Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Module-2
Corrosion and Metal Finishing

Corrosion and Metal finishing:

Corrosion and its control:
Introduction, Electrochemical theory of corrosion, Factors affecting the rate of corrosion: ratio of
anodic to cathodic areas, nature of corrosion product, nature of medium – pH, conductivity and
temperature. Types of corrosion - Differential metal and differential aeration (pitting and water line).
Corrosion control: Anodizing – Anodizing of aluminum, cathodic protection - sacrificial anode and
impressed current methods, Metal coatings – Galvanization. Corrosion Penetration Rate (CPR),
numerical problems on CPR.
Metal finishing: Introduction, technological importance. Electroplating: Introduction,
Electroplating of chromium (hard and decorative). Electroless plating: Introduction, distinction
between electroplating and electroless plating processes. Electroless plating of copper.
RBT Levels: L1 & L2)
Course outcome (CO-2): Explain the fundamental concepts of corrosion, its control and surface
modification methods namely electroplating and electroless plating.

Corrosion
Introduction:

The term corrosion is used to denote a change. A metal changes from its elementary state to the
combined state when it comes in contact with liquid medium. This is actually due to the
chemical interaction between the metal and the environment.
Definition: “The spontaneous deterioration and consequent loss of a metal/alloy due to
chemical/electrochemical attack by the environment”.
Example: When iron metal is exposed to the moist environment, the metal forms a hydrated
ferric oxide called rust which is relatively non-protective.
Most of the corrosion cases are electrochemical in nature taking place by an electrochemical
attack on the metal in the presence of air and moisture (H2O) called wet corrosion. The
mechanism of the wet corrosion is explained on the basis of electrochemical theory of corrosion.

Electrochemical theory of corrosion:

According to this theory,

1. When a metal is in contact with moist air or when dissimilar metals are contact with each
other in a solution, large numbers of galvanic cells are formed with the existence of anodic
and cathodic area on the metal.
2. In this corrosion, oxidation of the metal and reduction of species present in solution takes
place.
3. The anodic part of the metal undergo oxidation and suffers from corrosion, cathodic part
undergo reduction and protected from corrosion.
4. The electrons are transferred through the metal from anode to cathode.
5. During corrosion the following reactions takes place.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 1
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
At anode (oxidation reaction) : M → Mn+ + ne-
The reaction at cathode (reduction reaction) depends on the nature of the environment:
If the medium is acidic,
In the presence of dissolved oxygen : 2H+ + ½O2 + 2e-→H2O
In the absence of dissolved oxygen : 2H+ + 2e-→ H2
If the medium is alkaline/neutral,
In the presence of dissolved oxygen : H2O+½ O2 + 2e-→2OH-
In the absence of dissolved oxygen : 2H2O+2e-→2OH-+ H2
Example: Rusting of an Iron in the presence of moist air
Anodic reaction : Fe→Fe2+ + 2e-
Cathodic reaction : H2O+½ O2 + 2e-→2 OH 
Products of anode & cathode : Fe2+ +2 OH  → Fe(OH)2
In the presence of oxygen : 2 Fe(OH)2+ ½ O2→ Fe2O3.2H2O
(Rust)

Factors affecting the rate of corrosion

Ratio of anodic to cathodic area:
1) The rate of corrosion (x) is directly proportional to the ratio of area of anode to the area
of cathode. i.e., x = area of anode/ area of cathode
2) Higher the value of x, greater is the rate of corrosion.
3) When anode is small and cathode is large, all the electrons liberated at anode and are
consumed at the cathode. This further intensifies the anodic reaction leading to increase
in overall rate of corrosion.
For example, in the coating of Tin on Iron (Tin is cathodic Iron), if some part on Iron is
not covered, it results in smaller anodic area and larger cathodic area. In this case more
intense corrosion is observed at smaller anodic area.
Nature of the metal:

1) Metals with higher electrode potentials do not corrode easily. They are noble metals like,
gold, platinum, silver. Whereas metals with lower electrode potentials, readily undergo
corrosion.e.g. metals like, zinc, magnesium, aluminium. When two metals are in contact
with each other, higher the difference in electrode potentials greater is the corrosion.
For example, the potential difference between iron and copper is 0.78V which is more
than that between iron and tin (0.3V). Therefore, iron corrodes faster when in contact
with copper than that with tin.
2) Position of the metal/alloy in the galvanic series also decides the rate of corrosion.
3) The metal top in the series is more anodic and undergoes corrosion faster than the metal
below it.
Nature of the corrosion product:
1) In a moist atmosphere almost all metals get covered with a thin surface film of metal
oxide as the corrosion product.
2) The corrosion product formed like metal oxide may act as protective film, if it is stable,
insoluble and non porous. If it acts as protective film it prevents further corrosion by
acting as barrier between metal surface and corrosion medium.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 2
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
3) On the other hand if corrosion product is unstable, porous and soluble, it further enhances
corrosion.
For example, oxidizing environments, metals like aluminium, chromium, titanium, etc.,
are highly passive as their oxides as corrosion products form protective films on the metal
surface, preventing further corrosion. Metals such as iron, zinc, magnesium etc., do not
form any protective film and are highly susceptible for continuous corrosion, when
exposed to oxidizing environments.

Nature of Medium:
pH of the medium:
1) The rate of corrosion increases with decrease in pH of the medium.
2) Acidic media are generally more corrosive than alkaline/neutral media. This is due to
evolution of hydrogen at cathode.
3) When the pH < 4, the rate of corrosion increases due to higher concentration of H+ ions.
When pH > 10, the rate of corrosion decrease due to formation of insoluble metal
hydroxides on the surface of metal.
Conductivity:

1) The rate of corrosion increases with increase in the conductance of the medium.
2) As the conductance of the medium increases, ions can move easily trough the medium.
3) This decreases the polarization potential and due to this rate of corrosion increases.
For example metal immersed in sea water (more conducting) is more conduction than
metal immersed in river water (less conducting).
Temperature:
1) Generally rate of corrosion increases with increase in temperature.
2) As the temperature increases conductance of the ions in the medium increases which
reduces the polarization. Therefore the rate of corrosion increases.
3) A passive metal become active at high temperature and increases the rate of corrosion.

Types of corrosion: Corrosion can be classified into 3 types as follows

1) Differential metal corrosion (Galvanic corrosion)

2) Differential aeration corrosion

Differential metal corrosion (Galvanic corrosion)

1) When two dissimilar metals are in direct contact with one another and exposed to a corrosive
medium, the metal with lower electrode potential becomes anode and suffers from corrosion,
whereas the metal with higher electrode potential becomes cathode and protected from
corrosion. This type of corrosion is known as differential metal corrosion or galvanic
corrosion.
2) The rate of corrosion depends mainly on the difference in the position of the two metals in
galvanic series.
3) Higher the difference, faster is the rate of corrosion.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 3
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Example: Electrode potential of iron (-0.44 V) is less than that of copper (0.34 V). Therefore
when iron is in contact with copper, iron becomes anodic and undergoes corrosion, whereas
copper becomes cathodic and protected from the corrosion.

Differential aeration corrosion

1) When a metal is exposed to different concentration of air (O2), part of the metal exposed to
lower concentration of O2 becomes anodic and undergoes corrosion.
2) Other part of the metal exposed to higher concentration of O2 becomes cathodic and
protected from the corrosion.
3) The difference in O2 concentration produces a potential difference and causes corrosion. This
type of corrosion is called differential aeration corrosion.

Example: 1 Water line corrosion

1) It is observed in steel or iron water tank partially filled with water. Part of the tank just below
water level is exposed to lower concentration of O2 becomes anodic and undergoes corrosion.
2) Part of the tank above the water line which is exposed to higher concentration of O2 becomes
cathodic and protected from the corrosion.
3) More corrosion is observed just below the water line; hence this type is called water line
corrosion.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 4
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Reactions:

Example: 2 pitting corrosion

1. Pitting corrosion is observed when dust particles get deposited over the metal surface.
2. The portion of the metal covered by dust which is less aerated becomes anodic and suffers
from corrosion.
3. Thus, metal is lost below the surface of dust particle forming a deep and narrow pit.
4. The adjacent area of the metal which is exposed to higher concentration of O2 becomes
cathodic and protected from corrosion.

