Department of Chemistry Unit II NMIT Bangalore , NDU

UNIT II
CORROSION SCIENCE AND METAL FINISHING
Corrosion Science: Introduction; electrochemical theory of corrosion (taking Fe as
example), corrosion types – differential metal corrosion, differential aeration
corrosion, pitting corrosion; factors affecting corrosion – primary and secondary
factors; corrosion penetration rate – numerical problems; corrosion control – metal
coating (galvanization and tinning), anodization, sacrificial anode method,
Metal Finishing: Introduction; electroplating – definition, principle, factors affecting
electroplating, electroplating of chromium (hard chromium and decorative chromium);
electroless plating – definition, advantages, application of electroless plating of copper
in the manufacture of PCB; comparison between electroplating and electroless plating

CORROSION SCIENCE
. Corrosion can be defined as spontaneous destruction or deterioration of a
metal or alloys by the surrounding environment because of chemical or electrochemical
reaction. Free metals, as such possess high energy. Whenever favourable situation
arises, they combine with other elements like oxygen to form compounds and attain the
state of minimum energy with maximum stability. Following figure shows that
corrosion can be viewed as the reverse process of extractive metallurgy.

Some examples for corrosion:

Rusting of iron: 4Fe(s) + 3O2(g) → 2Fe2O3.H2O(s)
Tarnishing of silver: 4Ag(s) +2 H2S(g) + O2(g) → 2Ag2S(s) + 2H2O(l)
Scales on copper: 2Cu(s) + H2O(l) + O2(g) + CO2(g) → [CuCO3 + Cu (OH)2] (s)

1
Department of Chemistry Unit II NMIT Bangalore , NDU

TECHNOLOGICAL IMPORTANCE OF CORROSION STUDY

 Human life and safety: Loss of life results when structures collapse due to
combined effects of stress and corrosion. Safety issue can be due to release of
certain toxic product as a result of corrosion, sudden failure of equipment may
cause fire or explosion.
 The cost of corrosion: The annual losses due to corrosion are approximately 3-4%
of GDP in many advanced countries and it is even more in developing countries.

Economic impact of corrosion

 Maintenance and operating costs: One fourth of the iron produced is used to
replace bridges, buildings and other structures that have been destroyed by
corrosion. The corrosion causes damage to chemical process plants and other
equipment.
 Plant shutdowns, low efficiency of heat transfer, loss of production while the plant
is inoperable during repairs/replacement work

Corrosion classification
Corrosion of metals depends on the environment to which the metals are
exposed.
The corrosion of the metals can be classified into two major categories. They are
 Dry or chemical corrosion
 Wet or electrochemical corrosion

Dry or Chemical Corrosion

This type of corrosion occurs by direct chemical interaction between the
environment and the metals and alloys. Presence of an electrolyte/conducting corrosive
medium is not essential for dry corrosion to occur. Due to the direct interaction
between metal and corrosive environment, it is also known as direct corrosion. Dry
corrosion could be due to oxygen (O2), or by other gases (like SO2, Cl2, H2S and NOx etc.,)
or by liquid metals (Eg: liquid metal mercury dissolving most of the metals forming
amalgams there by corroding them)
Wet or Electrochemical corrosion

2
Department of Chemistry Unit II NMIT Bangalore , NDU

For wet corrosion to take place presence of conducting medium is very much
necessary. Wet corrosion occurs due to the formation of separate anodic and catholic
areas. It involves flow of electron between the anodic and cathodic areas through
electronic conductor. This is known as corrosion current. Metal ions formed a t the
anode will combine with anions of electrolyte and forms corrosion product somewhere
between anodic and cathodic areas.
Electrochemical theory of corrosion: (General mechanism)
According to electrochemical theory of corrosion, when a metal is exposed to
corrosive environment, the process of corrosion sets in by the formation of number of
anodic and the cathodic areas on the metal surface (micro galvanic cell). The potential
difference in between anodic and cathodic areas is the driving force for electrons to flow
from the anodic area to the cathodic areas. Corrosion always occurs at the anodic area
of the metal due to oxidation process and thus electrons are liberated.
Conditions necessary for electrochemical corrosion are :
An anodic reaction (oxidation)
A cathodic reaction (reduction)
A metallic path of contact between anodic and cathodic sites (electronic
conductor)
An electrolytic path of ions from corrosive medium towards cathodic areas.
Reactions which are taking place during electrochemical corrosion are summarised
below:
Anodic reaction:
−¿¿
M  Mn+ + ne
−¿¿
Ag  Ag+1 + e
−¿¿
Zn  Zn2+ + 2e
−¿¿
Fe  Fe2+ + 2e
Cathodic reactions:
The electrons set free at the anodic area flow through the metallic conductor and are
consumed at the cathodic area. Depending upon the nature of corrosive medium
different cathodic reactions are possible in the absence and in presence of oxygen. They
are:
(i) Hydrogen reduction in acid medium in absence of oxygen
2H+ (aq) + 2e− → H2

3
Department of Chemistry Unit II NMIT Bangalore , NDU

(ii) Hydrogen reduction in acidic medium in presence of oxygen

4H+ + O2 + 4e-  2H2O
(iii) Reduction of water in absence of oxygen
2H2O + 2e− → H2 (g) + 2OH− (aq)
(iv) Reduction of water in presence of oxygen
O2 (aq) + 2H2O + 4e− → 4OH−(aq)
Hydrogen reduction and oxygen reduction are the most common cathode
reaction, since any aqueous solution in contact with air contains dissolved oxygen.
From, electrochemical theory, it is clear that no corrosion take place at the
cathodic area, since cathodic reaction does not involve metal dissolution. Corrosion and
hence metal dissolution take place only at anodic area. Cathodic area stimulates
corrosion of the anodic part by utilizing the electrons produced at anodic area.

