Module -1

CORROSION SCIENCE AND ENGINEERING

Corrosion is defined as “the destruction or deterioration and consequent loss of metals or alloys through
chemical or electrochemical attack by the surrounding environment”.

In simple corrosion and metal extraction can be regarded as

Metal Metal ore

The primary factor that initiate corrosion on metals are atmospheric air, water and also conducting surface of
the metal.
Egs: Rusting of iron, green scales are formed on copper vessels

Corrosion of metal occurs either by direct chemical attacks or by electrochemical attack on the metal by the
corrosive environment.
If the corrosion takes place due to direct chemical attack ( in the absence of moisture ) that type of corrosion is
known as dry corrosion.
If the corrosion of metal takes place due to electrochemical attack in presence of moisture or a conducting
medium such a corrosion is known as wet corrosion or electrochemical corrosion.

Importance of Corrosion in Industry

The three main reasons for the importance of corrosion in industry are:
1. Economics 2. Safety 3. Conservation.

Economics: In India, losses due to corrosion could be around Rs. 2 lakh crores per annum. India loses
5-7% of GDP due to corrosion. To reduce the economic impact of corrosion, corrosion engineers, with
the support of corrosion scientists, aim to reduce material losses, as well as the accompanying economic
losses, that result from the corrosion of piping, tanks, metal components of machines, ships, bridges,
marine structures, and so on.

Safety: Corrosion can compromise the safety of operating equipment by causing failure of pressure
vessels, boilers, metallic containers for toxic chemicals, turbine blades and rotors, bridges, airplane
components, and automotive steering mechanisms. Safety is a critical consideration in the design of
equipment for nuclear power plants and for disposal of nuclear wastes. Sudden failure can cause fire,
explosion, release of toxic product, and construction collapse. For example: Bhopal Gas Tragedy- the
factory was licensed to produce Methyl Iso Cynate,(MIC) an extremely hazardous chemical which was
stored in the corroded reactor tank for more than 3 months as a result of which there was pressure built-
up, and the tank couldn’t resist the extreme pressure generated and exploded releasing gas into
atmosphere. In this disaster at least 15,000 people were killed. Hundreds, thousands are still suffering
from cancer and many are blind.

Conservation: Loss of metal by corrosion is a waste not only of the metal, but also of the energy, the
water, and the human effort that was used to produce and fabricate the metal structures. Loss of
efficiency—like corrosion products decrease the heat-transfer rate in heat exchangers.
Electrochemical theory of corrosion:

Most of the corrosion takes place on the basis of electrochemical reactions on the surface of metal such a type
of corrosion is known as wet corrosion.

Electrochemical theory of corrosion can be Explained by taking iron as an example.

When a metal like iron is exposed to the corrosive environment according to electrochemical theory, corrosion
of metal takes place due to the formation of anodic and cathodic regions on the same metal surface or when the
two metals are in contact with each other in a corrosive medium.

Fe2+ Fe2+ OH- OH-

Anodic region Cathodic region

Electrons

Iron Metal

These anodes and cathodes are formed due to the heterogeneities at the interfaces of the metal and environment.
The heterogeneities on a metal surface could develop due to several factors like
1. on a metal surface if the concentration of the oxygen is different ( if in the metal the area which is exposed to
more oxygen acts as cathode, the area which is exposed to less oxygen concentration acts as anode).
2. Due to contact of two different metals (egs: if copper and iron are in contact with each other , then Fe acts as
anode and copper acts as cathode due to change in electrode potential).
3. If metal surface subjected to stress (area under stress acts as anode).

Thus anodic and cathodic area are formed, in presence of corrosion medium ( like moisture etc.)
At anode oxidation takes place so that metal is converted into metal ions with the liberation of electrons.

M Mn+ + ne-

Egs: Fe Fe2+ + 2e-

At the cathodic regions, reduction takes place since the metal at cathodic region cannot be reduced further, so
some constituents of the corrosive medium take part in the cathodic reaction. Most common type of cathodic
reaction are 1. Liberation of hydrogen 2. Absorption of oxygen.

