[Link], Associate professor Dept.

of Chemistry

Corrosion science and Metal finishing

INTRODUCTION: The process of destruction or deterioration of metals and alloys by
chemical & electrochemical attack is called corrosion. The attack of metals by dry gases such
as O₂, Cl₂, SO2, HCl and H₂SO4, HNO3 fumes etc. are the examples of direct chemical attack
or dry corrosion, the attack of metals by moist air, moist soil, water and aqueous solutions are
the examples of electrochemical attack or Wet corrosion. Metal undergoes corrosion mainly
due to the oxidation by loosing its valence electron resulting in the formation of a corrosive
product called Rust. The rust generally contains oxides of hydroxides of carbonates &
sulphates of the metals. Due to corrosion metal looses all the valuable properties such as
shining, ductility, strength and conductivity
Causes of corrosion:
Corrosion is the reverse process of metallurgy. Metals have a tendency go back to their
original state such as the form by losing or gain of electron. In the ore form metals are more
stable and less energy than the purest form of metals. (less stable & more energy) This is the
main cause of corrosion
Theories of Corrosion:
There two important theories to explain the mechanism of corrosion.
1. Electro-Chemical theory of corrosion.
2. Chemical theory of corrosion

ELECTRO-CHEMICAL THEORY OF CORROSION OR WET CORROSION

This theory mainly explains on the basis of galvanic cell formation in the environment.
According to this theory, Metal undergoes corrosion due to oxidation by losing its valence
electron, oxidation & reduction takes place simultaneously and hence the other substance in
the environment get reduced by gaining of electrons. The metal surface where oxidation takes
place is called anode or anodic area and the metal structure in the environment where
reduction takes place is called cathode or cathodic area. These two reactions take place only
when electrons flow from anode to cathode through external circuit, moist air, soil, and
moisture. The combination of anodic area and cathodic area and the environment constitutes
a small galvanic cell in the environment. Due to the formation of these galvanic cell metals
undergo corrosion in the environment. The products formed are nonpolar, highly soluble in
water and more dangerous than direct chemical attack.
Example: Iron is taking as an example
Anodic reaction
Oxidation
Fe Fe2++ 2e (Iron goes in to the solution)
Cathodic reaction
Reduction
i) H2O +1/2 O2+2e 2OH- (with oxygen)
ii) 2H2O++2e 2OH-+H2 (without oxygen, Neutral media)\
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iii) 4H++O2+2e H2+2OH- (acidic media)

Thus the metal ion reacts with OH- get corrosion product
O2
Fe2+ + 2OH- 2 Fe(OH)2 Fe2O32H2O
Rust
TYPES OF CORROSION
1. Differential Metal or Galvanic corrosion.
2. Differential aeration corrosion (Pitting & Waterline corrosion)
3. Stress corrosion. (Caustic embrittlement)

Differential Metal (or) Galvanic Corrosion:

Metals undergo corrosion due to formation of a galvanic cell is called galvanic corrosion.
Galvanic cell is formed when two dissimilar Metals (Zn and cu) are electrically connected
and dipped in to their own solutions. The difference in electrode potential of the two metals
caused differential metal corrosion. The more active metal (Zn) acts as anode and undergoes
corrosion by loosing its valence electrons. The less active metal (copper) acts as cathode by
gaining of electrons and free from corrosion. The rate corrosion increases with increasing the
potential difference between two dissimilar metals.
Eg: Steel and iron undergoes corrosion, when they are in contact with a piece of copper wire.
Steel is more anodic to copper and hence steel undergoes corrosion but copper free from
corrosion.
Differential Aeration Corrosion
This is an extended form of electro-chemical theory corrosion. This theory explains corrosion
on the basis of 0₂ concentration cell formation on the metal structure, which is form when the
differential amount of air or O2 reacts at different part of metal structure and O2 play an
important role during the corrosion and it helps to cathode reaction.
According to aeration corrosion the metal surface which is more exposed to air or 0₂, act as
cathode and is free from corrosion, but the metal surface which is less exposed to air or 0₂
acts as anode and hence undergoes corrosion due to the formation of cell on the metal
surface.
Corrosion concentration smaller at anodic area than larger cathodic area leading to the
formation of pit, cavity or hole on the metal structure.
For ex: The metal surface is partially covered by dust or sand particle, the dust covered
area of metal surface is less exposed to air or 0₂ acts as anode and undergo corrosion, the
remaining part of the metal surface is more exposed to air or O2 act as cathode and free from
corrosion.

