Advanced protective coatings: Electroplating techniques

Advanced protective coatings: Electroplating
Coating metal is deposited as a thin layer of metal or alloy on the base metal by
passing direct current through an electrolytic solution, containing the soluble salt
of the coating metal.
Dr. A.A.NAPOLEON, M. Pharm., Ph.D.

Associate Professor,
Chemistry Division, SAS,
VIT University, Vellore – 14.
Electroplated metal
Protective coatings
Protective coating provide a physical barrier between the metal & the environment.
They not only give corrosion protection but also add to the decorative value of
the article.
Coatings are broadly divided as

a) Inorganic coatings : metallic and chemical conversion coatings
b) Organic coatings : paints, varnishes, enamels, lacquers
Protective coatings are classified as

i) Metallic coatings
ii) Chemical conversion coatings
iii) Organic coatings and linings
iv) Ceramic protective coatings
Protective coatings
The most important step before protective coatings are applied to metals is
surface preparation.
o Surface preparation is a process to remove rust, oxide scales, oil, grease, dust etc.
o If these materials are not removed, the protective coating will not be smooth,
uniform, cohesive and will not adhere to the metallic surface.
o Hence, mechanical and electrical methods are used to prepare the surface of the metallic
article to be coated clean and free of these impurities.
o Mechanical cleaning, sandblasting, solvent cleaning, alkali cleaning, acid

pickling and etching are normal processes followed for surface preparation of the
article to be coated.
a) Mechanical cleaning:
o Useful for removing loose scales and rust.
o Hammering, wire brushing, grinding, polishing are the methods commonly

used. 4
Protective coatings
b) Sandblasting:
o Fine sand or abrasive material along with air stream at a pressure of 25-100
atm. is impinged on the metal surface.
This will produce enough roughness for good adherence of the
protective coating.
Though the method is expensive, it is quite fast and useful.
c) Solvent cleaning:
o Solvent cleaning is mainly used to remove oil, grease and rust from the base
metal.
o Alcohols, xylene, toluene, chlorinated hydrocarbons are used.
Hot water cleaning is followed after solvent cleaning is done.
d) Alkali cleaning:
o Cleaning of the base metal with sodium hydroxide, trisodium phosphate,
soda ash etc., is carried out to remove old paint coatings soluble in alkaline
medium.
o After alkali cleaning, washing is done with 1% chromic acid solution.
5
Protective coatings
e) Acid pickling and etching:
Base metal is dipped inside the dilute acid solution at higher temperature for
long periods of time.
This treatment ensures cleaning of the base metal surface free from all kinds
of impurities including oils, greases, rust etc.,
H2SO4, HCl, HF, H3PO4, HNO3 are the acids commonly used for pickling
and etching
protective coatings Methods

Methods of metallic coatings:
a) Hot dipping
b) Metal cladding
c) Electroplating
d) Electroless plating
e) PVD
f) CVD
a) Hot dipping
Two types of hot dipping techniques are known:
Galvanizing: Dipping the base metal iron in molten zinc metal solution
Tinning : Dipping the base metal iron in molten tin metal solution.
Protective coatings
Metallic coatings:
By coating/depositing a thin layer of any other metal which does not corrode.
a. Anodic coatings b. Cathodic coatings
a. Anodic coatings: Zn, Al, Cd = anode; Fe = Cathode (more noble)
Anodic coatings are given on cathodic metals using metals which are more
anodic. E.g
Iron surface can be protected from corrosion by depositing a thin layer of

Zinc, Aluminium, Cadmium on it.
The anodic metal sacrifices itself to protect the base metal.
Anodic coating is done by a metal which is situated above the base metal in the
galvanic series. Eg. Coating of zinc over iron.
If any crack or pit is formed on the coating, Zn will act as anode and sacrifice
itself to protect the base metal (Fe).
Since corrosion occurs at Zn, it behaves as Anode.

Fe is protected and hence it behaves as Cathode.
(b) Cathodic coatings: Sn , Cr, Ni- cathode, (more noble); Fe = anode
Coating of tin, chromium, nickel on iron surface are cathodic coatings.
Cathodic coatings
Coating a base metal (Iron) with another metal (Tin) which is at a lower
position in the galvanic series than the base metal.
Copper/brass can be protected by coating it with a thin layer of tin.
Tinning of brass utensils is a very common practice in our country.
1. Cathodic protection of iron is successful only when there is no pit or crack

formation on the surface of metal.
2. If this coating layer is punctured, much rapid corrosion happens to the base
metal.
Why tinned containers are used to store food whereas zinc coated containers are
not used?
Zinc gets dissolved in dil. Acid (pH >4.6) to form highly poisonous
compounds. Hence, galvanized containers are not used for storing food.
Galvanizing Process: Coating iron or steel sheets , rods, screws

Not for Examination, Only for understanding
It is the process of coating iron or steel sheets with thin coat of zinc to prevent them
from rusting.
Zinc reacts with Iron to form Zn/Fe alloy that provide a protective layer against corrosion.
650 oC
1. At first, Iron sheets are degreased by immersing in dil. H2SO4 solution at 60-90 oC for 15
to 20min. (pickling process), then rinsed with water to remove the acidic traces and dried
with hot air.
2. The dried metal sheets are then immersed in molten zinc bath at 425 to 430 oC.
The zinc bath is covered with NH4Cl flux to prevent the conversion of Zn to ZnO.
3. The excess Zn coating is removed by passing the sheets in-between two hot rollers
which is used to control the final thickness of the Zn coating.
4. Finally, the galvanized metal sheet is annealed at higher temperature of 500-540 oC for
10-180seconds, and finally cooled down slowly.
Uses: To protect Iron from corrosion e.g. wires, bolts, screws, rods, roofing
sheets, wires, pipes, tanks, nails, screws etc.
Galvanized metal sheets
The iron article is first pickled with dilute sulphuric acid to remove traces of rust,
dust, etc. at 60-90'c for about 15 -20 minutes.
Then this metal is dipped in a molten zinc bath maintained at 430'c.
It is used to protect roofing sheets, wires, pipes, tanks, nails, screws, etc
Tinning Process: Not for Examination, Only for understanding
It is the process of coating iron or steel sheets with thin coat of Tin to prevent
them from rusting.
1. At first, Iron sheets are degreased by acid pickling (Dil H2SO4)at 60-90oC for 15 to 20min.
2. The sheets were then treated with ZnCl2 flux which helps in the adhesion of Tin over the
steel sheet and to prevent the conversion of Sn to SnO.
3. The sheet are then immersed in molten tin bath. Tin reacts with Iron to form Tin/Iron alloy.
4. The sheets are then coated with palm oil to protect the sheet surface against oxidation.
5.The excess tin coating is removed by passing the sheets in-between two rollers which is
also used to control the final thickness of the coating.
Uses: Tin coatings are non-toxic, exhibit high resistance against atmospheric
corrosion.
Widely used for coating the interior of containers used for storing foodstuffs, pickles,
oils, etc
Tinned steel
Metal Cladding Not for Examination, Only for understanding