Cathodic reactions:
(a) Liberation of Hydrogen type
(i) If the medium is acidic and in the absence of O2

2H+ +2e- H2

(ii) If the medium is neutral or alkaline in the absence of O2.

 2H2O + 2e - 2OH- + H2

(b) Absorption of oxygen type

(i) If the medium is acidic and in the presence of O2.

4H+ + O2 + 4e- 2H2O
(ii) If the medium is neutral or alkaline and in the presence of O2.
2H2O + O2 + 4e- 4OH-

The metal ions (Fe2+) liberated at anode and some anions (OH-) formed at cathode diffuse towards
each other through the conducting medium and form a corrosion product some where between the
anode and cathode as

2Fe2+ + 4OH- 2Fe(OH)2

In an oxidizing environment, the insoluble Fe(OH)2 oxidised to ferric oxide as follows

4Fe (OH)2 + O2 + 2H2O 2(Fe2O3 . 3H2O) + H2

yellow rust

if the concentration of oxygen is limited then Fe(OH)2 is converted into magnetic oxide of Fe and is known as
black rust.

3Fe(OH)2 + ½ O2 Fe3O4.3H2O
BLACK RUST

Types of Corrosion: Corrosion of the metals takes place depending on the nature of metals and depending on
the types of environment by different mechanisms, giving different types of corrosion.

1. Galvanic corrosion or differential metal corrosion:

This Type of corrosion occurs when two dissimilar metals are in contact with each other in a corrosive
conductive medium; a potential difference is set up resulting in a galvanic current. The two metals differ
in their tendencies to undergo oxidation. The metal with lower electrode potential or more active metal
acts as anode and the metal with higher electrode potential acts as cathode. The potential difference is
main factor for corrosion to take place. The anodic metal undergoes corrosion where as cathodic metal
gets un -attacked.

Egs: When iron is in contact with copper iron has lower electrode potential acts as anode and undergo
oxidation as,

At Anode: Fe Fe2+ + 2e-

At cathode: O2 + 2H2O + 4e- 4OH- (Reduction of oxygen)
 Where as copper which is having higher electrode potential acts as cathode gets unaffected. The rate of
galvanic corrosion depends upon potential difference between anodic and cathodic metals, ratio of
anodic and cathodic area and environmental factors and tendency of the metal to undergo passivity etc.

Other egs: When Fe is in contact with Sn then Fe acts as anode and Sn acts as cathode but when Fe is in
contact with Zn, Fe acts as cathode where as Zn acts as anode.

Some examples for differential metal corrosion are:

1. Bolts and Nuts made up of different metals
2. Steel Screws in Copper sheets
3. Steel Screws with copper washers

2. Differential aeration corrosion:

Differential aeration corrosion occurs when metal surface is exposed to the differential air or
oxygen concentration, that develops galvanic cell and initiate the corrosion. The part of the metal exposed to
lower oxygen concentration acts as anode and the part of the metal exposed to higher concentration acts as
cathode, so that poorly oxygenated region undergoes corrosion.
Example : When a metal strip of iron, partially immersed in an aerated solution of NaCl the concentration of O2
is higher at the surface than inside the solution. Since cathodic reaction requires oxygen, hence cathodic area
tends to concentrate near the water line so that bottom portion of the specimen acts as anode where corrosion
starts.

At anode: Fe Fe2+ + 2e-

At cathode (near water line): O2 + 2H20 + 4e- 4OH-

Example: Part of the nail inside the wall undergoes corrosion.

Water line corrosion: This is a case of differential aeration corrosion commonly observed in steel water
tanks, ocean going ships etc. in which portion of the metal is always under water.
The part of the metal below the water line is exposed to only to dissolved oxygen while the part above the water
is exposed to higher concentration of oxygen.
Thus the metal part below the water line acts as anode where as above the water line acts as cathode and process
of corrosion starts. The metal just below the water line is more anodic and the creep (meniscus) is the one which
is more oxygenated acts as cathode and unaffected. Amount of creep of the water determines the rate of
corrosion, but mass intense corrosion occurring at the water line, there a brown line is also formed due to the
deposition of corrosion products. This type of corrosion is commonly observed in ships floating in sea water for
a long period of time.