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Pitting Corrosion or Localised Corrosion:

Corrosion takes place in the form of pit, cavity or holes on the metal structure is known as
pitting corrosion. This type of corrosion can be explained on the basis of differential aeration
corrosion. The metal surface which is more exposed to O2 acts as cathode and hence free
from corrosion, but metal surface which is less exposed to O2 acts as anode and undergoes
corrosion. In this type of corrosion anodic area is very small compared to the cathodic area of
the metal, hence corrosion rate is more in the smaller anodic area resulting in the formation of
pit, hole on the metal surface.
Ex.

WATER LINE CORROSION

This type of corrosion usually takes place in metals or alloys which are partially immersed in
water. Water line corrosion can be explained on the basis of differential aeration corrosion.
The metal structure above the water level is more exposed to air or O2 act as cathode and free
from corrosion but the metal structure below the water level is less exposed to air act as
anode and undergoes corrosion due to the formation of 02 concentration cell.

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Ex: Water line corrosion usually takes place in shiphull, water tank and metal surface is
partially immersed in water or solutions.
This type of corrosion can be prevented by fixing more anodic material to the base metal or
immersing the metal surface completely in water because the concentration of 0₂ in water is
uniform.
CAUSTIC EMBRITTLEMENT
Metals like steel and iron become hard & brittle due to the combined effect of stress as well
as direct chemical attack, this type of attack is known at caustic embrittlement. This type of
corrosion is usually occurs in boiler, water heater, geezer etc. The boiler feed water
invariably contains certain proportions of sodium carbonate for softening purpose. At high
temperature and pressure boilers breaks up to give sodium hydroxide and carbon dioxide.

Hydrolysis
Na2CO3+H2O -----------> 2NaOH + CO2

The sodium hydroxide so formed makes the boiler water alkaline, which flows in to the
minute cracks and crevices in the inner surfaces by capillary action, because of the
evaporation of water in boilers, the concentration of NaOH solution in the cracks and
crevices increases.

2NaOH +Fe -----------> Na2FeO2 + H2

The sodium ferroate decomposes slightly away from the points of its formation

3Na2FeO2 + 4 H2O -----------> 6NaOH +Fe3O4 +H2

Magnatite

Caustic embrittlement leads to boiler get failure and there are chances of boiler surfaces
bursting out under pressure at the points of corrosion.
Caustic embrittlement can be prevented by adding chemicals such as NaNO3, Na2SO4, tannin,
lignin, calgon to the boiler feed water, which removes all scale forming materials and hence
corrosion is prevented.

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[Link], Associate professor [Link] Chemistry

A tube damaged by caustic embrittlement. White caustic deposits can be seen inside.

FACTORS AFFECTING THE RATE OF CORROSION

The following factors affecting of rate of corrosion process
(1) Nature of metal
(2) Nature of corrosion product
(3) Anodic and Cathodic area
(4) PH
(5) Temperature

