CORROSION

Department of Chemistry

GOVERNMENT COLLEGE OF TECHNOLGY

COIMBATORE-13
WHAT IS CORROSION?
 Corrosion is the process of gradual disintegration, degradation or
deterioration of metal /alloys due to chemical or electrochemical reaction
with environment.
 It is the one of the most severe problems faced by the advanced industrial
societies.
About 30-40 % of iron and steel produced annually is used to
replace the rusted materials.
WHY CORROSION OCCURS?
o Metals are generally available in nature in their compound forms
(ores).
o These are the stable form of metals. However, for getting useful
engineering materials,
i.e. the metallic form, a large amount of energy needed
to convert ores to their metallic form.
o So, metals are comparatively unstable and have a general tendency
to revert back to its compound form. This process is known as
corrosion.

𝐞𝐜𝐭𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐩𝐫𝐨𝐜𝐞𝐬𝐬
𝑴𝒆𝒕𝒂𝒍 𝒐𝒓𝒆 𝑴𝒆𝒕𝒂𝒍
𝐂𝐨𝐫𝐫𝐨𝐬𝐢𝐨𝐧

Ex: Rusting of Iron

2 Fe(s)+ 3/2 O2(g)+ x H2O → Fe2O3.xH2O(s)
(Chemical composition of Rust)
EFFECTS OF CORROSION:
Loss of metal leading to reduction in thickness which may cause
reduction in mechanical strength leading to sudden structural
collapse or breakdown.
Mechanical damage to valves, pumps etc. or blockage of pipes by
solid corrosion products.
Time is lost in making available of the parts to be replaced the
damaged parts or equipment.
The fluids stored in pipes or storage tanks get contaminated due to
chemical reaction.

TYPES OF CORROSION
(A) DRY CORROSION (CHEMICAL CORROSION)

 The corrosions that involve the direct attack of the atmospheric

gases, generally in the absence of moisture, (i.e., conducting
medium corrosion) is called as dry corrosion or chemical.
  There are three types of dry corrosion:
Atmospheric gases include
1. oxygen,
2. halogens,
3. oxides of sulphur,
4. nitrogen,
5. hydrogen sulphides etc.

(i) Oxidation Corrosion

 It occurs by direst attack of oxygen at low or high temperature on metals
usually in the absence of moisture.
At low temperature, alkali metals (Na, Li, K, Rb etc.)
and
alkaline earth metals (Be, Ca, Sr etc.) are rapidly oxidised.
However, all metals, except Ag, Au and Pt, are oxidised at high
temperature.
 Oxidation occurs first at the surface of the metal to form metal oxides as
per the following reaction:

 Further process of corrosion continues either due to the diffusion of oxide

ions into the inner metal layer or metal ions diffuse out of the surface.

 However, the nature of the metal oxide layer formed at the interface plays
an important role in determining the extent of further corrosion of the
metal.
 The metal oxides formed can be of the following types:
Stable metal oxides:
 It is impervious in nature and forms a protective coating, thus preventing
the further oxidation of metals.
Examples: oxide films of Al, Pb, Cu, Sn etc.
Unstable metal oxides:
 This type of oxide layer decomposes back to metal and oxygen as soon as it
is formed.
 So, no oxidation corrosion is observed for the metals.
Examples: Oxides of Ag and Au.

Volatile metal oxides:

 The metal oxide film volatises as soon as it is formed, thereby leaving the
underlying metal exposed to the environment for further attack. Thus, rapid
corrosion takes place.
Example: Molybdenum oxide (MoO3).

Porous metal oxides:

 The oxide layers have pores and cracks and allow the atmospheric oxygen
to access the underlying layers of metals.
 This results in unobstructed and rapid corrosion of the metal. The process
continues until the entire metal is converted into its oxides.
Examples: Oxides of Li, Mg, Na etc.
(ii) Corrosion by other gases, such as Cl2, SO2, H2S, NOx.
Depending on the chemical environment, these gases react with the metal
and forms the corrosion products, which may be protective or non-
protective.
Dry chlorine reacts with Ag to form AgCl, which is protective layer. On the
other hand, tin chloride (SnCl4) is volatile and porous.
In petroleum industries, at high temperature, H2S attacks steel forming
Fe-S scale, which is porous in nature.