Metal Cladding : Bonding together of dissimilar metals.
It is the process of sandwiching a base metal (mild steel, Duralumin) between two
corrosion resistant metals (nickel, copper, stainless steel, Aluminium) and then passed
through rollers under heat and pressure.
Eg.
Alclad sheets in which a plate of duralumin is sandwiched between two
layers of 99.5 % pure aluminum.
In aircraft industry: to make stronger, light weight and corrosion resistant wing
frames.
Duralumin:
An alloy of over 90% aluminium, 4% Copper,
Trace of Manganese, Magnesium, Iron and Silicon
Advanced protective coatings: Electroplating
o It is a process by which a coating metal is deposited as a thin layer of metal or
alloy on the base metal by passing direct current through an electrolytic solution,
containing the soluble salt of the coating metal.
o Electroplating is done for improving

a) corrosion resistance
b) wear resistance (more durable)
c) chemical resistance
d) surface hardness
e) appearance
o Both ferrous and non-ferrous metals are plated with Copper coating
Ni, Cr, Cu, Zn, Pb, Al, Ag, Au, Sn etc.
o Mainly used in automobile, aircraft, refrigerator & electrical appliances etc.
o Used in jewelry making to coat base metals with precious metals to make them
more attractive and valuable and sometimes more durable.
Electroplating or Electro-deposition- depositing a thin layer of metal

Objectives of electroplating:
Electroplating can be done on (a) metals and (b) non-metals.
(a) On Metals: To increase the corrosion/chemical/wear Copper plating on aluminium

resistance of the electroplated metal;
To improve surface properties;
To increase the decorative value of the metal.
(b) On Non-Metals:
For decorating the surfaces,
To make the surface conductive.
Eg. Indium Tin Oxide on glass.- OLED, LCD, LED, Cell phones, Organic transisters,
Biosensor.
Electroplating copper can be extremely valuable in applications in the

manufacturing of electronic parts and components
products used in the aerospace and defense industries.

Copper is also widely used for plating on plastics and other non-metallic surfaces.
Electroplating or Electro-deposition
Characteristics and factors affecting electroplating:
1. Thickness: Thin coating for decorative and thick coating for corrosion
protection purpose.
2. Adherence: Weak adherence leads to the peeling-off of the coating.
3. Protective value:
Many pores: Less protecting power.
Thick coating: More protecting power.
4. Decorative value: Should be

Bright, continuous and uniform, no staining, no discoloration.
5. Temperature: Plating temperature: 35 to 60oC.

At this temperature,
i) Solubility of electrolyte increases;
ii) Causes decrease in crystal size,
(iii) Less H2 evolution at cathode thereby leading to uniform coating.
Characteristics and factors affecting electroplating: contd
6. pH of the bath liquid: 4 to 8.
For a good electro-deposit, the pH range of plating bath 4 to 8.
pH <4 = evolution of H2;
pH > 8 = precipitation of metal hydroxides on the electrode surface.
7. Throwing power:
It is the ability of electrolytic cell to give a deposit of uniform
thickness over the entire cathode area.
Determined using Haring-Blum Cell. Maximum throwing power (≥ 100%) is exhibited
when the cathode is in regular shape.
For irregular shaped cathodes, the throwing power will be erratic (less than 100%).
Determination of throwing power:
(x-y) * 100 %, where x = d1/d2 and y = w2/w1
(x+y-2)
1. w1 and w2 = weight of the metal deposited on the two cathodes.
2. d1 and d2 = distance of the anode with respective to the two cathodes.
3. When w1 = w2 then the throwing power is considered as very good (100 %).
8. Composition of the electrolytic bath:

(a) Concentration of plating metal solution: ideal conc. is about 1-3 mol L-
Higher conc. of metal-ion slows down mass transfer process of the metal ion
resulting in poor quality of the coatings.
b) Complexing agents: Avoid the passivation of anodes so that they are

dissolved more easily. Enhance the throwing power of the plating bath
solution.
Eg. sulphamate, hydroxide.
(c) Organic additives:
(i) Brighteners: produce “microscopic fine deposits” which reflect the light
falling on the surface. Ex: Coumarin, thiourea.
(ii) Wetting agents: Added to release the gas bubbles (H2) from the surface of the
cathode before electroplating. Eg. Sodium lauryl sulphate ( synthetic detergent).
9. Choice of the electrolyte: Should be a

good conductor, highly soluble,
Should not undergo hydrolysis, oxidation, reduction and other chemical

changes.
It should possess sufficient covering power.
No single electrolyte satisfies all the above requirement.
Usually a mixture of electrolytes are used.

Eg. In Copper plating, CuSO4 is used along with dil. H2SO4.
What is the importance of cleaning the metallic articles before
electro-deposition?
Before electroplating, the base metal (cathode) should
(a) be free from dirt, grease and corrosion products;
(b) Have uniform, less porous surface to form a protective coating of long life.
1. Solvent Cleaning: using solvents like toluene, acetone, CCl4, xylene.
This treatment provides a metal surface which can be readily wetted by

aqueous solution, a pre-requirement for electroplating process.
2. Alkali Cleaning: used for removal of old paint coating from the metal surface.
Always followed by thorough rinsing with water to remove the last traces of
alkali. Eg. Trisodium phosphate, caustic soda.
3. Pickling and Etching: Metal is immersed in acid bath to give smooth, tough and
bright appearance.
4. Mechanical Cleaning: done by hand using a wire brush to remove loose rust
from the metal surface.
What is the importance of cleaning the metallic articles before electro-

deposition?
5. Flame Cleaning: done by heating the metal surface with a hot flame to remove
loosely adhering scales.
6.Sand-blasting: Process consists of introducing sand into an air stream under

pressure of 25 to 100 atm.
The sand blast impact removes any scale present and also hardens the cleaned
metal surface.
Plating bath solution: components:

Electroplating setup involves the following components:
1. Plating Tank: Rectangular tank made of steel coated on inside with a ceramic or
polymer layer to provide thermal insulation.
Volume of the tank varies between 25 to 2000L.
2. Plating bath solution: A highly conducting metal salt solution is used as the
electrolyte for electro-plating.
Non-participating electrolytes are also added to the bath solution to increase
conductivity and throwing power.
Buffer and other additives are added to maintain the pH and to get bright and
compact deposits.
Mixture of two or more electrolytes is used for
preparing electrolytic bath.
3. Heating arrangement: Heating is provided by

heating coils or hot gases.
4. Convection arrangement:
Air sparger or nitrogen sparger is employed to
introduce convection current in the plating bath
solution.
Plating bath solution:
5. DC voltage arrangement: DC source is used for electroplating with a voltage of
8-12V and a current density of 1-200 mAcm-2.
6. Provision of Filters: In large plating operations, pumps and filters are

employed to filter out the metallic particles (dust or grit) which may hinder in
smooth deposition.
7. Power supply to the electrodes: Copper, brass or Al bus bars are used for
supplying the power to electrodes.
The anodes and cathodes are suspended alternatively from the bus bars
through the entire width of the tank.
7. Pretreatment of cathodic surface:

(a) removal of organic impurities using organic solvents
(b) Acid pickling using dil. H2SO4;
(c) Polishing: using silicon carbide wheels followed by sand blasting

and/or mechanical buffing;
(d) Rinsing in water followed by drying.