1. Nature of Metal
The tendency of metal to undergo corrosion is dependent on the nature of the metal. In
general the metals with lower electrode potential values are more reactive than the metals
with higher electrode potential values. The more reactive metals are more susceptible for
corrosion. Thus the tendency of metal to undergo corrosion decreases with increase in
electrode potential
For Ex. The metals like K, Na, Mg, Zn etc. are more active with lower electrode potential
undergoes corrosion than the least noble metals such as Au, Pt, Ag etc
2. Nature of Corrosion product:
The corrosion product is usually the oxides of metal. The rate corrosion may increase or
decrease depending on the nature of corrosion product.
E.g.: If the corrosion product is more passive i.e., insoluble in water, non porous and low
ionic conductivity which prevent the rate of corrosion due to the formation of protective
oxide film on the surface of metal.
If the of corrosive product is less passive i.e. highly soluble in water, more porous and
relatively higher ionic conductivity which enhance the rate of corrosion due to the formation
of non protective oxide film on the surface of metal structure.
3. Anodic and Cathodic area:
Smaller anodic area and larger cathodic area are exposed to atmosphere, more intense and
faster corrosion occurring at the anodic area.
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For ex:- When tin is plated on iron in such a way some area not covered or some pin holes
are left, there result in small anode and large cathode, an intense localized corrosion occurs at
the exposed small anodic surface.
On the other hand zinc plating on iron gives an anodic coating to iron, since zinc is above the
iron in the electrochemical series, therefore intense corrosion of iron would not be occur, this
is because of formation of large anodic and small cathodic area.

4. PH: Generally the rate of corrosion is more at acidic media than in neutral or basic media.
This is because in basic medium the protective oxide layer is formed on the surface of metal
which prevent the rate of corrosion. But in acidic medium the rate of corrosion is more due to
the liberation of H₂ even in the absence of air at the cathode.
i.e., H+ + H2O + e- -----------> OH- + H2
5. Temperature: The rate of corrosion increases with increase in temperature, because as the
temperature increases the conductance of aqueous medium increases and passivity decreases,
as a result of rate of corrosion increases.
6. Conductance of medium: conductance of underground structure is influenced by the
conductance of the medium. Conductance of dry sandy soils is lower than those of clay and
mineralized solids

PREVENTION OF CORROSION:
It is better to control rather than to prevent corrosion. Since it is impossible to eliminate
corrosion. The following Methods are adopted to prevention of corrosion.
1) Protective coatings (Metallic, Organic & Inorganic coatings)
2) Cathodic Protection (Sacrificial and Impressed current method)
3) Anodising coating of aluminium
4) Organic coating (painting and varnishing)

PROTECTIVE COATINGS
The process of coating of materials on metals to prevent corrosion are protective coatings.
Protective coatings acts as physical barrier between the metal surface and the corrosive
environment and hence corrosion is prevented. Protective coatings are
1. Metallic coatings
2. Inorganic coatings
3. Organic coatings

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Metal coatings: Coating of one metal on another metal is known as metallic coating,
there are two types of metallic coating
1) Galvanization
2) Tinning

GALVANISATION
The process of coating of zinc on iron or steel or base metal to prevent corrosion is called
galvanization.
The base metal or iron to be galvanized is washed with organic solvent to remove oil or
grease present on the surface of metal. Then it is treated with hot dil H2SO4 and then rubbed
with sand paper to remove scale or rust and finally dipped in zinc chloride, ammonium
chloride which act as flux and dried. The clean and dried metal structure to be galvanized is
passed through a bath of molten Zinc which maintained above 4500C. Finally it is passed
under the rollers to remove excess of zinc and to adjust thickness of Zn layer. A thin and
uniform layer of zinc is coated on the outer surface of metal (iron), which is prevent the
corrosion.
Applications:
1. Galvanizing Iron articles are used for making wire mesh, wire fences, roofing iron
sheets, steel pipes, bolts, screws, buckets etc.
2. Galvanizing Iron articles cannot be used for storage of food stuffs because zinc reacts
with food acids forming zinc complex which is highly toxic and poisonous.
TINNING:
The process of coating of Tin on iron or steel articles to prevent the corrosion is known as
Tinning. Tin is cathodic to Iron and hence corrosion of iron is prevented. Tinning is done by
hot dipping process.
The metal structure to be coated is washed with organic solvents to remove oils or grease and
it is dipped with hot dil.H2SO4 (800C) and rubbed with sand paper to remove oxide film or
scale formation of the structure and it is dipped in a bath of zinc chloride flux which helps to
adhere the molten tin on the surface of iron sheet. The cleaned Iron sheet is passed through a
bath of molten tin which is maintained about 2600 C then the sheet is finally passed under the
roller to remove excess of Tin and to adjust the thickness of tin layer. After this the iron that
is again dipped in palm oil which protect the tin coated surface against the corrosion. A thin
and uniform tin layer is coated on the outer surface of the iron structure which prevents
corrosion.
Applications:
1. Tin coated articles are used for storage of food stuffs. Ghee, oils, Kerosene, packing
Materials because it avoids food poisoning.
2. Tin coated copper articles are used for making cooking utensils and Refrigerating
equipments etc.