PITTING CORROISON: Pitting corrosion is a localized and accelerated corrosion. When a small particles of
dust or water etc are get deposited on a metal (like steel). The portion covered by the dust will not be well
aerated area compared to the exposed surface hence the covered surface becomes anodic with respect to the
surface exposed. In presence of an conducting medium ( moisture) corrosion starts below the dust part and
forming a pit. Once pit is formed the ratio of corrosion increases, because of the formation of smaller anodic
and larger cathodic area intense corrosion takes place.
Pitting corrosion is one of the most destructive forms of corrosion. It causes equipment to fail because of
perforation with only a small percent weight loss of the entire structure. Because of the small sizes of the pits it
is highly difficult to identify the pitting corrosion. Pitting corrosion is an autocatalytic process, and once the
corrosion products are formed, it further provides the condition for differential aeration below the corrosion
product and surrounding metal parts. The pit grows and ultimately may cause failure of the metal.

Cell reactions: At anode : M Mn+ + ne- (Oxidation of metal M)

At Cathode: O2 + 2H20 + 4e- 4OH-

Factors affecting rate of corrosion:

Several factors affecting the rate of the corrosion which can be divided into two parts 1. Factors affecting on
metal ( related to the metal) 2. Factors affecting on corrosive environment.

Factors affecting the metals:

1. Surface state of the metal or nature of the corrosion product ( passivity):

The corrosion product is usually the oxide of the metal, the nature of the product determines the rate of
further corrosion process.
If the oxide layer which forms on the surface is stoichiometric, highly insoluble and non-porous in
nature with low ionic and electronic conductivity then that type of products layer effectively prevents
further corrosion which acts as a protective film. For egs: Al, Cr, Ti develop such a layer on their surface
and become passive to corrosion and some metal like Ta, Zr and Mo not only forms such a protective
layers but are capable of self repairing oxide films when it is damaged. Hence these are extremely
passive metals.
If the oxide layer forms on the metal surface is non-stochiometric, soluble, unstable and porous in nature
and have an appreciable conductivity, they cannot control corrosion on the metal surface for egs: oxide
layer formed on metals like Zn, Fe, Mg etc.
2. Anodic and Cathodic area:
The rate of the corrosion is greatly influenced by the relative sizes of cathodic and anodic areas.
If the metal has smaller the anodic area and larger the cathodic area exposed to corrosive atmosphere,
more intense and faster is the corrosion occurring at anodic area because at anode oxidation takes place
and electrons are liberated. At the cathode these electrons are consumed. When anode is smaller and
cathode region is larger all the liberated electrons at anode are rapidly consumed. This process makes
the anodic reaction to takes place at its maximum rate thus increasing the corrosion rate. If the cathode is
smaller and reverse process takes place decrease rate of corrosion.
For egs: If tin (Sn) coated on iron (Fe) and in that some area are not covered or some pin holes are left,
there forms smaller anodic area and larger cathodic area because tin is cathodic with respect to iron so
intense localized corrosion takes place. On the other hand if Zn coated to Fe then if there are some pin
holes are there creates larger anodic area and smaller cathodic area because Fe is cathodic with respect
to zinc so that rate of corrosion is very less.

Factors related to corrosive environment:

PH of the medium: Usually higher acidic nature (low PH) higher is the rate of corrosion.
If the PH is greater than 10 corrosion of iron is very less due to the formation of protective coating of
hydrous oxides of iron.
 If PH is between 10 and 3, then presence of oxygen is essential for corrosion of iron.

If the PH is 3 or lower than 3 severe corrosion occurs in the absence of air due to the continuous
evolution of H2 at cathode. However metals like Al, Zn etc undergo fast corrosion in highly alkaline
medium.