8. Process of electroplating:
Anodes connected to positive; Cathodes connected to negative terminals of
battery.
Thickness of the deposit = 10 nm to 100 mm. Time = few seconds to 30 min.
Electroplating- Silver coating on Spoon
Silver coating on
Spoon
26
Electroplating with Nickel coating on Copper
Copper Cathode is reduced Nickel Anode is oxidized

(accepts electrons) (gives electrons)
Ni2+ ions within solution become attracted

to Copper cathode
Electroplated metal
Wet corrosion or Electrochemical corrosion
Metallic pillar and outside

(b) Wet or Electrochemical corrosion
Wet corrosion occurs under the following conditions,

Corrosion in presence of aqueous conducting system (pH 1-14)
Corrosion occurs due to the formation of Anode and Cathode areas.
Electrons flows between the electrodes; ions flow through the electrolyte.
Oxidation occurs at the Anode; Reduction takes place at the Cathode.
At the anode: M Mn+ + ne- (oxidation)

Mn+ either dissolves in solution or forms compounds such as oxides.
(a) If the corrosion product is soluble in medium, corrosion rate will be high;
(b) If the corrosion product is insoluble in medium, corrosion rate will be very low.
At the cathode: The metals cannot be further reduced; but the dissolved
constituents in the electrolyte accept the electrons to form anions (½ O2 + 2e-
 O2-).
The metallic ions (at anodic part) and non-metallic ions (at cathodic
part) move towards each other through the electrolyte and form a
corrosion product somewhere between the anode and the cathode.
Important conditions/characteristics for electrochemical corrosion:
The important conditions/characteristics for electrochemical

corrosion:
(a) The formation of anodic and cathodic areas
(b) Presence of an electrolyte
(c) Corrosion of anodic part only
(d) formation of the corrosion product somewhere between the anodic and
the cathodic areas.
Wet or Electrochemical corrosion occurs in the

following types:
1. Hydrogen evolution type corrosion Mechanism of
electrochemical corrosion
2. Oxygen absorption type corrosion
3. Differential aeration corrosion or Concentration cell corrosion
4. Pitting corrosion
5. Crevice Corrosion
6. Stress corrosion
III. Galvanic corrosion

Wet or Electrochemical corrosion 1. Hydrogen evolution type corrosion
occurs when base metals are in contact with an acidic solution.
Eg. At Anode : Fe Fe2+ + 2e- (oxidation)
Anode : large area
At Cathode : 2H+ + 2e- H2
Cathode : small area
The overall reaction is:
Fe + 2H+ Fe2+ + H2
Metal ions produced at the anode dissolves in the electrolyte while hydrogen evolves at
the cathode.
Hence, this type of corrosion causes “displacement of hydrogen ions from the acidic
solution by metal ions”.
Acidic solution (electrolyte) H+

H+
H+ Cathodic
reaction
2 H+ + 2e-  H2
Fe  Fe2+ + 2e- Fe  Fe2+ + 2e- Anodic
No O2 Source: No oxide film reaction
Anodic area Anodic area

(large) Fe Cathodic area (large) Fe
(small)
In acidic environment, D.O. is not present in the water.
mechanism
Also, no protective oxide layer is formed over the metal surface.
Wet or Electrochemical corrosion 2.Oxygen absorption type corrosion:
Occurs when base metals are in contact with neutral solutions like NaCl containing
Dissolved oxygen (DO) or Water with pH 7 . Rusting of iron is an example of this.
Anode : Fe Fe2+ + 2e- (oxidation)
These electrons are used by the dissolved oxygen in aq. conditions
Anode : small area
Cathode : ½ O2 + H2O + 2e- 2 OH- (Reduction) Cathode : large area
The Fe2+ at the anode and OH- at the cathode diffuse and react to produce ferrous
hydroxide, Fe(OH)2 as rust: Fe2+ + 2 OH- Fe(OH)2
If sufficient oxygen is present, Fe(OH)2 gets oxidized to ferric hydroxide (Yellow rust)
4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3H2O)
aq. NaCl solution (electrolyte)

½ O2 + H2O + 2e-  2OH- More dissolved oxygen→
Thin oxide film more removal of electrons
rust e- rust from the oxidation of Metal
layer
OH- at the cathode → more corrosion!!!
Cathodic area Cathodic area

(large) Fe (large) Fe
Anodic area
(small) caused by cracks in the oxide film
Fe  Fe2+ + 2e- Mechanism
Fe2+ at the anode
Difference between Dry and Wet corrosion
Difference between Dry and Wet corrosion

Forms of Corrosion: 1. Differential aeration corrosion

It is a form of electrochemical corrosion (wet-type).
It occurs when a metal surface is exposed to Varying concentration of
electrolyte or varying concentration of oxygen.
(formed due to local temperature differences / inadequate agitation /slow
diffusion of metal-ions),
Thereby leading to the formation of a concentration cell.
Differential aeration corrosion is the most common type of concentration cell
corrosion.
It occurs when one part of the metal is exposed to lower concentration of O2 (acts
as anode) and the other part of the metal is exposed to higher concentration of O2
(acts as cathode).
Metallic pillar and outside
Differential aeration corrosion is the most common type of concentration cell corrosion.
It occurs when one part of the metal is exposed to lower concentration of O2 (acts as anode)
and the other part of the metal is exposed to higher concentration of O2 (acts as cathode).
Ex. Zinc rod dipped in brackish water solution (also called as water-line
corrosion).
½ O2 +H2O + 2 e- 2 OH- Zinc rod Anode: Zn Zn2+ + 2e-
More oxygenated part
(Cathode) Water-line
Cathode:½O2 + H2O+ 2e - 2OH-
e- Flow of electrons
NaCl solution
Corroding anode (less oxygenated part)
Zn2+ Zn Zn2+ + 2 e-
This type of corrosion also occurs when metals are partly covered with dust, oil marks, sand, etc.
Definition:
Pitting corrosion is a localized accelerated attack, By acidic environment resulting in the
formation of cavities around which the metal is relatively un attacked.
The protective oxide layer on the metal surface gets damaged at specific points due to
chemical attack.
scratches or cut edges, thereby giving rise to the formation of small anodic and
large cathodic parts.
Due to the above conditions, rapid penetration of oxygen takes place through some
cracks in the oxide film, and pitting takes place leading to the destruction of their
passivity and the metal corrodes more and more.
Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic environment.
(Just for your

understanding)
Presence of crevice or Damage of the passive film due to external crack,

Damage of the passive film due to Cl- ions
Electrochemical corrosion: 3. Stress corrosion cracking:
Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive
environment.
It can lead to unexpected sudden failure of normally ductile metals subjected to a

tensile stress, especially at elevated temperature.
Caused by the effect of local corrosion and tensile strength

in a particular environment.
Eg. Brass in the presence of ammonia.