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Cathodic protection:
It is a process in which the base metal to be protected from corrosion made as cathode w.r.t
another metal is known as cathodic protection.
It is one of the important methods to prevent the corrosion of base metal such as water-tank,
buried pipelines, underground cables, marine structures ship hulls and the metals are
immersed in water. Cathodic protection can be done in 2 ways.
1) By using sacrificial Anode
2) Impressed current method.
i) Sacrificial anode method:
In this method the base metal to be protected is made as cathode by connecting the more
anodic metals like Al, Mg, Zn etc using wire, which are called sacrificial metals (Anode).
The sacrificial metal act as anode and undergoes corrosion but the base metal acts as cathode
and hence free from corrosion. Periodically replace the sacrificial metals otherwise base
metal is corroded.

For e.x. Several hundred kilometers long Zinc wire buried along the oil pipeline in Alaska is
an example for above method.
ii) Impressed Current method:
In this Method the metal structure to be protected from corrosion is made as cathode by
connecting it to the -ve terminal of the battery while the +ve terminal is connected to the inert
anode like graphite, silica and iron alloy. When the Electric energy is applied, the metal
structure becomes cathode and hence free from Corrosion.

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[Link], Associate professor [Link] Chemistry

This type of cathodic protection is applied to water coolers, water tanks, buried oil pipes,
water pipes, Marine Condensers, transmission line towers.

Anodizing coating of aluminium

The process of coating of oxide layer on the surface of metal structure by passing electric
current in presence of suitable electrolyte is known as anodizing.

The article which is to be anodized is first degreased then it is polished and connected to the
anode and lead or steel or copper is generally used as a cathode, The electrolyte consists of
5-10% chromic acid, the tempetarature of the bath is maintained 350C. The voltage is
increases from 0-50v, so as to maintain an anode current density of 10-20 MA/cm2. During
the first 10 minutes, the potential is increased from 0-40v. When the potential reaches 40v.
Anodizing is continued for 20 minutes. After 20 minutes the potential is increased from 40-
50v and held at 50v for five minutes, an opaque oxide layer is obtained. For higher thickness
10% sulphuric acid is used as the electrolyte. The article can be dyed by immersing for about
20 minutes in an aqueous solution of the dye stuff. To improve the corrosion resistance, the
article is treated with nickel or cobalt acetate followed by boiling water treatment. The
strength and resistance for corrosion of the anodized film can be increased by sealing.
Anodized article are used as window frames, soap boxes, tiffin carriers
CORROSION PENETRATION RATE
The corrosion penetration rate is the speed at which any metal Or alloy deteriorates in a
specific corrosive environment through chemical or electrochemical reactions. It is also
defined as the amount of weight loss per year in the thickness of metal or alloy due to
corrosion. The corrosion penetration rate also referred as corrosion rate. CPR depends on the
following factors
I) Nature of metal
II) Nature of corrosive Environment/ medium
III) Nature of metal
IV) Speed at which corrosion spreads in the inner portion of metal

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Calculate CPR in a metal, a known weight of test metal is taken. It is allowed to corrode in a
specific environment for a specific time period. Then, the surface is thoroughly cleaned to
remove the corrosion product and then the weight of the metal is checked. From the weight
loss of the metal, corrosion penetration rate (CPR) can be calculated using the following
equation.
The CPR is calculated as follows:

CPR = (k x W) / (D x A x T)