Reactions:

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 5
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Corrosion control
Inorganic coatings (Chemical conversion coatings)
These coatings are produced at the surface of the metal by chemical/electrochemical reactions.
Examples: Anodizing and Phosphating

Anodizing:

Anodizing is the process of oxidation of outer layer of metal to its metal oxide by electrolysis.
Oxide layer formed over the metal itself acts as protective layer.

Anode : Aluminium
Cathode : Steel or Copper
Electrolyte : 5-10% chromic acid
Temperature : 30-40 °C
Applied potential : 0-40 V
Aluminum is made as anode and copper or steel is used as cathode. The electrodes are immersed in
an electrolyte consisting of 5-10% chromic acid. The temperature is maintained at 30-40 °C.
Potential of 0-40 V is applied which oxidizes outer layer of Al to Al2O3 and that get deposited over
the metal. The reactions involved are as follows

The anodized coatings are thicker than the natural oxide film and possess improved corrosion
resistance as well as resistance to mechanical injury.

Cathodic Protection:

The principle is to force the metal to be protected to behave as cathode. There are two types of
cathodic protections namely,

1) Sacrificial anodic protection.

2) Impressed current cathodic protection.

Sacrificial anodic protection:

1) The metal to be protected is connected to a more anodic metal using a metallic wire.
2) The more active metal gets corroded while the parent structure is protected from corrosion.
3) The more active metal so employed is called sacrificial anode.
4) The sacrificial anodes to be replaced by fresh ones as and when it is required.
5) Commonly used sacrificial anodes are: Mg, Zn, Al etc.
Example: steel pipe is protected by connecting it to a block of Zn. In such cases steel acts as a
cathode and is unaffected or protected from corrosion and Zn act as anode and undergoes
sacrificial corrosion.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 6
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Impressed current protection:

1) In this method, electrons are supplied from a source of direct current.

2) Metal structure to be protected acts as cathode and connected to –ve terminal of battery.
3) The inert metal like graphite act as anode and connected to + ve terminal of battery.
4) When DC current is applied in a reverse direction to nullify the corrosion reaction.
5) Since anode is inert metal no reaction takes place at anode therefore the cathodic metal is
protected from corrosion.

Metal coatings:

Metal coatings can be applied on the base metal by hot dipping process. This method is used for
producing a coating of low melting metals such as Zn, Al, Sn etc, on iron/steel metals which
have relatively high melting point. Example: Galvanizing and Tinning

Galvanization:

Coating of zinc on iron or steel by hot dipping process is called galvanizing. (M.P of Zn=419 °C)
It is carried out as follows,

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 7
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
1) The iron sheet is subjected to pretreatment by degreasing with organic solvent.
2) The sheet is passed through dilute H2SO4 to remove any rust.
3) Washed with distilled water and dried by supplying hot air.
4) Then iron sheet is dipped in molten bath of Zn at 419°C and surface is covered with NH4Cl
flux which prevents the oxidation of Zn metal.
5) The excess of coated metal is removed by passing through a pair of hot rollers and cooled
gradually.