(iii) Liquid metal corrosion

 This type of corrosion occurs due to chemical action of flowing liquid metals
at high temperature on solid metal or alloy.
 In several industries, molten metal passes through metallic pipes and
causes corrosion due to dissolution or internal penetration.
 For example, liquid mercury dissolves most metals by forming amalgams,
thereby corroding them.
 Also occurs in devices used for nuclear power plant in cooling system.
  Coolant (liquid sodium metal) leads to corrosion of cadmium in nuclear
plant.

(B) Wet or Electrochemical Corrosion

 The corrosion, that occurs when a metal or two dissimilar metals or alloys
are immersed or dipped partially in a conducting liquid (aqueous), is called
as wet corrosion.
 According to wet corrosion theory, the corrosion takes place due to
development of separate anodic and cathodic area/parts between which
corrosion current flows through the conducting liquid or solution.
 At the anodic part, corrosion occurs due to oxidation, i.e., dissolution of
metals with liberation of electrons.

 Cathodic reaction consumes these electrons and these reactions are

dependent on the constituents of the corrosion medium.
 The nature of corrosion medium may broadly be classified into following
four types.

If the medium is aerated and almost neutral, the oxygen is reduced in the
presence of water (H2O) to OH- ions.
O2 + 2H2O + 4e- 4OH-
If the medium is aerated and acidic, the oxygen is reduced to form water
(H2O).
O2 + 4H+ + 4e- 2H2O
If the medium is de-aerated and almost neutral, the hydrogen is liberated
along with OH- ions.
2H2O + 2e- H2 +2OH-
If the medium is de-aerated and acidic, hydrogen gas is liberated.
2H+ + 2e- H2

Example: Rusting of Iron in an aerated and neutral medium

 When a piece of iron is in contact with an aerated and neutral medium, the
corrosion process takes place due to the following reactions:

Anodic reaction: Fe Fe2+ + 2e-

Cathodic reaction: ½ O2 + H2O + 2e- 2OH-

  The metal ions formed at anode combine with hydroxide ions at cathodic
region due to high mobility of Fe2+ ions and form Fe (OH)2.
 This ferrous hydroxide further oxidized to hydrated ferric oxide (rust).

Fe2+ + 2OH- Fe (OH)2

2Fe (OH)2 + ½ O2 + (x-2) H2O Fe2O3. xH2O

 Under the limited supply of oxygen gas, the corrosion product may be black
anhydrous magnetite, Fe3O4.
3Fe (OH)2 + ½ O2 Fe3O4. 3H2O

Types of Electrochemical Corrosion

(i) Differential Metal corrosion (Galvanic Corrosion)
 It occurs when two dissimilar metals are in contact with each
other in a corrosive medium (environment).
 The metals with low reduction potential undergo oxidation
(corrosion).
 The greater is the electrode potential difference between the
anode and cathode, the greater is the corrosion rate.

Examples of galvanic corrosion include:

Underground iron pipelines connected to Zn bar, steel pipe connected
to copper plumbing, zinc coating on mild steel.