Where k = a constant
W = total weight lost
T = time taken for the loss of metal
A = the surface area of the exposed metal
D = the metal density in g/cm³

CPR can be calculated in terms of mil per year or in terms of mm per year.1mil=0.001 inch.
To calculate CPR in terms of mil/year, the value of constant k is taken as 534 and weight, W
in mg, density, D in g/cm3, area, A in inch2, and time T in hours.
Whereas to calculate CPR in terms of mm/year, the value of constant k is taken as 87.6 and
area A in cm2. Other values are taken as above i.e. weight, W in mg, density, D in g/cm3 and
time, T in hours.

Numerical Problem on CPR

1. A 5.5 kg of iron metal piece of density 8.1 g/cm3 with area 10.0 inch2 was submerged
in sea water for 10.5 years. Weight of the remaining metal is found to be 2.4kg.
Calculate corrosion penetration rate in mil per year.
Sol. Corrosion Penetration Rate (CPR)= k×W/D×A×T
Here k=534
W=total weight lost= (5.5-2.4) kg = 3.1 kg = 3.1×103×103 mg.
T=time taken for the loss of metal = 10.5 years×365×24 hours.
A=the surface area of the exposed metal = 10.0inch2
D=The metal in g/cm3 = 8.1 g/cm3
Corrosion Penetration Rate (CPR) =534×3.1×103×103/8.1×10.0×10.5×365×24
Corrosion Penetration Rate (CPR) =222.19 mil per year.
2. 5.5 kg of iron metal piece of density 8.1g/cm3 with area 10.0 inch2 was submerged in
sea water for 10.5 years. Weight of the remaining metal is found to be 2.4kg.
Calculate corrosion penetration rating mm/ year.

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Sol. Corrosion Penetration Rate (CPR)= k×W/D×A×T

Here k= 87.6
W=total weight lost= (5.5-2.4) kg = 3.1 kg = 3.1×103×103 mg.
T=time taken for the loss of metal = 10.5×365×24 hours.
A=the surface area of the exposed metal = 10.0inch2
D=The metal in g/cm3 = 8.1 g/cm3
Corrosion Penetration
Rate(CPR)=87.6×3.1×103×103/8.1×10.0×6.4516×10.5×365×24
Corrosion Penetration (CPR)= 5.65mm per year.

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Metal finishing
Introduction
Many of the elements known to us are metals. A large number of metals are common use for
example gold and silver which are used in ornaments, aluminum, copper and stainless steel
are used in house hold articles and manufacture of machines and machinery parts but none of
these metals possess all properties such as
1) Resistance to corrosion
2) Resistance to wear and tear
3) Resistance to impact etc. required for their use in variety of engineering applications.

The surfaces of metals are suitably modified and any such surfaces modification is called
metal finishing.
Or
Metal finishing is defined as the deposition of a thin layer of a noble metal on a base metal or
polymer
ex- Electroplating and Electroless plating

Technological importance of metal finishing.

The process of metal finishing is improving the certain properties of material such as
1) Increases corrosion and wear resistance
2) Improving thermal and electrical property.
3) Improving hardness of metal.
4) Increases abrasion and impact resistance
5) Improving durability and to get decorative appearance of the metal.
6) Reducing frictional loss.
Electroplating
It is a process of coating of one metal on the other metal using electrolytic process is known
as electroplating. Electroplating is a one of the best and important method in order to prevent
the corrosion of the base metal using coating metal such as Cr, Ni, Cu, Zn, Cd, Pb, Ag, Au
and Pt.
Alloys such as Cu-Zn, Pb-Sn, Cu-Sn, Ni-Co etc.
Proces: The metal structure to be plated is first washed with organic solvent to remove oil
and grease then washed with hot dil H2SO4 and rubbed with sand paper to remove any
metallic oxide on the metal structure finally it is washed with H2O and dried. The metal
structure to be plated is made as cathode and coating metal is made as anode in presence of
suitable electrolyte, when applied electrical energy either electrolyte or anode dissolved in
electrolyte and is deposited on the cathode, a thin uniform layer is formed on the outer
surfaces of the metal structure which prevent the corrosion of base metal.