CORROSION CONTROL: Corrosion of a metal is a natural spontaneous process, by which metal is

converted into a more stable compound so that corrosion control is more realistic than corrosion prevention. In
general corrosion can be controlled by preventing the formation of galvanic cells.
The methods used to control corrosion are as follows

1. Protective coatings: Corrosion of metal can be controlled by isolating them from the corrosive
atmosphere. This can be done by covering the metal (base metal) with a layer of another metal. This
process is known as metal coating.
The Principal type of coatings applied on the metal surface are
1. Metal coating 2. Inorganic coating 3. Organic coating.

Metal coating: This coating is the deposition of a protective metal over the surface of the base metal. The
method can be applied by electrodeposition, flame spraying, cladding, hot dipping etc.
On the basis of coating there are two classes:
1. Anodic coating: It is produced by coating a base metal with more active metal which are more anodic
with to the base metal for egs: Iron is coated with Zn, Mg, Al etc.,
One of the imp. Properties of these type of coating is that, even if the coating is ruptured, the base metal
does not undergo corrosion. The exposed part of the base metal is cathodic with respect to the coating
metal and coating metal only undergone corrosion there by protecting the base metal. The protection is
there as long as coating is there. Galvanisation is one of the best egs in anodic coating.

Galvanisation: It is a process of coating a base metal (iron) with zinc(Zn) metal. This process usually
carried out by hot dipping method.
Process : The iron sheet to be galvanized is washed properly with organic solvents to remove any
organic impurities ( like oil, grease etc) on the surface afterwards it is washed with dil. H2SO4 to remove
any inorganic impurities (like rust). The iron sheet is treated with a flux of NH4Cl and ZnCl2 finally the
iron sheet is washed with water and air dried. The iron sheet is then dipped in a bath of molten zinc
maintained at 430oc-470oc . Then excess zinc on the surface is removed by passing through a pair of hot
rollers. So that a proper thin coating is obtained.
 Application: Galvanized articles are mainly used in roofing sheets, fencing wire, buckets, bolts nuts,
pipes and tubes etc. but galvanized articles are not used for preparing and storing food stuffs. Since zinc
dissolves in dil. Acids and become toxic.

Inorganic coating or surface conversion coating or chemical conversion coating:

Here a surface layer of the metal is converted into a stable compound by chemical or electrochemical reactions
which forms a barrier between the base metal and corrosion environment. These types of coating are different
compared to that of metal coating because they are integral part of the metal itself and in addition to corrosion
resistance they also provides increased electrical insulation and also physical appearance of the metal. In surface
conversion coating two imp. Type are

1. Anodized coating or anodizing:

Anodizing is usually carried out in non-ferrous metals like Al, Mg, Cr, Ni, etc or their alloys by anodic
oxidation process in which base metal is made as anode, in an electrolytic bath of suitable composition and by
passing direct current. However commercially only Al and its alloy are anodized for corrosion resistance.

Process: The article to be anodized is degreased properly and polished. Then made as anode and copper or lead
is made as cathode. The electrolyte consists of 5- 10 % chromic acid, the temperature is about 350c. The
voltage is programmed to increase from 0-50V (optimum 40v) So as to maintain an anode current density of 10-
20milli amp/cm2. In first ten minutes the potential is increased from 0-40V and at 40V continue anodizing for
about 20min after wards the potential is increased from 40 v- 50v and maintained at 50vc for 5min an opaque
oxide layer of 2-8micrometer thickness is obtained. If higher thickness is required 10% sulphuric acid is used as
an electrolyte at 220c with around 160milliamp/cm2 of current density at 24V a colorless 25micrometer
thickness layer is obtained. Afterwards the article should be dyed properly and finally treated with boil water
containing cobalt or nickel sulphate or Acetate to improve corrosion resistance.
Cathodic protection:

It is a method of protecting the metal or alloy from corrosion and no part of it is allowed to act as anode.
The technique of offering cathodic protection to a specimen (metal) against corrosion by providing electrons
from an external source.
There are two methods for providing electrons for cathodic reactions there are