(ii) Differential Aeration corrosion (Concentration cell corrosion)

 It occurs when a metal is exposed to differential air

concentration or oxygen concentration.
 Since the cathodic reaction requires oxygen, the part of the
metal exposed to higher concentration of oxygen acts as
cathode.
  On the other hand, the metallic part exposed to lower oxygen
concentration acts as anodic region and corrosion occurs at
this region.
Some examples of differential aeration corrosions are described below:

a. Water-line Corrosion

 Ocean-going ships, water storage steel tanks or steel pipes carrying

liquid when exposed to atmosphere, undergoes this type of corrosion.
 The metallic part just below the waterline is more anodic to part
above the waterline.
 Therefore, the metal just below the waterline undergoes corrosion.
The reactions are:
Anodic reaction: Fe Fe2+ + 2e-
Cathodic reaction: ½ O2 + H2O + 2e- 2OH-
Fe2+ + 2OH- Fe (OH)2

 Ocean-going ships undergo corrosion; whereas ships sunk under the

sea water for several years, do not undergo corrosion.
 Because the ship sunk under the sea water is exposed to almost
uniform concentration of air and hence does not undergo differential
corrosion.
 Preventive measures: By using metallic coatings, using inhibitors in
fluids.

b. Pitting Corrosion
 It involves localized attack resulting in the formation of cavities.
 this corrosion occurs when a small portion of the metal surface
is defective (with cracks) or occupied by dust/ scale/
sand/water drop.

 The metal below the water drops or dust deposit is exposed to

lower concentration of oxygen and undergoes corrosion.
  Once a pit is formed, the rate of corrosion increases.

 The accelerated corrosion takes place below the deposit due to

small anodic area and large cathodic area.

c. Crevice Corrosion
It occurs generally at the crevices between two metallic objects,
e.g. bolts, nuts, rivets etc.
In contact with liquids. Crevice area has lack of oxygen and
thus becomes anodic region with respect to remaining part of
the metal, which acts as cathode.
Craves corrosion can thus be explained as accelerated attack
at the junction of two metals exposed to a corrosive
environment.

d. Stress Corrosion
o It is a localized electrochemical corrosion resulted due to the
combined effect of static tensile stress and the corrosion environment
on a metal.
o stresses during their manufacturing processes, which involve cold
working, quenching, bending, rolling, pressing, heat treatment.
o The energy levels as compared to stress and act as anode and other
areas act as cathode corrosive environment.
o The corrosion initiates crack which propagates through the metal.
However, pure metals are relatively immune to the stress corrosion.
o Typical examples of stress corrosions are: Seasonal cracking, Caustic
embrittlement of steel Metal components are subjected to uneven
metal atoms under stress are always at higher stress-free atoms.
 o Therefore, the stressed parts are more reactive cathode, resulting in
corrosion at stressed part in boiler.

e. Seasonal cracking (stress corrosion of brass)

o This type of corrosion was first observed during the British rule in
India during monsoon season.
o Due to diminished military activity during monsoon season, brass
cartridges are stored for later usage.
o After some days, it was found that cracks are developed on the
surface of the cartridges.
o It takes place due to action of susceptible agents like Cu and its alloys
and attacking agents like ammonia or amine and the residual stress.

f. Caustic embrittlement of steel Boiler

 It occurs in mild steel when exposed to alkaline solution at high
temperature and stresses.
 This is often associated with steam-boiler and heat transfer
equipment’s, in which mild steel is attacked by water of high
alkalinity at the stressed part of the boiler, when operating pressure
is between 10-20 atm.
 Fine cracks may develop at the stressed part of the boiler and
alkaline impurities pass into these cracks by capillary action.
 This water evaporates and leaves behind caustic soda in the cracks,
whose concentration thus increases.
 Thus, a galvanic cell is set up between iron at the iron under stress
and the iron in the main body.
 The cell can be represented as:
iron (under stress) | Conc. NaOH (in cracks) | dil NaOH (in
boiling water) | Iron (main body)
 Iron under stress thus act as anode and gets corroded resulting in
boiler failure.
 The boiler water contains Na2CO3, which hydrolysed at high
temperature to give NaOH.
Na2CO3 + H2O heat 2NaOH + CO2
 The so-formed NaOH flows into the hair-line cracks and crevices,
where it reacts with the iron and forms sodium ferrate (Na2FeO2).
  This sodium ferrate decomposes under heat to give NaOH, which
further reacts with iron to cause corrosion. This is called caustic
embrittlement.