Mechanism of rusting:
Rusting is the name more commonly referred for the corrosion of iron. When
iron is exposed to atmosphere, in the presence of moisture, it undergoes corrosion.
Depending upon the concentration of oxygen present in the environment different types
of corrosion products are produced. Following figure illustrates the mechanism of
rusting:

Reactions :
At anodic sites: Fe → Fe 2+ + 2e−
Electrons liberated at the anode migrate to the cathode causing corrosion current. The
Fe2+ ions formed at the anode combine with OH - liberated at the cathode to form the
corrosion product (ferrous hydroxide) somewhere between the anode and cathode,
after diffusing towards each other through the conducting me

4
Department of Chemistry Unit II NMIT Bangalore , NDU

At cathodic sites: O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)

Overall reaction: 2Fe + O2 (g) +2H2O (l) → 2Fe2+ (aq)+ 4OH−(aq)  2Fe
(OH)2
In presence of enough oxygen, ferrous hydroxide reacts with moisture and oxygen to
give yellow rust.
4 Fe (OH)2 + 2 H2O + O2 → 2 [ Fe2O3. 3H2O] (Yellow rust)
If the supply of oxygen is limited, the corrosion product is black rust - anhydrous
magnetite.
6 Fe (OH)2 + O2 → 2 [ Fe3O4. 3H2O] (Black Rust)
Rust is a brittle substance that easily flakes off the surface to expose more iron atoms
and the process starts over again. It is too porous to shield the underlying metal from
further oxidation.
Differences between dry corrosion and wet corrosion
Dry Corrosion Wet Corrosion
Involves direct attack of Occurs due to existence of separate
atmospheric gases like anodic and cathodic areas between
O2, SO2 and liquid metal which current flows through the
medium
No need of aqueous
corrosive electrolyte Needs an aqueous conducting
corrosive electrolyte
Types include oxidation Types include galvanic, pitting, stress
corrosion, liquid metal and inter- granular
corrosion and corrosion
by gases
Less prevailing More common

CORROSION TYPES:
1. Galvanic corrosion / Differential metal corrosion
This form of corrosion occurs when two dissimilar metals are in physical contact
with each other in presence of aqueous electrolyte. Metal with lower standard
reduction potential will undergo oxidation and undergoes corrosion. Metal with higher
standard reduction potential will acts as cathode and remains un-attacked. Driving force
for galvanic corrosion is potential difference between two metals.

5
Department of Chemistry Unit II NMIT Bangalore , NDU

When zinc is made to be in contact with copper, zinc acts as anode and undergoes
corrosion because of lower standard reduction potential ( - 0.76V) and copper remains
unaffected since its SRP is high ( + 0.34V)
Anodic reaction : Zn  Zn2+ + 2e− ( corrosion )
Cathodic reaction depends upon the nature of corrosive environment:
2H+ (aq) + 2e− → H2 ( Hydrogen evolution)
O2 (g) + 2H2O (l) + 4e− → 4OH−(aq) ( oxygen absorption)
Some examples of galvanic corrosion are given below:
 Copper piping connected to steel tanks.
 Zinc coated screws in a sheet of copper
 Steel propeller shaft in bronze bearing
Galvanic corrosion also occurs in the atmosphere. The severity depends largely on
the type and the amount of the moisture present. Corrosion is greater in the seashore
than in a dry rural atmosphere. Condensate near a sea shore contains salt and therefore
is more conductive (and corrosive) and a better electrolyte than condensate in an inland
location.
Accelerated corrosion due to galvanic effects is usually greatest near the junction
with attack decreasing with increasing distance from that point. In the galvanic couple
like Zn/Fe, Fe/Sn, Fe/Cu, Zn/Sn, Zn/Cu; the first metal is anodic with respect to the
second metal and hence undergoes corrosion. It is to be noted that nuts, bolts, and
hinges are made up of one single metal or alloy in order to prevent the galvanic
corrosion.
[Link] aeration corrosion
Differential aeration corrosion, which is also known as concentration cell
corrosion happens when a metal is exposed to different concentrations of air or oxygen.

6
Department of Chemistry Unit II NMIT Bangalore , NDU

The part of the metal exposed to less oxygen acts as anode and part of the metal
exposed to more oxygen acts as cathode.
−¿¿
At the anode (less oxygen concentration) : M -> Mn+ + ne
At the cathode ( More oxygen concentration) : O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)

Eg: A plate of pure zinc which is partially immersed in an aerated solution of sodium
chloride.