Stainless steel in the presence of NaOH at high temperature.
Stress corrosion cracking can be prevented through:

 Avoid the chemical species that causes SCC.
 Control of hardness and stress level (residual or load).
 Introduce compressive stress by shot-peening for example.
 Use of materials known not to crack in the specified environment.
Electrochemical corrosion: 4. Crevice Corrosion
Crevice Corrosion refers to the localized attack on a metal surface at, or

immediately adjacent to the gap or
crevice between two joining surfaces.
Localized near to the coupling between two mechanical parts in the presence of a
wetting environment.
The gap or crevice can be formed between two metals or a metal and non-metallic material.
This form of attack is generally associated with the presence of small volumes of stagnant solution in
occluded interstices, beneath deposits and seals, or in crevices,
e.g. Sharp corners, Incomplete weld penetration, Overlapping surfaces, at nuts and rivet heads.
Deposits of sand, dust, scale and corrosion products can all create zones where the liquid can only be
renewed with great difficulty.
This is also the case for flexible, porous or fibrous seals (wood, plastic, rubber, cements, asbestos, cloth, etc
Images of Crevice Corrosion
III. Galvanic corrosion:

 When two dissimilar metals are in contact with each other in the presence
of an aqueous solution or moisture.
 When two dissimilar parts of the same metal are in contact with an
aqueous solution of an electrolyte.
Occurs when two dissimilar metals (zinc and copper) in the galvanic series are in contact
with each other (joined by welding) and exposed to corroding environment.
• Similar metals are compatible (Based on redox potential value); Steel and Aluminium are
reasonably compatible;
• dissimilar metals are not compatible. (zinc and copper)
When dissimilar metals contact in the presence of an electrolyte, a galvanic action occurs
which causes one of the metals to corrode at a much faster than normal rate, while the other
corrodes more slowly, if at all. Anodic Mg
(+ve) Zn
Al
Cd
Fe
The rate, location and extent of the corrosion depends on three factors: Pd
• the difference in electrical potentials Cu
Ni
• the conductivity strength of the corroding medium, and Ag
• the relative sizes of the contacting areas Ti
(-ve) Au
5. Galvanic corrosion:
Occurs when two dissimilar metals are electrically contact and exposed to electrolyte,
Metal has high anodic character tends to undergo corrosion
o The metal with more redox potential (more higher in the galvanic series) will become
anode and corrodes. This type of corrosion is called galvanic “corrosion”.
Galvanic series Galvanic Series
Tendency to get oxidized is arranged in the

increasing order from bottom to top.
The species higher in the series is more

anodic and hence corrodes faster than the
metal below it.
Deals with metals and alloys.
The position changes with respect to the

combination of metals/alloys.
More practical and useful in comparing
the corrosion behavior.
Depends upon the nature of e- donation and
e- accepting property, metals were arranged as
redox potential values.
5. Galvanic corrosion:
o In Zn-Cu, Zn acts as anode (oxidized) and Copper acts as cathode (reduced).
o The electron flows from anode to cathode. E.g.
 Steel screws in a brass marine hardware;
 Lead-antimony solder around a copper wire;
 Steel pipe connected to copper plumbing.
This can be avoided or minimized by:
a) coupling metals which are close in the electrochemical series.
b) Making the cathode metal smaller in area than the anodic metal.
Galvanic Series suggests that Steel and Aluminum are

reasonably compatible.
Steel and Aluminum are

reasonably compatible.
Copper and Aluminum

not compatible
Advanced protective coatings:
Electroless plating / Chemical or
auto-catalytic plating
Electroless plating


Electroless plating / Chemical or auto-catalytic plating
Electroless plating involves the production of coatings from solutions of
metal ions without the use of an external source of electrical energy.
It is the most extensively used electroless coating within the manufacturing

industry.
Involves several simultaneous chemical reactions in an aqueous solution and

is autocatalytic, which occur without the use of external electrical power.
It is mainly different from electroplating by not using external electrical power.

It is a non-galvanic plating method
Electroless plating is a ‘self-reduction’ process,

This relies upon the auto-catalytic reduction process of metal ions in an aqueous
solution containing a chemical reducing agent (typically sodium hypophosphite,
NaH2PO2).
It is one type of surface finish deposition method in electronic packaging.
With advancements in electronic products, the industry is shifting toward this

process based on its advantages.
Eg. Electroless nickel, electroless gold, Electroless nickel and copper.
Electroless plating- Electroplating- Silver coating on Spoon
In Electroless plating or In autocatalytic platings,

The metal ion is reduced to a metal in an aqueous solution containing a
chemical reducing agent (typically sodium hypophosphite, NaH2PO2).
form a coating on only on a specific metal surface, or substrate, like metal or
plastic which must have a catalyst present before the reaction can begin.
Electroless plating involving a nickel sulfate bath has the following reaction:
Electroless
plating of Nickel
Electroless plating
In the case of nickel Electroless plating- , the deposits are dense, relatively
hard and brittle.
Electroless Nickel is not as bright as electroplated, easy to solder and braze,
but difficult to weld.
Electroless plating- Limitations
With advancements in electronic products, the industry is shifting toward this

process based on its advantages. However,
The electroless plating process itself is unstable.
Its stability fully depends on the

substrate material, the pretreatment process,
the type of solution used, pH and temperature during plating.
Difference between Electroplating and Electroless Plating
Electroplating Electroless
Plating
Electroless nickel plating

• Electroless nickel plating is an auto-catalytic reaction that deposits an even layer of
nickel-phosphorus or nickel-boron alloy on the surface of a solid material, or
substrate, like metal or plastic.
Source of Metal
Most acid solutions use nickel sulphate, whilst
Nickel chloride is used in alkaline solutions.
Reducing Agent
Sodium hypophosphite is widely used due to its low
cost and availability.
Complexants: The type of complexants used to

maintain a low concentration of free nickel ions.
Depend on the nickel concentration and the

chemical structure of the complexing agents
themselves.
Commonly used complexants include glycolic or lactic

acid for acid-based solutions, and ammonium
hydroxide for alkaline solution.
Electroless nickel plating
Buffers:
Since pH is a major factor in controlling deposition rate and the phosphorus
content of the deposit.
Common buffers include acetic or propionic acids and their salts.
Stabilizers
Stabilizers are used to prevent spontaneous decomposition of the plating solutions.
Traditionally, these included heavy metals such as lead or cadmium at very low
concentrations (<1ppm).
Electroless Nickel Plating: Process
Electroless Nickel Plating Process

The step-by-step process for electroless nickel plating is as follows:
The metal is submerged in a series of pre-treatment baths.
Each of these baths contains specific chemicals that remove oil, grease, dirt and other
pollutants on the metal surface. This improves the adhesion of the deposits onto the
substrate surface.
The cleansing chemicals used depend upon the surface material.
After cleaning, certain metal substrates require further treatment in an aqueous zincate
solution. This tends to be a proprietary solution supplied by the electroless nickel
chemistry manufacturer.
Once immersed in the plating solution, nickel and phosphorus ions are deposited onto
the metal substrate surface.
Depending upon how thick the surface needs to be, the deposition process can be
carried out from between 5 microns to 25 microns per hour.
Once the desired plating thickness is achieved, the substrate is removed from the
plating solution and inspected.
Use Electroless Nickel Plating
Industries that Extensively Use Electroless Nickel Plating
Automotive: Cylinders, gears, shock absorbers, brake pistons, heat sinks, etc.
Aviation and Aerospace: Components for rockets and satellites, valves, rams pistons, etc.
Chemical Processing: Mixing blades, filter units, heat exchangers, pump housings,
impellers, etc.
Petroleum and Gas: Plugs, gates, balls and other valve components, pipe fittings, barrels,
pumps, packers, etc.
Plastic Manufacturing: Injection molds and dies, low and blow molding for plastics
components, rollers, extruders, etc.
Textiles: Machine parts, threaded guides, spinnerets, printing cylinders, etc.
Food and Pharmaceuticals: Food molds, food processing machinery components, capsule
machinery dies, etc.
Modules: 5. Electrochemical Energy Systems 6Hrs