2NaOH + Fe heat Na2FeO2 + H2

3Na2FeO2 + 4H2O heat Fe3O4 + 6NaOH + 4H2

Preventive measures: By applying protective coatings, using corrosion

inhibitors, performing stress releasing heat treatment.

Difference between Dry corrosion and Wet Corrosion

Dry Corrosion
1. It takes place in absence of moisture
2. It involves direct attack of atmospheric gases.
3. It is less prevalent
4. It can be explained by chemical reactions
5. It is comparatively a slow process
6. This corrosion is uniform.
Wet corrosion
1. It takes place in presence of moisture
2. It involves development of a large number of tiny galvanic cells.
3. It is more prevalent
4. It can be explained by electrochemical theory.
5. It is a fast process
6. This corrosion is non-uniform as corrosion takes place
only at the anodic region, not at the cathodic part.

Pilling–Bed worth rule

An oxide layer is protective (or) non-porous, if the volume of the metal oxide
formed is at least as great as the volume of the metal from which it is
formed.
Protective or non-porous:
Example: Al, Sn, Pb, Cu, etc.
VMO > VM
An oxide layer is non-protective (or) porous, if the volume of the metal oxide
formed is less than the volume of the metal from which it is formed.
VMO < VM

Non-protective or Porous:

Example: Alkali metals: Li, Na, K, etc.

Alkaline earth metals: Mg, Ca, Si etc.
Galvanic cell and Galvanic Series: -

These cells are formed due to 2 dissimilar metals in contact in the

presence of an electrolyte in which one metal becomes anodic and
gets corroded.
For example – Iron pipe, carrying water is anodic to copper pipe.
The questions arise as to which metal will be anode OR cathode.
This can be predicted from galvanic series by taking pairs of metal
and alloy in a given medium such as sea water and observing which
become the anode.
We can prepare a series known as the Galvanic series.
The galvanic series of many metals and alloys are given in the table.
Platinum
Gold
Graphite
Titanium
Silver
Chloriment -3 (62 Ni, 18 Cr, 18 Mo)
Haste alloy C (62 Ni, 17 Cr, 15 Mo)
18 – 8 Mo stainless Steel (Passive)
18 – 8 Stainless steels (Passive)
Chromium Stainless Steel (Passive)
Inconel (80 Ni, 13 Cr, 7 Fe) (Passive)
Nickel (Passive)
Silver Solder
Monel (70 Ni, 80 Cr)
Cupro Nickels (60 – 90W, 40 – 10 Ni)
Bronets (Cu – Sn)
Copper
Brasses (Cu - Zn)
Chloriment – 2(66 Ni, 20 Mo, 1 Fe)
Haste Alloy B (60 Ni, 30 Mo, 6 Fe, 1 Mn)
Inconel (Active)
Nickel (Passive)
Tin
Lead
Lead Tin Solders
18 – 8 Mo Stainless Steel (Active)
18 – 8 Stainless Steel (Active)
Ni – Resist (High Ni Cast iron)
Chromium Stainless Steel (active)
Cast iron
 Steel
2024 aluminium (4.5 Cu, 1.6Mg, 0.6Mn)
Cadmium
Commercial Pure Aluminium
Zn
Mg

Active OR Anode
The following inference can be made from the Galvanic Series-
1. The metals and alloys are the top of the series are less corroded while the
metal in the bottom is highly corroded.
2. The farther the metals and alloys in the series the greater is the potential
generated. Therefore, metals and alloys which are farther apart in the series
should not be coupled together.
3. When metals and alloys of the same group are coupled together there is
little danger of corrosion.
4. Same metal achieved different positions in the series. For Example –
Stainless Steel in passive state occupy more noble position as compared to
active cell.
5. Galvanic cell may also be formed in the same metal consisting of dissimilar
sections the dissimilarity may be due to any of the reason given below.
a) Different Thermal Treatment
b) Scratches and Abrasions
c) Differential Strain
d) Differential Grains
e) Grain Boundary
f) Differential Grain Size
g) Surface Condition