Anodic reaction at lower immersed portion of metal : Zn  Zn2+ + 2e

Cathodic reaction near the water surface : ½ O2 + H2O + 2e −¿  2OH-
Water line corrosion is the best examples for differential aeration corrosion
Water line corrosion:
Waterline corrosion is common in water lifting pipes under water. When a
storage tank is used to collect water upto certain level, just below the water line
concentration of oxygen is less. Above the water line metal is exposed to large excess of
oxygen/air. Just below the water line material will become anode and corrosion
products will be deposited. A distinct yellow line is formed just below the water line.
Ocean going ships also suffer from this type of corrosion. Ships sunk under water for
several years do not undergo corrosion, as they are exposed to equal concentrations of
oxygen.

7
Department of Chemistry Unit II NMIT Bangalore , NDU

3. Pitting Corrosion
Pitting corrosion is a localized and accelerated corrosion resulting in the
formation of pits or pin holes around which the metal is relatively un-attacked. It is the
most destructive type of corrosion. Surface appears rough as pits are sometimes
isolated or close together. Generally a pit may be described as a cavity or hole with the
surface diameter about the same length as or less than the depth. Pitting is localized and
intense form of corrosion and failure often occurs with extreme suddenness without
prior indication.
Pitting corrosion is initiated by deposition of extraneous matter, scale, water
drop, dust or due to the break down of the protective film. Whenever dust particles are
deposited, owing to the different amount of oxygen in contact, with metal, the small part
beneath the impurity becomes the anodic areas and the surrounding large parts become
the cathodic areas. Intense corrosion starts just underneath the impurity. It is shown
schematically in the following figure :

Pitting corrosion is characterized by small anodic area and large cathodic area,
resulting in accelerated corrosion at the anodic area. It is an autocatalytic process, with
the initially formed pit produces conditions which are both stimulating and necessary
for the continuing activity of the pit. Even though there is only a small percent weight
loss .it causes equipment to fail because of perforation of the entire structure. It is often
8
Department of Chemistry Unit II NMIT Bangalore , NDU

difficult to detect pits because of their size and because corrosion products cover the
pits.

Other examples for pitting corrosion include: peeling of tin coat on iron

Factors affecting corrosion

The rate of corrosion of a material in a given environment is influenced to a varying
degree by several factors. These factors can be classified into two types given below:
Primary factors - the factors associated mainly with the metal
Secondary factors - the factors which vary mainly with the environment
Primary factors
Factors related to the corroding metals are known as primary factors.
(a) Nature of metal and relative electrode potentials of metals
In general the metals with lower electrode potential values are more reactive
than the metals with higher electrode potential values.. The larger the potential
difference between the anode and cathode higher is the corrosion rate. When two
different metals with large difference in their electrode potential are in contact with
each other, the more reactive metals undergo corrosion. Example; Corrosion of zinc is
faster than iron when in contact with copper in a medium. This is because the electrode
potential difference between Zn and Cu is greater than that of Fe and Cu.

(b) Relative Cathodic and Anodic area

The rate of corrosion is greatly influenced by the relative areas of anode and
cathode. If a metal has a small anodic area and large cathodic area, then the corrosion is
more intense and faster at the anodic region. At anode oxidation takes place and
electrons are liberated. At the cathode these electrons are consumed. When the anode is
smaller and cathode region is large, electrons liberated at the anode are rapidly
consumed at the cathode region. The demand for electrons by the large cathodic areas
can be met by the smaller anodic areas by undergoing corrosion at a faster rate. This
makes the anodic reactions to take place at its maximum rate thus increasing the
corrosion rate. Example; Small steel pipe fitted in a large copper tank, iron bolt and nuts
in copper boilers

9
Department of Chemistry Unit II NMIT Bangalore , NDU

(c) Hydrogen Overvoltage

The difference between the observed potential at which reduction of H + ions to
H2 gas occurs at a cathode and the theoretical potential at which it should have occurred
is known as hydrogen overvoltage. Increased hydrogen overvoltage at a cathode reduces
corrosion rate, when the reduction of H+ ions is the cathodic process. When the
hydrogen evolution reaction on the metal surface is low, H 2 gas is liberated easily and
then the cathodic reaction rate is faster. This makes the anodic reaction also faster,
thereby promoting overall corrosion reaction.

(d) Nature of corrosion product

The corrosion product is usually an oxide of the metal which may or may not
form a protective layer on the metallic surface. If the corrosion product deposits and is
insoluble, stable, uniform adherent and non-porous, it acts as a protective film
preventing the further corrosion of metal. Ex: formation of aluminum oxide on the
surface of aluminum protect aluminum from corrosion. If the corrosion product is not
deposited and is soluble, unstable, non- uniform, non-adherent and porous, the
corrosion continues unabated since in such cases fresh metal surface is continuously
exposed to the corrosion environment. Ex: corrosion of iron. If corrosion product is
volatile, as in case of molybdium accelerated corrosion take place.

Secondary factors
Factors related to the environment are known as secondary factors

(a) Concentration and nature of electrolytes

Rapid corrosion rate is observed at high ionic concentration. Conductivity of
deionized water is 1-10 milli-mhos per meter. Conductivities of tap water and sea water
are 10-20 milli-mhos per meter and 5.3 mhos per meter respectively. Therefore,
corrosion rate in sea water is nearly 500 times as fast as that in tap water and 5000
times as fast as that in demineralized water, based on their conductivity. In the marine
atmosphere, the presence of sodium and other chlorides leads to increased conductivity
of the liquid layer in contact with the metal surface. So the corrosion rate is increased
and the salt air of coastal cities is very damaging to exposed metal when compared to
that at interior places.