Modules: 5 Electrochemical Energy Systems 6Hrs

Module: 5
• Brief introduction to conventional primary and secondary batteries;
• High energy electrochemical energy systems: Lithium batteries – Primary

and secondary, its Chemistry, advantages and applications.
• Fuel cells – Polymer membrane fuel cells, Solid-oxide fuel cells- working
principles, advantages, applications.
• \
• Solar cells – Types – Importance of silicon single crystal, polycrystalline

and amorphous silicon solar cells, dye sensitized solar cells - working
principles, characteristics and applications.
The 2019 Nobel Prize in Chemistry awarded to trio for development of

The prize went to: lithium-ion batteries
•John B. Goodenough of the University of Texas.

• M. Stanley Whittingham of the State University of New York- Binghamton
.
•Akira Yoshino of Asahi Kasei Corporation and Meijo University in Japan.
John B. Goodenough M. Stanley Whittingham Akira Yoshino
The 2019 Nobel Prize in Chemistry was awarded to John B. Goodenough,

left, M. Stanley Whittingham, centre, and Akira Yoshino
Goodenough, who at 97 becomes the oldest winner of a Nobel Prize,

doubled the lithium battery's potential in the following decade and
Yoshino eliminated pure lithium from the battery, making it much safer to use.
Applications using Batteries

Battery is an electrochemical device that stores chemical energy for latter release
as electricity in the form of direct electric current at a constant voltage.
4
• Battery is an electrochemical device
Convert stored chemical energy into
electrical energy
• Reaction between chemicals take place
• Consisting of electrochemical cells
• Contains
– Electrodes
– Electrolyte
Cathode
Positive terminal
Chemical reduction occurs (gain electrons)
Anode
Negative terminal
Chemical oxidation occurs (lose electrons)
Electrolytes allow:
Separation of ionic transport and electrical transport Ions to move between
electrodes and terminals
Current to flow out of the battery to perform work 5
An electrochemical cell- Basic

An electrochemical cell is a device which is used to convert the chemical
energy produced in a redox reaction to get electrical energy.
(This occur during discharging)
Device in which the electrical energy is converted to chemical energy

thereby resulting in a chemical reaction (during charging).
Or
•
The electrode where oxidation occurs is called anode while
The electrode where reduction occurs is called cathode.
An example for Electrochemical cell or galvanic cell - Daniel Cell

Zinc Electrode dipped in ZnSO4 solution’ Oxidation
Copper Electrode dipped in CuSO4 solution; Reduction
Each electrode is referred to as half cell

which are connected through a salt bridge.
Electrode reactions:
At anode:
At cathode:
Electrode on the left:
Electrode on the right:
A salt bridge is indicated by two vertical lines, separating the two half cells
Battery-Basic
Definition:
• Battery is an electrochemical device that stores chemical energy for
latter release as electricity in the form of direct electric current at a
constant voltage.
• The anode or negative electrode — which gives up electrons to the

external circuit and is oxidized during the electrochemical reaction.
• The cathode or positive electrode — which accepts electrons from the

external circuit and is reduced during the electrochemical reaction.
The electrolyte: The ionic conductor— which provides the medium for
transfer of charge, as ions, inside the cell between the anode and cathode.
The electrolyte is typically a liquid, such as

• water or other solvents, with dissolved salts, acids, or alkalis to impart
ionic conductivity.
• Some batteries use solid electrolytes, which are ionic conductors at the
operating temperature of the cell.
Battery Basics: Cell vs. Battery:

Cell vs. Battery:
A cell is the basic electrochemical unit providing a source of electrical
energy by direct conversion of chemical energy.
The cell consists of an assembly of electrodes, separators,

electrolyte, container and terminals.
A battery consists of one or more electrochemical cells, electrically

connected in an appropriate series/parallel arrangement to provide the
required operating voltage and current.
Nominal voltage:
The nominal voltage of a cell is the potential difference between the
positive and negative electrodes in fully charged condition (secondary)
or freshly prepared condition (primary).
Eg. Nominal voltage of dry cell : 1.5 V

Nominal voltage of lead‐acid cell : 2.0 V
Capacity of the battery

A battery's capacity is the amount of electric charge it can deliver at the
rated voltage.
The more electrode material contained in the cell, the greater its
capacity.
The capacity of the cell = discharge current x discharge duration in hours

during which the cell will maintain voltage above a specified terminal
voltage (above the specified cut off voltage)
Capacity is measured in units such as ampere hours (Ah).
Example:
If a lead‐acid cell is discharged at a current of 5 amperes and it lasts
for 10 hours before reaching the cut‐off voltage, then the capacity of
the cell is 5 amp. x 10 hours = 50 Ah
A small cell has less capacity than a larger cell with the same chemistry,
although they develop the same open‐circuit voltage.
Self discharge of batteries

Self discharge:
The loss in capacity of a cell when stored at specified temperature
conditions without actually discharging, is called self discharge.
This is estimated by storing the cell at the specified temp. (eg. 25oC
for 1 year) and then discharged to check the residual capacity.
For an ideal cell (battery), the self discharge should be low.

Batteries
Batteries - chemical reaction - produce a voltage
 Batteries are devices where several electrochemical systems are

connected together in series.
 Can store chemical energy for later release as electricity
 Basic element in a battery - electrochemical cell - makes use of an

oxidation/reduction reaction.
 Voltages generated by such cells - referred to as emf (electromotive force).
 Source of direct electric current at a constant voltage.
Battery
Definition:
• Battery is an electrochemical device that stores chemical energy for latter
release as electricity in the form of direct electric current at a constant voltage.
• The anode or negative electrode — which gives up electrons to the external

circuit and is oxidized during the electrochemical reaction.
• The cathode or positive electrode — which accepts electrons from the

external circuit and is reduced during the electrochemical reaction.
• The electrolyte: The ionic conductor— which provides the medium for
transfer of charge, as ions, inside the cell between the anode and cathode.
The electrolyte is typically a liquid, such as

• water or other solvents, with dissolved salts, acids, or alkalis to impart ionic
conductivity.
• Some batteries use solid electrolytes, which are ionic conductors at the
operating temperature of the cell.
Types of batteries
Types of batteries :
1. Primary battery (Primary cells)
 In which the cell reaction is not reversible.
 When all the reactants have been converted to product, no more electricity
is produced and the battery is dead.
Eg: Dry or lachlanche cell Alkaline battery Lithium batteries.
2. Secondary battery (Secondary cells)

 In which cell reactions can be reversed by passing electric current in the
opposite direction. Thus
 It can be used for a large number of cycles.
Eg: Conventional Secondary batteries: Lead acid Nickel-Cadmium.