Cathodic protection
In cathodic protection, the corroding metal is forced to act as cathode. (i.e.)
The base metal to be protected can be converted into cathode.
This is achieved by the following methods.
(i) Sacrificial anodic protection
(ii) Impressed current cathodic protection

(i) Sacrificial anodic protection

 The metal to be protected is converted into cathode by connecting it
with more active metal (anode), The artificially made anode thus gets
gradually corroded protecting the base metallic structure.
 This process is known as sacrificial anodic protection. The metals
commonly used as sacrificial anode are Zn, Mg, Al and their alloys.
 Sacrificial anodic protection

e.g.,
(i) Protection of pipe lines, cables from soil corrosion.
(ii) Protection of ship hulls from marine corrosion.
Advantages
(i) No need of external power supply.
(ii) Installation and maintenance cost is low.
Limitations
(i) Not suited for large objects due to limited driving potential.
(ii) Uncoated parts cannot be protected.

Impressed current cathodic protection

 In this method an impressed current is applied in the opposite direction of
the corrosion current to nullify it, which converts corroding metal from
anode to cathode.
 The negative terminal of DC source is connected to metallic structure to be
protected and positive terminal to an inert anode graphite surrounded by
back fill.
 The backfill provides good electrical contact to anode. Hence the current
from the external system is impressed on the metallic structure to be
protected which act as the cathode.

Impressed current cathodic production

Advantages
(i) Larger objects can be protected due to larger driving voltage.
(ii) Uncoated parts can be protected.
Limitations
(i) Larger installation cost.
(i) Higher maintenance cost.

PROTECTIVE COATINGS
  Protective coatings are the physical barrier between the metal surface
and the environment which prevents corrosion.
 They are also used for decorative purpose and to impart some special
properties such as hardness, electrical properties, oxidation
resistance, and thermal insulation
Classification
They are broadly classified in to two types:
1. Inorganic coatings
2. Organic coatings
Organic Coatings:

 These coatings are of materials that are applied to protect or beautify

a surface.
 These include paints, varnishes, industrial maintenance coatings
and they can be applied to stationary and/or mobile sources.
 Coating of metal surface with organic paints is the most widely used
anti-corrosion coatings.
 Organic paint is a dispersion of one or more finely divided solids in
a medium, which consists of non-volatile, film-forming materials like
drying oils and resins in thinners.
 When a properly treated metal surface is painted, the thinner
evaporates leaving behind a film formed and pigments on the surface.

Inorganic Coatings (Ceramic Coatings):

 For thin film coatings, hard materials are suitable which includes
carbides, nitrides, borides and silicides of Group 14, 15 & 16 of
periodic table.
 These coatings are formed by introducing nitrogen, hydrocarbons or
silicides during the sputtering process (depositing a metal on the
surface of another by using fast ions).
 Thus, the ceramic compound is formed at the surface of the
substrate.
 Commonly available ceramic coatings are TiN, CrN, TiCN and TiAlN.
 Alloyed elements such as Al, V, Cr etc. improve the oxidation
resistance of ceramic coatings.