10
Department of Chemistry Unit II NMIT Bangalore , NDU

(b) pH of the medium

In general, lower the pH of corrosion medium, higher is the corrosion rate.
However some metals like Zn, Al etc., undergo severe corrosion in highly alkaline
solution. pH of the solution also decides the type of cathode reaction
(c) Temperature
The rate of a chemical reaction in general, increases with rise in temperature. At
elevated temperature, there will be increase in the conductivity of the medium, which
contributes to increased corrosion rate.
(d) Presence of impurities in atmosphere: Atmosphere, in the vicinity of industrial
areas, contains corrosive gases like CO2, H2S, SO2, and fumes of HCl, H2SO4, etc. In
presence of these gases, the acidity of the liquid, adjacent to the metal surfaces,
increases. This consequently results in an increase of corrosion current, flowing in the
local electro-chemical cells on the exposed metal surfaces. Similarly, in the marine
atmosphere, the presence of sodium and other chlorides (of sea water) leads to
increased conductivity of the liquid layer in contact with the metal surface, thereby
corrosion is speeded up.

CORROSION CONTROL TECHNIQUES:

Different techniques are being adopted to control corrosion. The technique
adopted to control/minimise corrosion largely depends upon the nature of corrosion

1. PROTECTIVE COATING :
Base metal which is to be protected from corrosion can be coated with either
another metal, or can be subjected for inorganic coating or organic coating
Metal coating : Deposition of a protective metal over the surface of the base metal is
called metallic coating. It could be anode metal coating and cathode metal coating .
Anodic coatings are produced by coating the base metal with more active metal
which are anodic to the base metal . Ex Coating of iron with Zn, Mg and Al. When coated
metal rupture no damage happens to the base metal, as it is cathodic to the coated metal
Cathodic metal coating are produced by coating a base metal with metal which is
more noble and cathodic. Ex: Metals like Cu, Ni, Sn, Ag are used for cathode coating. If
discontinuity or rupture happens on cathodic coating base metal will under go severe
corrosion as it is anodic to the coated metal.

11
Department of Chemistry Unit II NMIT Bangalore , NDU

Galvanisation:
Giving a Zn metal coating on iron / mild steel is known as galvanization.
When the coating covers the entire surface of the substrate metal, the coating isolates it
from the environment and protects it against corrosion. When the coating breaks or
cracks zinc act as anode and the substrate iron and mild steel acts as cathode. Thus, zinc
becomes sacrificial anode and provides protection to iron and mild steel sheets, pipes,
wires are usually galvanized. Galvanisation is done by hot dipping process as discussed
below:

Pretreatment: The metal surface is cleaned to remove organic matter like grease/oil by
washing with organic solvents. The rust and other deposits are removed by washing
with dilute sulfuric acid and the surface is finally washed with water and air dried.
Process: Galvanization is done by hot dipping processes. Melting point of Zn is 419 oC.
Zn is melted and kept at 425-430 oC. Ammonium chloride flux is spread over it to
prevent its oxidation of molten zinc by air.
Iron and mild steel objects are degreased, pickled and cleaned. They are then
dipped in molten Zn bath. Pair of hot rollers wipes out excess of zinc coating to produce
a thin uniform coating on the objects which are then cooled. It is shown schematically in
above figure. Galvanized sheets cannot be used to prepare tins or cans for storing food
materials, because zinc salts are toxic.
Applications: Used in the manufacture of fencing wire, roofing sheets, buckets, bolts,
nuts, nails and screws
Main advantage of galvanisation is that, base metal will never undergo corrosion
even if the coating is ruptured.

12
Department of Chemistry Unit II NMIT Bangalore , NDU

However galvanised articles should not be used for preparing and preserving
food stuffs since zinc dissolves in dilute acids present in food stuffs producing toxic zinc
compounds

Tinning:
Steel sheet is washed with organic solvents to remove grease/oil deposits. It is
then treated with dilute sulfuric acid to remove rust deposits and finally washed with
water and air dried.
Process: Tinning is done by hot dipping. Melting point of Sn is 232 oC. Cleaned sheet is
passed through molten ZnCl2 and NH4Cl flux to help molten tin to adhere on the metal
surface. It is the dipped into molten tin maintained at 250 ℃ . Finally passed through
series of rollers immersed in palm oil. The rollers wipe out excess tin and oil prevents
oxidation of tin
Metal coated with tin are mainly used for storing food stuffs such as jam , food
items, milk products etc., However, tin coating provides complete protection against
corrosion only if it covers the steel surface completely. If small crack is formed in the
coating the galvanic cell formed with exposed steel/iron as anode and tin coating as
cathode. An intense localised corrosion occurs at the exposed iron surface because of
large cathodic area (tin) and small anodic area.
Differences between galvanisation and tinning:
Galvanization Tinning
A process of coating Zn over A process of coating Sn over
iron/steel to prevent it from iron
rusting (anode metal coating) to prevent it from corrosion
(cathode metal coating)
Hot rollers used to wipe excess Hot rollers are immersed in
coat are not immersed in oil Palm oil
Galvanized containers cannot be Tin coated containers can
used to store acidic foodstuffs be used to store foodstuffs
because zinc reacts with food acids because tin is nontoxic and
forming highly toxic zinc does not react to cause any
compounds. food poisoning
Zinc protects the underlying iron Tin protects the base metal
by sacrificial action iron due to its noble nature.