Advanced secondary batteries: Nickel Metal hydride Lithium ion.
3. Flow battery and fuel cell

In which materials (reactants, products, electrolytes) pass through the battery
continuously, which is simply an electrochemical cell that converts chemical
to electrical energy.
Fuel Cells: Hydrogen – oxygen fuel cells (HOFC) or alkaline fuel cells, Solid oxide
fuel cell (SOFC)
Examples for Primary, Secondary and Advanced Primary and secondary

batteries
Examples for Primary, Secondary and Advanced Primary and
secondary batteries
Difference between Primary battery & Secondary battery.
Primary battery Secondary battery

Electrochemical cell reaction is Electrochemical cell reaction is reversible
irreversible.
The reactants cannot be regenerated, The reactants can be regenerated by
passing D.C. in the opposite direction to
the discharging direction
disposable after complete discharge; reusable after complete or partial
usable for only once. discharge.
Cheaper in cost. Expensive than primary batteries
Higher charge density, Lesser charge density
e.g. Carbon-zinc (dry cell), e.g. Lead-acid, Ni-Cd, Ni-MH,
Alkaline and Lithium cells Lithium-ion rechargeable cells
Primary batteries
Primary batteries
1. primary cell in which irreversible electrochemical reactions take place.
2. Once discharged, the cell reaction cannot be reversed by passing

direct electric current through the cell
Dry or Leclanche cell

Alkaline battery
Lithium batteries
DRY (or) LACLANCHE CELL- Not for Examn.

DRY (or) LACLANCHE CELL
The venerable carbon-zinc cell or Lechlanche' cell was invented in 1866 by
Georges lachlanche.
It was the most common small battery throughout most of the 20th century.
Ammonium chloride as the electrolyte.
Cathode)
Dr. Georges Leclanché (1839 –1882)

He was a French electrical engineer
Important characterisitics of the dry cell:

1. The dry cell is a primary cell in which irreversible electrochemical reactions
take place.
2. Once discharged, the cell reaction cannot be reversed by passing direct
electric current through the cell.
3. The nominal voltage of the dry cell is 1.5 V.
Dry cell (or) laclanche cell
Dry (Or) Laclanche Cell: Applications- Not for Examn

Applications:
 Used in flash lights, transistor radios, calculators etc
Advantages of the dry cell:

1. Dry cell is cheaper to make than the secondary cells.
2. It has much higher charge density than in secondary cells.
3. Better low-temperature service.
4. Good charge - leak resistance.
Disadvantages:
 Voltage of this cell is initially about 1.5 v, but decreases as energy is taken
from the cell due to the accumulation of the products on electrodes.
 Has a short shelf life because of its acidic medium.
 Deteriorates rapidly in in cold weather.
 Oxidation of the zinc wall eventually causes the contents to leak out, so
such batteries should not be left in electric equipment for long periods.
 While these batteries have a long history of usefulness, they are declining
in application since some of their problems are overcome in ALKALINE
BATTERIES.
Alkaline Dry Cells: :- Not for Examn
 Potassium hydroxide is a base or alkaline material, hence "alkaline"
batteries.
 The active materials used are the same as in the Leclanché cell – zinc and
manganese dioxide.
Alkaline cells overcome some of the problems with carbon-zinc batteries by using potassium
hydroxide (KOH) in place of ammonium chloride as the electrolyte.
 These cells have much longer shelf life.
 Perform better under drain and in cold weather.
They avoid the use of the zinc-corroding ammonium ions & do not produce any gaseous
products.
Alkaline battery
Alkaline battery: It is an improved form of the dry cell in which the NH4Cl is
replaced by KOH as the electrolyte.
Basic structure :
Anode (-ve terminal):
Made up of zinc powder (increased surface area for increased rate of reaction
and hence more electron flow) with the exposed bottom as the negative (-ve)
end of the battery.
Cathode (+ve terminal): made up of a carbon(graphite) as positive (+ve) end and

mainly surrounded by electrolytically produced manganese (IV) dioxide (MnO2)
(higher purity than naturally available MnO2 used in Dry cell case) and carbon
powder (for increased conductivity).
Electrolyte:
Potassium hydroxide (KOH, electrolyte) mixed at 35 to 50 wt.-% with the zinc
powder and a small quantity of a gelling material to get a thick paste.
A metal pin or a sheet (serving as electron collector) is inserted into the

anode mixture provide contact to the anode electrode.
Discharging Chemistry of Alkaline Cell
The zinc anode does not form the container but it is in the form of a powder, giving a
large surface area.
The following half-cell reactions take place inside the cell:
Advantages and Uses:

1. Zinc does not dissolve as readily in alkaline medium.
2. Long life maintain its voltage.
3. Used in calculators and watches .
4. These cells have much longer shelf life and perform better under drain and in cold
weather.
5. They avoid the use of the zinc-corroding ammonium ions and do not produce any
gaseous products.
Li Primary Batteries
• In the 1980s progress was made in the use of
• Li as an anode material with MnO2,
• Liquid SO2 or thionyl chlorides as the cathode, and
• Hexaflurophosphate dissolved in propylene carbonate as a
typical organic electrolyte.
• Li cells are generally properly sealed against contact with air and
moisture.
The main attractions of lithium as an anode material is

 It is the most electronegative metal in the electrochemical series
 It has very low density,
Means, the largest amount of electrical energy per unit weight.
• But Li cannot be used with the traditional aqueous electrolytes

 due to the very vigorous corrosive reaction between Li and water.
 with flammable hydrogen as the product.
Primary Lithium batteries

One of the main attractions of lithium as an anode material is its position as the most
electronegative metal in the electrochemical series combined with its low density, thus
Offering the largest amount of electrical energy per unit weight among all solid
elements.
•Li cannot be used with the traditional aqueous electrolytes due to the
Very vigorous corrosive reaction between Li and water with flammable hydrogen as
the product.
• In the 1980s progress was made in the use of Li as an anode material with MnO2,
Liquid SO2 or thionyl chlorides as the cathode, and
Hexaflurophosphate dissolved in propylene carbonate as a typical organic electrolyte.
•Li cells are generally properly sealed against contact with air and moisture.
Lithium acts as the anode electrode.
Cathodes: Solid or Liquid.