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Electroplating of Chromium
It is one of the widely used metals for electroplating, there are two types of chromium plating
1) Decorative coating
2) Hard plating
Chromium does not give good deposit directly on the article, hence the article is first
electroplated with copper and then with chromium
Composition of Electrolytic bath:
Anode: Insoluble Pb-Sn or Pb-Sb alloys coated with PbO2
Cathode: Article to be coated (Electroplated with copper)
Electrolyte: CrO3 (Chromic acid), H2SO4 (100:1)
Optimum temperature: 40-500C
Current density: 100-200 MA/Cm2
Reactions
Anode reaction: Cr →Cr3++3e
Cathode reaction: Cr3++3e → Cr
On electrolysis chromium ions are reduced to metallic chromium which gets plated over the
article
Discussion:
The chromium plating provides excellent hardness, bright appearance and resistance to
corrosive environment. The electrolytic bath is extremely acidic with pH of zero. In the
chromic acid the chromium is in the +6 state, which is reduced to Cr3+ due to sulphate ions,
then the unstable Cr2+ and finally to Cr. However high concentration of Cr+3 can cause black
deposit. The difficulty is overcome by using insoluble anodes coated PbO2 oxidizes Cr3+ to
Cr6+ and hence the concentration of Cr3+ decreases. Further chromium anode may get
passivity in the acid medium, hence chromium metal is not used as anode in chromium
plating.

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Applications
Electroplating of Cr is mainly used in importing decorative and corrosion resistance coating
of metals
Electroless plating
It is a technique of deposition of noble metal on catalytically active surface of less nobel
metal by employing a suitable reducing agent.
Advantages:
* No electrical energy is required.
* It has a better throwing power.
* No levelers are required
* Semiconductor and insulator can also be coated.
* Deposition is more and compact and highly adherent
*Electro less Coating posses unique properties such as chemical, mechanical and magnetic
properties.
Difference b/w electroplating and electroless plating:

Description Electro platting Electroless plating

Driving force Power supply Auto Catalytic redox reaction
Cathode reaction Mn++ne- →M Mn++ne- →M
Anode reaction M → Mn++ne- M → Mn++ne-
Site of Anodic reaction Separate anode Article to be plated-
Site for cathode reaction Surface is drastically Surface is catalytically
prepared prepared
application Only for conductors Both conductors and
non-conductors
Nature of deposit Pure metal and alloy Metal with reducing agent
and oxidized product

Electroless plating of Nickel.

Electroless plating of Nickel involves following steps
(1) Pretreatment or activation of the surface.

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The surface to be plated is first degreased (using organic solvent or alkaline) followed by acid
treatment. Stainless steel is activated by dipping dilute H2SO4, Nonmetallic objects are
activated by dipping in SnCl2, followed by palladium chloride to get thin layer of palladium.
(2) Plating bath solution.
A solution of - NiCl2 (20gm/lt)
Reducing agent - Sodium hypo phosphate (20gm/lt)
Complexing agent - Sodium succinate (15 gm/lt)
Buffer - Sodium acetate (10gm/lt),
PH – 4-5
Temp. 93°C
The following reactions occurs during the plating process
Ni2++2e- Ni (cathode)
H2PO2- + 2H2O H2PO3- + 2H+ + 2e- (anode)
Ni2++ H2PO2-+2H2O Ni+ H2PO3-+ 2H+
Both oxidation and reduction takes place on the same surface, the reducing agent reduces the
nickel ion from the surface to Ni atom and deposits on the activated surface. Due to oxidation
of hypophosphate H+ ions releases into solution. The pH decreases the plating quality gets
affected in acid, therefore buffer is used to get good quality coating.
Applications:
1. It is used in industrial components such as pumps, valves, piston shaft and gears.
2. Coating of inner surface of perfumed bottles in order to avoid corrosion.

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