Corrosion Penetration Rate (CPR)

The corrosion penetration rate (CPR) is defined as “the speed at which any metal in a specific environment
deteriorates due to chemical reactions when it is exposed to a corrosive environment” or the amount of
corrosion loss per unit time in thickness or the speed at which corrosion spreads to the inner portions of a
material. Corrosion rate depends on the metal and the environmental condition.
The CPR is given by
k×W
CPR =
D×A×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
The corrosion penetration rate is expressed in terms of thickness or weight loss when the surface of the
metal corrodes uniformly across an area.
This method involves the exposure of a weighed piece of test metal or alloy to a specific environment
for a specific time. This is followed by a thorough cleaning to remove the corrosion products and then
determining the weight of the metal after corrosion.
The rate may vary if the rate expressed by the formula above is used to compare corrosion rates for a
period longer than one year with rates calculated over short periods. This is because the short time
periods are prone to fluctuating environmental changes from season to season and from day to day.
Note:-
1. Unit of CPR is mils per year if W is in mg, A in Inch2, D in g/cm3, t in hrs and k value will be 534.
(1mil = 0.001 inch)
2. Unit of CPR is mm per year if W is in mg, A in cm 2, D in g/cm3, t in hrs and k value will be 87.6.
(1inch = 2.54 cm)
3. If CRP is less than 20m/year or 0.5 mm/year, it is acceptable for most of the application.

Numerical Problems on CPR

1. A steel of area 100 inch2 is exposed to air near the seashore. After 1 year it was found that the steel
sheet has lost 485g due to corrosion. What is the value of CPR in mils/year and in mm/year? Can
such steel sheet be applicable for the construction purpose where the steel sheet is exposed?
Given - Area (A) =100 inch2, total weight lost (W) =485g = 485 x103 mg, T = 1 year =1 x 365 x
24hrs, D = 7.9g/cm3 and k=534.

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 8
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
k×W
CPR =
D×A×T

534 × 485000
CPR =
7.9 × 100 × 365 × 24

CPR = 37.42mils/year

Area =100 inch2 = 100 x 2.54×2.54 cm2 (1 inch = 2.54 cm) and k =87.6
k×W
CPR =
D×A×T
87.6 × 485000
CPR =
7.9 × 100 × 2.54 × 2.54 × 365 × 24

CPR = 0.9516 mm/year

Since CPR is not less than 20m/year or 0.5 mm/year, it is not applicable for the construction purpose.
2. A piece of corroded steel plate was found in a submerged ocean. It was estimated that the original
area of the plate was 12 inch2 and the approximately 2.5 kg had corroded during the submersion.
Assuming a corrosion penetration rate of 100 mpy for this alloy in seawater. Estimate the time of
submersion in year. The density of steel is 7.9g/cm3.
Given - Area (A) =12 inch2, total weight lost (W) =2.5kg = 2.5 x 103 x 103 mg, CPR = 100 mpy, D =
7.9g/cm3 and k=534.
k×W
CPR =
D×A×T

534 × 2.5 × 103 × 103

100 =
7.9 × 12 × T

534 × 2.5 × 103 × 103

T=
7.9 × 12 × 100

T = 140822.79 hrs

140822.79
T=
365 × 24

T = 16.1 years
3. A weight loss of 1mg for an exposed area of 0.01m2 per day was observed for iron rod. This
corresponds to corrosion penetration rate of 4.65mm/year. If same type of iron rod suffers weight
loss of 0.5 mg/per day if the exposed area is 0.02 m2, what is the corrosion penetration rate?
CPR1 = (k x W1) / (D x A1 x T)
CPR2 = (k x W2) / (D x A2 x T)
CPR1 / CPR2 = (W1 x A2) / (W2 x A1)
4.65 / CPR2 = (1 x 0.02) / (0.5 x 0.01)
CPR2 = 1.16 mm/year.
Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 9
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY

Metal Finishing
Introduction:
Metal finishing covers the wide range of processes carried out in order to modify the surface
properties of a metal. These processes involve deposition of a layer of another metal or a
polymer, conversion of a surface layer of atoms into oxide films which ultimately modify the
surface of the metal.
Definition:
“It is a process of modifying surface properties of metals by the deposition of a layer of another
metal or polymer on its surface or by the formation of an oxide film”.