Liquid SO2 or thionyl chlorides as the cathode,
Electrolytes:
Organic solvents such as
Tetrahydrofuran, Dioxalone, Dimethyl ethane,
polypropylene carbonate (PC) 1,2 dimethoxy ethane etc.
Lithium salts: Lithium perchlorate, lithium tetrafluoro borate / phosphate,

etc.
Lithium in the presence of electrolytes form a very thin film, which

is conductive for Li+ ions.
Battery sizes: Coin cells to Cylindrical cells with high energy density –
energy stored per unit volume.
Types of Li Batteries
Lithium Primary Battery- Solid cathode type
Chemistry of Li/MnO2(s) cell

Anode (-): Lithium Anode reaction: xLi(s) ---- xLi+ + xe-
Cathode (+): MnO2
Cathode Rxn: MnO2 + xLi + e- --- LiMn1-x 4+ MnX3+O2
Overall reaction:
MnO2 + xLi ---LiMn4+ Mn3+O2
Electrolyte: Lithium perchlorate, lithium tetrafluoroborate etc.,
Organic solvents:
polypropylene carbonate and 1,2 dimethoxy ethane.
Voltage: 3 volts.
Li/I2 Batteries – for Cardiac Pacemakers
Li/I2 Batteries – for Cadiac Pacemakers

Can only support for extremely low current rate applications such as a
pacemaker.
Anode: Li
Cathode: I2
Electrolyte: poly(vinyl pyrrolidone) (PVP) .
Cell reaction: 2Li + I2------ 2LiI
High storage capacity.
EMF: 2.4 - 2.8 V
Lithium Batteries
Applications:
Used in portable consumer electronic devices, as backup batteries in
computers and communication equipment, and in remote car locks.
lithium batteries can easily support the brief, heavy current demands of
devices such as digital cameras, and they maintain a higher voltage for a
longer period than alkaline cells.
Conventional Cells using aqueous (containing water) electrolytes are limited in

voltage to less than 2 Volts but Lithium batteries which use non-aqueous
electrolytes are available in higher voltages between 2.7 and 3.7 Volts. How?
because water dissociates to O2 and H2 in the presence of voltages above 2V.

Lithium batteries which use non-aqueous electrolytes do not have this
problem.
Lithium Batteries
Advantages of the lithium cell:
 High energy density; provide very high current;
 long shelf-life of around 10 years;
 though costly, Li cells require low maintenance;
 lithium cells can produce voltages more than twice the voltage of an ordinary
zinc-carbon battery or alkaline cell;
 The higher voltage reduces the number of cells in a battery pack by a factor
of at least 2;
 less self-discharge rate compared to Ni-Cd batteries;
 Does not generate gas even under short circuit; Operation over a wide
temperature range (-40 to 70oC).
 Advantages of Lithium Primary Batteries Lithium Primary Batteries are known to have many
functionalities. Some of which include the following. • High energy density, double that of
premium alkaline batteries • Low weight • High cell voltage • Flat discharge characteristic •
Low self discharge • Very long shelf life • Very long operating life (15 to 20 years for lithium
thionyl chloride) • Wide operating temperature range ( -60 ° C to +85 ° C for lithium sulfur
dioxide) • Excellent durability • Small cell size
Disadvantages of the lithium cell:
Disadvantages of the lithium cell:
Require protection circuit to maintain voltage and current within safer
limits;
Lithium batteries can provide extremely high currents and can

discharge very rapidly which can result in overheating of the battery
and even explosion.
Hence, lithium batteries incorporate vents in order to prevent
explosion.
Transport of lithium batteries by air is restricted;
expensive to manufacture; about 40% higher in cost than Ni-Cd

battery;
Li cannot be used with the traditional aqueous electrolytes
Due to the very vigorous corrosive reaction between Li and water with
flammable hydrogen as the product.
lithium metal scrapped from the batteries can be illegally used as a

reducing agent in methamphetamine (used as drugs) labs.
Advantages and Uses
• High energy density

• Long shelf life
• Low self discharge
• Need less maintenance
• Can provide very high current
• Used in auto focus cameras
Modules: 5: Fuel Cells
Fuel cells – Polymer membrane fuel cells-

Hydrogen – oxygen fuel cells (HOFC)
Solid-oxide fuel cells- working principles, advantages, applications.

Fuel cell
Fuel cell technology offers clean, efﬁcient, reliable power generation to almost
any device requiring electrical power.
Fuel Cell Today categorises the use of fuel cells into three broad areas:
• portable power generation,
• stationary power generation, and
• power for transportation
Home heating and power to cars.
Fuel cells
A fuel cell is a device that converts chemical energy (by combining hydrogen
and oxygen) into electrical energy, water and heat through electrochemical
reactions.
Fuel + O2 ------ Oxidation products + Electricity.
Fuel cells use an external supply of chemical energy (From Fuel), they can
run indefinitely, as long as they are supplied with a source of hydrogen and a
source of oxygen.
Fuel Cell
A fuel cell is a device that converts chemical energy (by combining hydrogen
and oxygen) into electrical energy, water and heat through electrochemical
reactions.
Fuel + O2 ------ Oxidation products + Electricity.
Fuel cells use an external supply of chemical energy (From Fuel), they can run
indefinitely, as long as they are supplied with a source of hydrogen and a source
of oxygen.
A stream of hydrogen is delivered to the anode side of the MEA.

At the anode side it is catalytically split into protons and electrons.
How does a Fuel cell works?
Electro chemical reactions
Parts of a Fuel Cell

Fuel Cells-Anode and Cathode
Major Types of Fuel cells
Fuel Cells Classifications
Types of Fuel cell

(HOFC)
Polymer membrane fuel cells / proton exchange membrane fuel cell (PEMFC)
polymer electrolyte membrane (PEM) fuel cells (PEMFC),
These are a type of fuel cell being developed for
For transport applications,
For stationary fuel-cell applications and
For portable fuel-cell applications.
It has a semipermeable membrane

generally made from ionomers
Designed to conduct protons while acting

as an electronic insulator and reactant
barrier, e.g. to oxygen and hydrogen gas.
This uses a water-based, acidic polymer

membrane as its electrolyte, with platinum-
based electrodes.
PEMFC cells operate at relatively low temperatures (below 100 degrees Celsius)
and can tailor electrical output to meet dynamic power requirements.
Polymer membrane fuel cells / proton exchange membrane fuel cell
(PEMFC)
(i) Hydrogen – oxygen fuel cells (HOFC) or alkaline fuel cells (AFCs)
Materials used:
Anode: Inert and porous graphite
electrode + finely divided Platinum catalyst
Cathode: Inert and porous graphite

electrode + finely divided Platinum catalyst
Electrolyte: 25% KOH hot solution.

Chemistry:
H2 and pure O2 gases are bubbled through
the anode and cathode respectively, and
the fuel cell produces power through a red-
ox reaction between H2 and O2.
Pt loading: 0.2-0.8 mg/cm2
At anode (-): 2 H2 (g) + 4 OH-(aq) → 4 H2O (l) + 4 e- (oxidation)

The electrons flow through an external circuit and enter the cathode.
At cathode (+): O2 (g) + 2 H2O (l) + 4 e- → 4 OH- (aq) (reduction)

Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (l)
1. Hydrogen – oxygen fuel cells (HOFC) or alkaline fuel cells (AFCs)
The net reaction consumes one O2 molecule and two H2 molecules in the
production of 2 H2O molecules.
Electricity and heat formed as by-products of this reaction were used to drive the
motor.
The standard EMF of the cell: Eo = Eo ox + Eo red = 0.83 V + 0.40 V = 1.23 V.
By stacking a number of cells together in as series to make a battery, the required

voltage to drive a motor is achieved.
Electrode specifications:
(i) must be good conductors;
(ii) must be good electron sink;
(iii) must not be consumed or deteriorated by the electrolyte heat or
electrode reactions.
Advantages:
 AFCs consume H2 and pure O2 producing potable water, heat, and electricity.
 Efficiency is around 70% which is highest among the fuels cells used at
present.
 Operating temperature are 150 to 200oC suitable for automobile applications.
 For low-temperature (-54oC to 72oC) operation, potassium thiocyanate (KSCN)

dissolved in liq. NH3 is used.
Disadvantages:
 Require pure H2 and O2 fuel;
 Platinum electrodes used as catalyst are expensive;
 As the electrolyte is aqueous medium, it may leak.
Applications: Compared to conventional energy generators, fuels cells occupy
Less space and weight and hence used as auxiliary energy source in
space vehicles, submarines, etc;
In case of H2/O2 fuel cells, the water obtained as product is a valuable source
of fresh water for the astronauts.
Fuel cell poisoning:

AFCs can become poisoned if the oxygen is contaminated with CO2 resulting
in the conversion of aq. KOH into K2CO3. Hence,
AFCs require the supply of pure O2 thereby increasing the cost.