1. Sacrificial anode method:

The method involves the use of more active metals as sacrificial anode in contact with specimen ( like iron,
copper or brass). The active metals like Zn, Mg, Al, and their alloy acts as an auxiliary anode, and undergo
preferential corrosion protecting the metal structure. Here the anode metals are sacrificed to protect the metal,
the method is known as sacrificial anode method, exhausted anodes are replaced by new ones as and when
required.
Egs: 1. A Mg or Zn block connected to a buried oil tank
2. Mg bars are connected to ocean going ships

Sacrificial anode methods are simple with low installation cost and do not require power supply but involves
recurring expenditure of replacement of consumed anodes.
2. Impressed current method:
This is another method to provide cathodic protection by supplying electrons. These can be provided by a
source of direct current.
The structure to be protected should be made negative (connected to negative terminal of a D.C source). Resin
bonded graphite rod, platinised Ti, Pb are used as anode and connected to the positive terminal. The main
structure being cathode does not undergo corrosion, and anode being inert remains unaffected.

This technique is used to protect marine structure, water storage tanks and other gas or oil pipe lines. This
method is simple, can protect large metal area with low maintenance cost but expensive, because it needs high
current.

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 =
ρ×A×T

Where k = constant
W = total weight loss
of metalρ = density of
metal
T = time taken for the loss of metal
A = the surface area of the exposed metal
The corrosion penetration rate is expressed in terms of thickness or weight loss when the
surfaceof the metal corrodes uniformly across an area.
Note:-
 Unit of CPR in mils per year (mpy) Unit of CPR in mm/year
k = 534 k = 87.6
W = mg W = mg
ρ = g/cm 3
ρ = g/cm3
A = inch2 A = cm2
T = hours T = hours

Numerical problems on CPR

1) A steel of area 100 inch2 is exposed to air. After 1 year it was found that the steel
sheet has lost 485 g due to corrosion. What is the value of CPR in mpy? The
density of steelis 7.9 g/cm3.
Given: K = 534 ρ = 7.9 g/cm3
W = 485 g = 485 x 103 mg A =100 inch2 T = 1 year = 24 x 365
1)

k×W
CPR =
ρ×A×T

534 × 485 x 103

CPR =
7.9 × 100 × 24 × 365

CPR = 37.42 mpy

2) A 10 inch2 steel rod is exposed in an ocean for 10 years. The steel rod corrodes over the
years and experienced a weight loss of 2.6 kg. Determine the CPR of the steel in mpy.
Density of steel is 7.9 g/cm3.
Given: K = 534 ρ = 7.9 g/cm3
W = 2.6 kg = 2.6 x 106 mg A =10 inch2 T = 10 year =24 x 365 x 10

k×W
CPR =
ρ×A×T

534 × 2.6 x 106

CPR =
7.9 × 10 × 24 × 365 x 10

CPR = 200 mpy

3) A piece of corroded steel plate was found in a submerged ocean. It was estimated that
the original area of the steel plate was 10 inch2 and approximately 2.6 kg had corroded
during the submersion. Assuming a CPR of 200 mpy for this alloy, estimate the time of
submersion in years. The density of steel is 7.9 g/cm3.
Given: K = 534 ρ = 7.9 g/cm3
W = 2.6 kg = 2.6 x 106 mg A =10 inch2 CPR = 200 mpy

k×W
CPR =
ρ×A×T

534 × 2.6 x 106

T=
7.9 × 10 × 200

T = 87848.10 hours
T = 10.03 years
4) A piece of corroded alloy was found in an atmosphere. It was estimated that the
original area of the alloy was 800 cm2 and approximately 7.6 kg had corroded during
the exposure. Assuming a CPR of 4 mm/year for this alloy, estimate the time of
exposure in years. The density of the alloy is 4.5 g/cm3.
Given: K = 87.6 ρ = 4.5 g/cm3
W = 7.6 kg = 7.6 x 106 mg A =800 cm2 CPR = 4 mm/year

k×W
CPR =
ρ×A×T

87.6 × 7.6 x 106

T=
4.5 × 800 × 4

T = 46233.33 hours
T = 5.27 years
5) Find the corrosion penetration rate in mm/year when the iron
metal has lost 489 g due to corrosion after 6 years of exposure to
the corrosive environment. The density of the metal is 7.9 g/cm3
and the area of metal is 200 cm2.
Given: K = 87.6 ρ = 7.9 g/cm3
W = 489 g = 489 x 103 mg A =200 cm2 T = 24 x 365 x 6
6)

k×W
CPR =
ρ×A×T

87.6 × 489 x 103

CPR =
7.9 × 200 × 24 × 365 × 6

CPR = 0.515 mm/year

METAL FINISHING:

Metal finishing is a surface process carried out in order to modify the surface properties
of a metal by deposition of a layer of another metal or an alloy or a polymer film.
Egs: electroplating of metals, electroless plating, chemical conversion coating etc.

Technological importance of metal finishing:

Metal finishing imparts desirable surface characteristics such as

1. Imparting higher corrosion resistance.
2. Imparting improved wear resistance.
3. Imparting thermal resistance, hardness, improved solderablity etc.
4. Providing optical or thermal conducting surface.
5. Manufacturing electrical and electronic components such as PCB, capacitors etc.
6. Electroforming of articles.
7. In electro polishing and electrochemical etching.

Electroplating: It is a process of depositing a metal or an alloy or a composite on to a

surface by means of electrolysis.

Electroplating of Chromium:

Pretreatment: Article to be plated has to be degreased with organic solvent followed by

acid pickling. Before electroplating copper and Ni has to be given as undercoat

Bath condition Decorative Cr Plating Hard Cr Plating

Bath Composition Chromic acid and Sulphuric Chromic acid and Sulphuric
acid in 100:1 ratio acid in 100:1 ratio
Temperature 45oC- 60oC 45oC- 60oC
Current Density 100-200 mA/cm2 215-430 mA/cm2
Current Efficiency 8-12% 10-15%
Anode Insoluble anodes such as Insoluble anodes such as
Pb-Sn or Pb-Sn coated with Pb-Sn or Pb-Sn coated with
PbO2 or stainless steel. PbO2 or stainless steel.

Cathode Article to be plated Article to be plated

Application decorative and corrosion Used in automotive
resistant finish, Premium industry: Shock absorbers,
tools and Taps Cylinders
In aerospace Industry:
Landing Gear and
Aluminium piston Heads
In chromium plating sulphate ion provided by the sulphuric acid is believed to act as a
catalyst. Cr is present in the hexavalent state Cr(VI) as CrO3 in the bath solution. This is
converted into trivalent Cr (III) by a complex anodic reaction in the presence of sulphate
ions and then coated, as Cr on the cathode surface the amount of Cr (III) ions should be
restricted in order to get proper deposit. Insoluble anodes are used to maintain the Cr (III)
concentration as they oxidize Cr (III) to Cr(VI). Chromium anodes are not used in Cr
plating because Cr metal passivates strongly in acid sulphate medium and Cr anode gives
Cr (III) ions on dissolution. In the presence of large concentration of Cr(III) ions, a black
Cr deposit is obtained.

CrO3 + H2O H2CrO4

2 H2CrO4 H2Cr2O7 + H2O
H2Cr2O7 Cr2O72- + 2H+
Cr2O72- +14 H+ +6 e_ SO42- 2Cr3+ + 7H2O
Cr3+ + 3e- Cr
3+
2Cr + 3O2 PbO2 2CrO3 + 6e-

Electro less plating: Electro less plating is a method of depositing a metal or alloy over a
substrate (conductor or non-conductor) by controlled chemical reduction of the metal
ions by a suitable reducing agent without using electrical energy.