Zinc continues to protect iron by Tin protects the iron till the
sacrificial action in the event of coating is perfect and any
puncture/break in coating break causes rapid
corrosion of iron

13
Department of Chemistry Unit II NMIT Bangalore , NDU

[Link] coating ( Chemical conversion coating ):

Anodization is an example for inorganic chemical conversion coating. In this
surface of metal is converted into a compound by chemical or electrochemical reactions.
The resultant product forms a barrier between the metal and corrosive environment.
These chemical conversion coatings are integral part of metal itself. Eg: Al, Zn, Mg etc.,
Anodization of aluminum :

Anode: Aluminium
Cathode: Steel/copper/lead
Electrolytic bath: chromic acid/sulfuric acid/phosphoric acid
Temperature: 35 ℃
Current density: 10-20 mA/cm2
Thickness of oxide layer formed: 2-8 μm
Anodization carried out by using phosphoric acid bath tends to be porous and provides
good adherence for paints and dyes.
Anodised articles are used as in soap boxes, tiffin carriers and window frames etc.,

[Link] anode method

In sacrificial anode method, more reactive metal is kept in contact with the metal
structure to be protected. The reactive metal becomes anodic part and the structure
becomes cathodic part of the corrosion cell. The anode is sacrificed to protect the
structure. Hence this method is called sacrificial anode method.

14
Department of Chemistry Unit II NMIT Bangalore , NDU

Mg is generally used as sacrificial anode for protecting iron article. Mg is more reactive
metal than iron and hence it is usually used as anode. It becomes anodic part when in
contact with iron. Following reaction take place when Mg is made to couple with Iron.
At Anode: 2Mg(s) → 2Mg2+ (aq) + 4e−
At Cathode: O2 (g) + 2H2O (l) + 4e− → 4OH−(aq)
Net reaction: 2Mg (s) + O2 (g) + 2H2O (l) → 2Mg(OH)2
Advantages: No external power supply is necessary.
Can be used in remote and difficult to reach areas.
Low installation and maintenance cost.
Replacement is much cheaper than replacing the tank/oil pipeline

Corrosion penetration rate: (CPR)

Rate at which material losses its weight as a consequence of corrosion is known
as corrosion rate. Corrosion rate is a measure of corrosion resistance. Corrosion rates
can be expressed in a variety of ways. They are % weight loss, mg /cm 2/day, g/inch2/hr
etc, However, these do not express corrosion resistance in terms of penetration.
From an engineering view point, the rate of penetration, or thinning of a
structural piece is a useful tool to predict the life of a given component. The expression
mils per year (mpy) is the most desirable way of expressing corrosion rate. It can also
be expressed by milli mils per year (mmpy) (1mil = 0.001inch)
K xW
In general corrosion penetration rate (CPR) =
D xA x T
Parameters Significance CPR ( in mpy) CPR ( in mmpy)
( Units to be taken) ( Units to be
taken)

15
Department of Chemistry Unit II NMIT Bangalore , NDU

K Constant 534 87.6

W Weight loss mg mg
D Density g/cm3 g/cm3
A Area inch2 cm2
T Time duration Hours Hours
1inch2 = 6.4516cm2
1 year = 1x365 x24 = 8760hr
1kg = 106 mg
Numerical Problems:
1. A 5.5 kg of iron metal piece of density 8.1g/cm 3 with area 10.0 inch2 was
submerged in sea water for 10.5 years. Weight of the remaining metal was found
to be 2.4 kg. Calculate CPR in mpy and mmpy
K xW
CPR =
D xA x T
6
534 x 3.1 x 10
= = 222.19 mpy
8.1 x 10 x 10.5 x 365 x 24
6
87.6 x 3.1 x 10
= = 5.64 mmpy
8.1 x 10 x 6.4516 x 10.5 x 365 x 24
Numerical problem for practice:
1. Corrosion penetration rate of square iron metal weighing 5.5 kg was reported to be
222.19mpy and 5.65 mmpy. It was submerged in sea water for 16.2 years. At the
end of this time period, metal weighed 1.9 kg . What was area of the metal? Express
your answer in cm2 and inch2 [Given density = 8.1g/cm3]
2. 7.8 kg of iron piece of density 8.1g/cm3 with area 12.5 inch2 was submerged in sea
water for 13.5 years. Weight of the remaining metal was found to be 4.8 kg. Calculate
CPR in mpy and mmpy

16
Department of Chemistry Unit II NMIT Bangalore , NDU

METAL FINISHING
Introduction
The term metal finishing applies to all surface processes which are carried out in
order to change the metal surface properties by deposition of layer of another metal or a
polymer or by the formation of an oxide film.
The important metal finishing techniques are
(i) Electroplating of metals, alloys and composites.
(ii) Electrolessplating of metals, alloys and composites.
(iii) Immersion plating of metals (involves chemical displacement of metals).
(iv) Chemical conversion coatings based on metal compounds (involves the deposition
of inorganic coatings such as oxides, chromates, phosphates and their mixtures. E.g.,
anodizing,
phosphating, chromating).
(v) Electrophoretic painting which involves painting on electrically charged conducting
surface such as motor car body