Electroplating (Electrodeposition)
Electroplating is the process of deposition of coating metal on the
base metal by passing a direct current through an electrolytic solution
which contains the soluble salt of the coating metal.
Objectives of electroplating
On metals
(i) To increase the resistance to corrosion of the plated metal.
 (ii) To improve the hardness and physical appearance.
(iii) To increase the decorative and commercial values of the metal.
(iv) To increase resistance to chemical attack.
(v) To improve the surface properties.
On non-metals
(i) To increase strength.
(ii) To decorate surfaces of non-metals like wood, plastic, glass.
(iii) For obtaining surface conductivity.
Principle
 It follows electrolytic cell principle. In electroplating the base metal to
be plated is taken as cathode and the metal to be coated is taken as
anode.
 The soluble salt of coat metal is used as electrolyte.
 During electrolysis, concentration of the electrolyte remains
unchanged, as the metal ions deposited from the electrolyte solution
on the cathode are replenished continuously by the ions from the
anode.
Plating Procedure
The pretreated object is placed in the plating bath for the required
time. The reduction reaction occurs and nickel gets coated over the object,
which is shown in Fig.
Reactions
At cathode: Ni2+ + 2e– Ni
At anode: H2PO2– + H2O– H2PO3– + 2H+ + 2e–
Net reaction: Ni2+ + H2PO2– + H2O Ni + H2PO3– + 2H

Applications
1. It is extensively used in electronic appliances.
2. It is used in domestic and automotive fields (e.g., jewellery, tops of perfume
bottle)
3. Electroless nickel coated polymers are used as decorative material.
4. Copper and nickel coated plastic cabinets are used in digital and electronic
instruments.

Advantages of electroless plating over electroplating

i. No electricity is required
ii. It can be easily plated on insulators
iii. Complicated parts can be plated uniformly.
iv. This coating possess unique mechanical, chemical and magnetic
features.
Chromate Conversion Coating
  Chromate Conversion Coatings are formed on metal surfaces as a result of
the chemical attack that occurs when a metal is immersed in or sprayed
with an aqueous solution of chromic acid, chromium salts such as sodium
or potassium chromate or dichromate, hydrofluoric acid or hydrofluoric
acid salts, phosphoric acid, or other mineral acids.
 The chemical attack facilitates the dissolution of some surface metal and
the formation of a protective film containing complex chromium
compounds.
 This type of coating is applicable to zinc, aluminum, magnesium and
cadmium.
 This coating typically provides superior corrosive resistance and is broadly
used in giving protection to usual household products such as hinges,
screws and other hardware items.
Bath conditions
 Coated components were immersed in acidic baths (pH < 1.8) with
chromates, dihydrogen phosphates and fluorides.
 The temperature of these baths was maintained at 25 – 30°C and the
immersion time was only 2 – 5 minutes.
 Modern working baths are based on these acidic baths with addition of
other anions (fluorides, phosphates, ferricyanides etc.) to speed up the
formation of coating.

Chemistry of Chromating
 Chromate conversion treatments actually use of a strong oxidizing
agent such as chromic acid, CrO3, a redox reaction occurs at acidic
pH (pH~2) where hexavalent chromium, either in the form of Cr2O72-
or HCrO4-, is reduced to trivalent chromium while aluminum is
oxidized to trivalent aluminum: Probably due to the presence of
fluoride ion, another reduction reaction besides that involving
chromic acid can occur.
 This reaction involves the reduction of water, hydronium ion, or
dissolved oxygen to form hydroxyl ions at the metal surface.
 This surface-localized increase in pH results in the precipitation of
an amorphous mixture of hydrated aluminum plus chromium oxides.
 The presence of fluoride ion is important for building films of
significant thickness; without its presence, film growth is extremely
slow. Fluoride presumably serves two roles.
 First, it solubilizes the aluminum oxide initially present on the
surface and allows the redox and deposition reactions to proceed.
 Second, it solubilizes a portion of the growing film, which allows
penetration of the electrolyte to the surface and ion transport from
the surface into the growing film.
Uses of chromate coating
 Low-cost option for corrosion and wear protection
 A bonding agent for paint and adhesives
 A lubrication carrier
 Final finish
 Minimal electrical resistance

Characteristics of chromate coating

 Electrical conducting coating.
 Effective protection against oxidation in the case of products applied
internally in machines.
 As a result of the excellent adhesive characteristics, chromating is a
suitable pre-treatment for further coating processes.
 Chromating has hardly any negative consequences for dimensions.
 Applications Aircraft building, aerospace industry, automotive,
electrical engineering, etc ..