares,
basin etc. are found to be used in many hospitals

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Applying Coating Materials: Surface Conversion
 These coatings are applied on the metal surface by both physical and chemical methods such as immersion,
spraying or electro-chemical process.
 The metal on which coating is to be applied is immersed in a solution of suitable chemical substances, which
reacts with metal surface producing an adherent coating.
 These coatings serve as excellent bases for the application of paints, enamels and other organic protective
coatings.
 The most commonly used surface corrosion preventive coatings are chromate, phosphate and oxide
coatings.

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 Organic coating

 Paint: mixture of insoluble pigments (metal oxides; e.g. TiO2, Pb3O4,

Fe2O3, ZnCrO4, PbCO3, BaSO4, clay etc.) in organic vehicle (natural
oil).
 Paint is not useful to protect buried structures.
 Natural oil based paints not recommended for metal structures totally
immersed in water.
 Varnishes: mixture of drying oil, dissolve resin and volatile thinner.
 Lacquers: resin dissolved in volatile thinner.
Corrosion control
Proper designing
 Use always simple design and structure
 The design must avoid more complicated shapes having more
angles, edges, corners etc.
 Avoid the contact of dissimilar metals as they may lead to
galvanic type corrosion.
 As far as possible, crevices (gap or crack) should be avoided
 Bolts and rivets should be replaced by proper welding
Prevention of Corrosion
Importance of Preventing Corrosion
 Increases equipment availability in defense service.
 Reduces rehabilitation costs.
 Means to incorporate best particles and best value products.
 Allows testing of new technologies.
 Compliance with environmental laws and regulations.
 Decreases intervals in calibration requirements.
 Extends life expectancy of equipments