Electroplating

The techniques of metal finishing include electroplating of metals and alloys and
electroless plating of a modified surface. Electroplating can be defined as a technique by
which a coating metal is deposited on the substrate metal by passing direct current
through an electrolytic solution, containing the soluble salt of the coating metal. The
deposited material bestows desired properties like extra thickness on undersized parts,
abrasion and wear resistance, corrosion protection and aesthetic qualities to a surface
that otherwise lacks it. The common metals used for coating purposes are Zn, Cu, Ni, Cr,
Ag, Au and Pt.

Theory of electroplating

Electroplating is the technique of electrodeposition of a metal on a substrate

made up of another metal, alloy, or non-metal by the process of electrolysis. The
electroplating device is an electrolytic cell in which two electrodes (anode and cathode)
are dipped in an electrolytic solution. The substrate to be plated acts as the cathode and
the coating metal will be the anode. Both the electrodes are introduced in an electrolytic
solution containing dissolved metal salts that permit the flow of electricity. A rectifier
provides direct current to the anode, oxidizing the metal atoms, allowing them to go into

17
Department of Chemistry Unit II NMIT Bangalore , NDU

the electrolyte. The dissolved metal ions in the electrolyte are reduced at the interface
between the solution and the cathode, and deposit on to the cathode. The anode
dissolution rate is equal to the cathode plating, equivalent to the current flowing
through the circuit. Thus, the anode continuously replenishes the ions in the electrolyte.
The device used for electroplating is an electrolytic cell in the form of a tank having two
electrodes immersed in the electrolyte solution. The schematic representation of
various components of electroplating unit is shown in following figure

Components include:

• An electroplating bath containing a conducting salt and the metal to be plated in

a soluble form as well as a buffer and additives.
• The article to be plated - electronically conducting cathode.

• The electronically conducting anode, either the coating metal itself, or an inert
material of good electrical conductance.
• An inert vessel to contain the above-mentioned materials made up of either
rubber lined steel, concrete, or wood.
The electrolytic bath concentration remains unaltered during electrolysis when the
anode is made of coating metal itself as the metal ions deposited from the bath are
continuously replenished by the reaction of free anions with the anode metal.
Example, CuSO4 solution is used as an electrolyte.
CuSO4 → Cu2+ + SO42−

18
Department of Chemistry Unit II NMIT Bangalore , NDU

Cu2+ ions migrate to the cathode and get deposited there on passing current.
Cu2+ + 2e − → Cu
The free SO42- ions move to the copper anode and dissolve an equivalent amount of
copper to form sulphate.
Cu + SO42- → CuSO4 + 2e
Thus, a continuous replenishment of electrolytic salt occurs during the process of
electrolysis.
In some electroplating processes inert anodes like lead or graphite are used, wherein
metal ions to be plated must be intermittently replaced to maintain proper coating
metal ion concentration in the bath. Moreover, the process of electroplating goes on
nonstop, since the anode is not consumed, and its replacement is not required.

Factors influencing the nature of deposit

(a) Current density

Current density of deposition: The current density (c.d.) of deposition is defined

as the current per unit area generally expressed in milliamperes per square centimeter
(mA /cm2) of the electrode surface. As the applied voltage is increased the current
density rises, till it reaches a limiting value. At low current densities, surface diffusion is
fast compared with electron transfer and the adatoms finds the most favourable position
(kink sites) resulting in a well-formed deposit. As the current density is increased,
surface diffusion is slowed down compared to the electron transfer and the adatoms
may not reach the most favourable positions. Further, at high potentials, number of
nuclei formed may also ncrease. These may lead to a less ordered deposit with
macroscale [Link] very high current densities (below limiting current region) mass
transport predominates in solution resulting in a bad deposit with rough and powdery
texture which is poorly adherent to surface At very high current densities above the
limiting current, hydrogen evolution on the surface predominates causing a fast
depletion of H+ions in the vicinity of the cathode. This results in dispersed powders
containing oxides and hydroxides of the metal. In practice, optimum current density for
a particular deposition is actually determined and used so as to get a good deposit.

(b) Metal ion concentration

As the electroplating involves discharge of free metal ions, the concentration of

free metal ions play an important role. If concentration of metal ion is low the crystal

19
Department of Chemistry Unit II NMIT Bangalore , NDU

size will be smaller and a fine adherent film may be coated. Thus ideal situation is low
free metal ion concentration in a concentrated solution of metal compound which can be
attained by addition of a compound with a common ion or by the formation of complex
compound and ions. e.g., when copper is deposited from electroplating bath containing
copper sulphate solution, sulphuric acid is added to increase the concentration of
sulphate ion. The concentration of cupric ions is reduced due to common ion effect.