Technological importance of metal finishing:

The main technological importance of metal finishing include
[1] Imparting the metal surface to higher corrosion resistance.
[2] Providing electrical and thermal conducting surface.
[3] Imparting thermal resistance and hardness.
[4] In the manufacture of electrical and electronic components such as PCB’s, capacitors
contacts, etc.
[5] To increase the decorativeness of metal surface.
Electroplating

Definition: “It is a process of deposition of a metal by electrolysis, over the surface of substrate.
The substrate may be another metal, polymer, ceramic, or a composite”.

Electroplating of chromium:
Chromium is one of widely used metal in electroplating industries. In the field of electroplating
two types of Chromium are employed, decorative Chromium and hard Chromium.
Pretreatment: Before the application of the electroplated coatings, it is essential to clean the
surface of the base metal. The impurities present on the surface like grease, oil, oxide layer, dust
etc are removed by solvent cleaning or alkali cleaning or mechanical cleaning.

Decorative chromium Hard chromium

Bath 250 g Chromic acid + 2.5 g H2SO4 250 g Chromic acid + 2.5 g H2SO4
composition proportion/dm3 proportion/dm3
Temperature 45-60° C. 45-55° C
Current Density 145- 430 A m-2 290-580 A m-2
Anode Insoluble anodes like pb-sb Insoluble anodes like pb-sb
Cathode Object to be electroplated Object to be electroplated

Mode of plating: The plating bath contains CrO3 in which Cr is in +6 oxidation state. This is
reduced to +3 oxidation state in the presence of SO42- furnished by H2SO4. Cr3+ ions are reduced
to elemental Cr which gets deposited on the surface of cathode. The reactions taking place are
given below.
2H2 CrO4 → H2 Cr2 O7 + H2 O
H2 Cr2 O7 → Cr2 O2−
7 + 2H2 O
Cr2 O2−
7 + 14H +
+ 6 e− → 2Cr 3+ + 7H2 O
3+ −
2Cr + 3 e → Cr

Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 10
 Dept of Chemistry - SAI VIDYA INSTITUTE OF TECHNOLOGY
Applications:
1. Decorative chromium provides a durable finish on cycles, automobiles, furniture’s,
household fittings, air craft, surgical instruments etc.
2. Hard chromium is used in the manufacture of cutting tools, piston rings, cylindrical liners
etc.
Note: Chromium anodes are not used in Chromium plating because
1. Chromium metal deactivates strongly in acid medium.

Electroless plating (Auto catalytic redox reaction)

Definition: “The process of depositing a metal over substrate by controlled chemical reduction
of metal ion by a reducing agent without using electric current is called electroless plating”
Metal ions + reducing agent Metal + oxidized product

Differences between electroplating and electrolessplating:

Property Electro plating Electroless plating

1) Driving force Passage of current Auto catalytic redox reaction
2) Anode A separate anode is used Catalytic surface of the
substrate acts as anode
3) Reducing agent Electrons bring about reduction Chemical reagents bring
about reduction
4) Applicability Applicable only to conductors Applicable to both conductors
and nonconductors
Electroless plating of copper:
Electroless plating of copper involves the following features.

Pretreatment and activation of the surface: The surface to be plated is first degreased by using
organic solvents followed by acid treatment. PCBs are activated by first dipping in SnCl2
solution containing HCl followed by dipping in palladium chloride solution.

Composition of the bath:

Coating solution : CuSO4.5H2O (15g/L)
Reducing Agent : Formaldehyde (8g/L)
Buffer : NaOH (15g/L) + Rochelle salt (14g/L)
Complexing agent : EDTA solution (20g/L)
H
P 11
Temperature : 25 °c
Chemical Reactions:
Anodic Reaction : 2HCHO + 4OH 2 HCOO - + 2H2O + H2 + 2e-
Cathodic Reaction : Cu2+ + 2 e- Cu
Net reaction : Cu2+ + 2HCHO + 4 OH- Cu + 2HCOO- + 2H2O + H2

Note: Buffer is added because; above redox reaction involves the consumption of OH- ions, so
the pH of the solution decreases as the reaction proceeds.
Prof. Bhagya N.P/ Prof. Raveendra R.S. /Prof. Anil kumara K V/ Prof. Mutthuraju M Page 11