.Distinguish between electro less and electroplating:

Property Electroplating Electro less plating

Driving force Power supply Autocatalytic redox reaction

Cathodic reaction Mn+ +ne- M Mn+ +ne- M

Anodic reaction M Mn+ +ne- or
n/2 H2O n/4 O2 +nH+ R O + ne-
-
+ne
Site of cathodic reaction Article to be plated Article to be plated
(catalytically active)
Site of anodic reaction separate anode Article to be
plated(catalytically active)
Nature of deposit pure metal or definite alloy Metal with reducing agent
And oxidized products as
Impurities.
Advantages of electro less plating:

1. Does not require electrical power source.

2. It is applicable to conductors, semiconductors and non-conductors like plastics.
3. Electro less plating are less porous than electroplates and posses unique
characteristic chemical, mechanical and magnetic properties.
4. Electro less plating baths have better throwing power and deposit a more uniform
metal coating over an article irrespective of its shape or size.

Electro less plating of nickel: The surface to be plated is first degreased by using
organic solvents or alkali, followed by acid treatment.
1. Al, Cu, Fe and brass need no activation.
2. Stainless steel surface is activated by dipping in hot solution of 50% dilute H2SO4.
3. Mg surface is activated by giving zinc or Cu coating
4. Non-metallic articles are activated by dipping in SnCl2 + HCl solution, followed by
dipping in PdCl2 solution. Then it is dried.

Bath Composition:

Coating solution: NiCl2 solution (20g/L)

Reducing agent: sodium hypophosphite (20g/L)

Buffer: Sodium acetate (10g/L)

Complexing agent: Sodium succinate (15g/)

PH: 4.5

Temperature: 93oc

Reactions: At cathode: Ni2+ + 2e- Ni

At anode: H2PO2- + H2O H2PO3- + 2H+ + 2e-

Net redox reaction: : Ni2+ + H2PO2- + H2O Ni + H2PO3- + 2H+

Both oxidation and reduction takes place on the same substrate surface. In the reaction
there is a liberation of H+ ions, which alter the PH this may affect the quality of plating.
Hence buffer solution is essential.
Plating process will starts at a temperature of 70oc and it is maximum at 93oc. Further rise
in temperature may lead to the decomposition of organic additives, hence temperature
range should be 70-93oc.
Applications:
1. Electro less Ni plating is extensively used in electronic appliances (egs knobs of
hi-fi equipments).
2. Finds application in domestic as well automotive fields (egs: consume jewellery,
car trims, tops of perfume bottles etc.).
3. Electro less Ni coated polymers (like ABS plastics) find preferred decorative as
well as functional applications.
4. Also used in instrumentation and computers in view of its magnetic properties.
5. Heat-treated electro less nickel-plated appliances finds applications in hydraulic
compressors, pressure vessels, pumps and fuel injection assemblies.

Electroless plating of copper [Copper on PCB]:

Pretreatment and activation of the surface: The surface to be coated is first degreased
by organic solvents or alkali followed by acid treatment.
1. Metals like Fe, CO, Ni etc do not need pretreatment.
2. Non-metallic materials (e.g. glass, plastics, printed circuit boards, PCB) are activated
by first dipping in SnCl2 and HCl solution, followed by dipping in PdCl2 solution
and dried.

Composition of bath:

Coating solution: CuSO4 solution (12g/L)

Reducing agent: Formaldehyde (8g/L)
Buffer: NaOH (15g/L) + Rochelle salt (14g/L)
Complexing agent: EDTA (20g/L)
PH: 11.0
Temperature: 25oc

Reactions:
Cathode: Cu2+ + 2e- Cu
Anode: 2HCHO + 4OH- 2HCOO- +2H20 + H2 +2e-

Net redox reaction: Cu2+ + 2HCHO + 4OH- Cu +2HCOO- +2H20 + H2

Applications:
1. Mainly used in printed circuit boards (PCB).
2. For plating on non-conductors.
3. Applied on wave-guides and for decorative plating on plastics.

Preparation of printed circuit boards (PCB): A PCB is made of glass-reinforced rubber

like GR-P or epoxy or phenolic polymer. A thin layer of copper is electroplated over the
PCB. Then, selected areas are protected by employing electroplated image and the
remaining part of the plated copper is removed by etching so as to get required type of
circuit pattern (or track). Connection between the two sides of PCB is made by drilling
holes, followed by electroless Cu plating through holes.