(c) Temperature:

Generally, the solution to be deposited is used at room temperature. However, warm

baths are used for increasing solubility of electrolyte and current density. The size of the
crystals increases with increasing temperature and renders lower adherence. But on
the other hand the solubility and metal dissociation increases at higher temperature
leading to higher conductance of the solution. Also, the mobility of ions increases at
higher temperature and decreases the viscosity of the electrolyte solution so that
cathode film is replenished at a faster rate. There are disadvantages also of using high
temperatures. Possibility of corrosion of equipment, decomposition of organic addition
agent and evolution of hydrogen gas at cathode would increase at higher temperature.

So the optimum range of temperature needs to be selected.

(d) pH of the electrolyte

The pH of the electrolyte solution should be properly maintained. The range of

the pH varies for different types of plating bath. If pH is more towards acidic side the
nature of the deposit will be affected adversely as evolution of hydrogen gas is expected
at cathode thereby forming burnt deposit. If pH is more towards basic side the plating is
delayed, so uneven and thick deposit is obtained. Suitable buffers may be used for
maintaining the appropriate pH.

(e) Presence of additives:

To obtain electroplating with desired qualities and specifications, additional

substances called additives are added in small quantities to the electrolyte bath. These
additives have capacity to modify the structure, appearance and characteristics of the
deposit.

20
Department of Chemistry Unit II NMIT Bangalore , NDU

The different types of additives used are (i)

Complexing agents:

(ii) Brighteners:

(iii) Levellers:

(iv) Wetting agents:

(v) Structure modifiers:

(f) Throwing power of the plating bath

Throwing power is defined as the degree of uniformity of metal distribution or evenness

of deposit thickness obtained on a cathode of irregular shape. If the distribution of the
deposit is uniform throughout the surface of the article to be coated, the throwing
power is considered good.

Electroplating of chromium

Chromium plating is a finishing treatment utilizing the electrodeposition of a thin

layer of chromium on a metal substrate. This layer can either be decorative or corrosion
protective to the base surface.

Pretreatment :

Metallic surfaces (substrate) are normally associated with greasy materials or a thin
film of metallic oxide. The substrate surface should be made free from dirt, oil and
grease before electroplating. Degreasing of substrate surface is done either by treating
the surface with organic solvents or aqueous alkali treatment. This is followed by
“Pickling” which involves neutralization of alkali and dissolution of oxide layer by
immersion in 10% sulphuric acid. Further, polishing of the substrate is done either
through mechanical grinding and buffing or anodic dissolution of the surface of the
substrate known as

Chromium coatings are generally thinner and have micro pores in it. As the
thickness of the coating increases, cracks develop in the coatings. Hence, chromium
coatings are always plated on nickel/copper undercoats. Ni gives protection and
chromium gives decorative finish.

21
Department of Chemistry Unit II NMIT Bangalore , NDU

• Chromium anodes are not used in electroplating of chromium. The anode

efficiency is nearly 100 % whereas cathode efficiency is at best around 20 %. The
metal going into the solution is five times of the metal getting deposited,
resulting in building up of excessive chromic acid concentration. This disturbs
the ratio of Cr (III) to Cr (VI) and the conductivity of the bath. The electrodes
become passive in acidic medium, and they result in a black and burnt deposit. To
avoid this, inert material is used as anode and chromium electrolyte in the bath.
• Chromium has higher electrode potential and can be easily coated on iron to
protect from rusting/corrosion.

Reactions:

The plating bath contains CrO3 in which Cr is in +6 oxidation state. This is reduced
+3 oxidation state by a series of complex reactions in the presence of SO 4 2-(catalyst)
furnished by H2SO4. Cr3+ ions are reduced to elemental chromium which gets
deposited on the substrate.

The amount of Cr3+ ions should be restricted in order to obtain good deposit.
Insoluble anodes like Pb-Sb or Pb-Sn alloys covered with a layer of PbO2 (which oxidize
Cr3+ to Cr6+) are used thus controlling the Cr3+ concentration

Table 1. Comparison of decorative and hard coating of chromium

Decorative coating Hard coating
Bath composition Chromic acid (250 g) + Chromic acid (250 g) +
H2SO4 (2.5 g) + H2SO4 (2.5 g) +
Trivalent chromium (1g) Trivalent chromium (1 g)

Operating 45 – 55 °C 45 – 55 °C
Temperature

22
Department of Chemistry Unit II NMIT Bangalore , NDU

Anode Insoluble anodes like Lead – lead: 6%

Pb – Pb: 6% Sb – Pb: 7%
Sb - Pb--7% Sn
Sn
Cathode Article to be coated Article to be coated
Current density 145--430 A/ft2 290--580 A/ft2
Cathode efficiency 10 – 15 17 – 21
Applications Decorative applications with Coating of industrial
corrosion resistance finish on components like gauges,
cycles, automobiles, furniture, dies, cutting tools, piston
household fittings, aircraft, rings and hydraulic rams.
surgical and dental
instruments.

ELECTROLESS PLATING

Electroless plating is a method of deposition of a metal film on a substrate surface

(conductor or non-conductor) from metal salt solution using a suitable reducing agent
without using electrical energy. The reaction can be depicted as

Metal ions + Reducing agent Metal + Oxidized product the method

involves the deposition of metals such as Cu, Ag, Ni, Au or Pd on the surface of base
material by means of a reducing agent. Electroless plating also results in a fine-grained
deposit of metal that has comparable finishing as that of traditional electrodeposit
finishing. In industries, such process is used to obtain an extremely uniform plate on
non-conductors like plastic, electroformed dies, hard memory disks, printed circuit
boards (PCBs) etc. This technique is also used for prevention of corrosion.

Process of electroless plating: The steps involved in electroless plating techniques are
as follows:

(i) Preparation of active surface: This is the most important step and surface is
activated by any of the following ways.
(a) etching – by acid treatment
(b) electroplating with a thin layer of metal or insulators like plastic surfaces
followed by heat treatment.
(c) Alternate treatment with SnCl2 and PdCl2 on the plastic surface

23
Department of Chemistry Unit II NMIT Bangalore , NDU

SnCl2 + PdCl2 Pd + SnCl4 Pd is coated on

plastic.

(ii) Preparation of plating bath:

(a) Metal to be coated in the form of chloride or sulphate solution.

(b) Reducing agents like formaldehyde and sodium hypophosphate for reduction
of metal ion to metal
(c) Complexing agents like EDTA, tartrates, citrates to form metal complexes to
prevent excess deposition.
(d) Stabilizers like thiourea, calcium ions too prevent decomposition of the bath
and to impart stability to the solution.
(e) Exaltants (accelerators) like succinates, glycinates and fluorides to increase
the rate of plating.
(f) Brighteners like thiosulphate to give lustrous appearance.

(g) Buffers like boric acid to maintain the pH.

(iii) Reduction step: Active surface is dipped in the bath and deposition is carried
out. The plating is carried out in a series of tanks where the object is immersed to
plate the desired metal. The rate of deposition is controlled by the amount of
reducing agent present and the type of chelating agent used. The deposition rate is
normally 12.5 – 25 µm, although, it has been done up to 650 µm in thickness.
Advantages of electroless plating
The following are main advantages of electroless plating.
1. More uniform coating on surface of object whatever shape it may have. Even the
objects having irregular shapes, holes, recesses, internal surfaces, valves, or
threaded parts get uniform deposit since it has better throwing power than
electroplating.
2. Electrical power and other accessories are not required.
3. Coating is harder than regular plating and better wear resistance.
4. Deposits have compatible wettability for oils, inherent lubricity, and non-galling
characteristics, unlike electrolytic nickel.
5. Deposits are much superior to electroplated nickel and hard chrome, as they are
less porous and provide better corrosion protection to steel substrates.

24
Department of Chemistry Unit II NMIT Bangalore , NDU

Electroless plating of Ni on aluminium substrate enhances the solderability

together with providing a non-magnetic under lay in magnetic components. The
deposits are less porous and possess unique characteristic chemical, mechanical
and magnetic properties.
6. Additives or levellers are not required in the process nor the complex filtration
method requirement.
7. It is a simple process, so requires simple equipment.
Disadvantages of electroless plating
The main disadvantages of the process are the following.
1. Due to speedy chemical renewal, cost of waste treatment is high.
2. The frequency of dumping electroless bath is high as it is sensitive to
contamination.
3. Costs per unit weight of the deposited metal are more.
4. It needs pure chemicals.
5. Chemical reductants are more expensive than electricity.
6. Metal salts and reductant used in electroless plating solutions are
thermodynamically not stable.
7. Impurities or dust or colloidal matter (even if present in trace amount)
promote the decomposition of bath components.
Comparison of electroplating and electroless plating
Property Electroplating Electroless plating
Driving force Electric current Autocatalytic redox reaction
Anode reaction
Cathode Article to be plated Article to be plated with
catalytic surface
Anode Separate anode Article to be plated
Reducing agent Electrons bring about Chemical reagents bring
about reduction reaction

Anode reactant M or H2O R, reducing agent in solution

Nature of deposit Pure metal or alloy Usually metal contaminated
with species derived from
redox reaction

Thickness limit 1 - 100 1 – 100

25
Department of Chemistry Unit II NMIT Bangalore , NDU

(µm)
Applicability Applicable to conductors Can be used for conductors
only and non-conductors

Throwing power Less throwing power; More throwing power and

cannot be used for can be used for irregular and
irregular shapes and uneven shaped objects
intricate parts

Electroless plating of copper on double sided PCB

Plating bath solution:
A solution of copper sulphate (12 g/dm3)
Reducing agent- Formaldehyde (8 g/dm3)
Buffer - Sodium hydroxide (15 g/dm3) + rochelle salt (14 g/dm3)
Complexing agent and exaltant – EDTA (20 g/dm3)
pH – 11 ; Temperature – 250 C

Through hole connections are necessary when double sided printed circuit
boards are fabricated. The electrical connections between two sides of the board are
made by drilling hole and then plating through holes by electroless plating
The plastic board is initially covered with copper layer by cladding thin layers of
electroformed copper foils. The copper clad board is printed with an etch-resistant
pattern of the circuit or the tracking required on both sides. On etching with suitable
etching agent the copper except below the printed pattern is removed, leaving the
circuit pattern. The connection between two sides is made by drilling hole followed by
activation and plating by electroless plating.
Various steps involved are shown in following figure:

26
Department of Chemistry Unit II NMIT Bangalore , NDU

27
Department of Chemistry Unit II NMIT Bangalore , NDU

28