Leading to subsequent decrease in ionic conductivity of the electrolyte.
The poisoning effect can be reversed by replacing the poisoned electrolyte

with aq. KOH which returns the cell back to its original output.
2. Solid oxide fuel cell (SOFC)

Fuels used:
Lighter fuels: Methane, propane and butane;
Heavier fuels: Gasoline, diesel,
jet fuel or biofuel.
Operating temperature: 800 to 1000oC
Ni+ YSZ
Solid oxide fuel cells LSM
work at very high temperatures, - around 800ºC to 1,000°C.
They can have efficiencies of over 60% when converting fuel to electricity;
If the heat produced is also harnessed; their overall efficiency in converting

fuel to energy can be over 80%.
Anode: Nickel mixed with YSZ (yttria stabilized zirconia);

Cathode or Air electrode: Lanthanum strontium manganite (LSM);
Fuels used: (ii) Solid oxide fuel cell (SOFC)
Lighter fuels: Methane, propane and butane;
Heavier fuels: Gasoline, diesel, jet fuel or biofuel.
Operating temperature: 600 to 1000oC

Anode or fuel electrode:
Nickel mixed with YSZ (yttria stabilized zirconia);
It is a porous ceramic layer to allow the fuel to
flow towards electrolyte.
Cathode or Air electrode:

Lanthanum strontium manganite (LSM);
Thin porous ceramic layer coated over the solid
electrolyte where oxygen reduction takes place.
.
Electrolyte: Solid ceramic electrolyte
Yttrium oxide stabilized zirconium oxide (YSZ) +
Gadolinium doped ceria (GDC) or
Mixture of Zirconium oxide + Calcium oxide instead

of a liquid or membrane.
At anode (oxidation): H2 (g) + CO + 2O2- → H2O + CO2 + 4e- + energy
At cathode (reduction): O2 (g) + 4e- → 2O2-
(ii) Solid oxide fuel cell (SOFC)
Interconnect:
Its purpose is to connect each cell in series, so that the electricity generated
from each cell can be combined.
Can be either a metallic or ceramic layer that sits between each individual cell.
Nickel- and steel-based alloys are used as interconnects in SOFCs operating

at 600-800°C.
The most common intermetallic materials used today
Doped lanthanum chromites as they exhibit

High temperature thermal stability and
Excellent electrical conductivity.

(ii) Solid oxide fuel cell (SOFC)- Advantages and Disadvantages
SOFCs are used extensively in large and small stationary power genern.
Micro-tubular SOFCs with output in the watt range are also being
developed for small portable chargers.
A further advantage of the high operating temperature is that the reaction kinetics
are improved, removing the need for a metal catalyst.
There are however some disadvantages to the high temperature:

these cells take longer to start up and reach operating temperature,
they must be constructed of robust, heat-resistant materials,
they must be shielded to prevent heat loss.
Difference between Battery and Fuel cell
Battery Fuel Cell

A battery generates electrons from the A fuel cell make electrons from the
electrochemical reaction between the reactants electrochemical reaction only when the
already stored in the cell reactants are supplied from outside the
cell
A battery stores a limited amount of chemical A fuel cell uses the reactants which are
reactants internally inside a metal case, which stored externally and constantly filled up.
when used up,
must be either recharged or disposed. A fuel cell vehicle is refueled instead of

recharged.
It is a thermodynamically closed system It is a thermodynamically open system

Module 4: Corrosion Control methods
Anodes are energized by an external DC
power source
Sacrificial anode cathodic protection Impressed current cathodic protection

Module 4: Corrosion Control Methods- Overview

Corrosion protection :
Cathodic protection
Sacrificial anodic and impressed current protection methods;
Electroplating and Electroless plating,
Physical Vapor Deposition (PVD)-Used in Surgical/Medical, Cutting tools-1mm
Decorative coatings on plastic parts
Chemical Vapor Deposition (CVD)
Depositing a solid material from a gaseous phase.
Fabrication of semiconductors, integrated circuits, sensors,
Optical fibers for telecommunications etc
Alloying for corrosion protection –

Basic concepts of Eutectic composition and Eutectic mixtures
Ferrous alloys: Selected examples
Sheet for automobiles, appliances, and containers.
plates for ships, boilers and bridges
Non-ferrous alloys.
Copper Alloys: Cu is probably in coins, Euro coins,
Lead-Tin alloy for solder
Magnesium Alloys: Aerospace industry, High speed machinery
Nickel Alloys: Corrosion resistant parts: Valves, pumps,
Control of Corrosion
Corrosion can be controlled by:
a) Proper designing
b) Use of pure metals
c) Use of alloys
d) Cathodic protection
e) Anodic protection
f) Application of protective coatings
a) Galvanizing coating process (Anodic coatings (Zn on Fe))
b) Tinning coating process (Cathodic coatings (Sn on Fe))
Corrosion control methods

a. Proper designing:
 Proper selection of metal or alloy or design will play an important part in corrosion
control.
 To the extent possible, contact of dissimilar metals far apart from each other in the
electrochemical series should be avoided.
 Metals which are close in electrode potentials in the electrochemical series are
preferable. Zn-Aluminium, Steel-Aluminium.
 While working with dissimilar metals, larger anodic area and lesser cathodic area are
necessary to minimize corrosion.
 When two dissimilar metals are together, painting or electroplating the
anodic metal will help in reducing corrosion
 Weld rather than rivet
 Easy replacement of vulnerable parts

4
 Avoid excessive mechanical stress
Electrochemical series
Steel:
The carbon content of steel is between
0.002% and 2.1% by weight for plain
iron–carbon alloys.
These values vary depending on

alloying elements such as manganese,
chromium, nickel, iron, tungsten,
carbon and so on.
stainless steel contain a maximum of

0.15% carbon, a minimum of 16%
chromium, and sufficient nickel and/or
manganese.
Grade 316 is the standard molybdenum-bearing grade, second in importance to 304 amongst
stainless steels.
The molybdenum gives 316 better overall corrosion resistant properties than Grade 304,
particularly higher resistance to pitting and crevice corrosion in chloride environments.
Grade 304 steel: The most widely used austenite steel also known as 18/8 for its composition
of 18% chromium and 8% nickel.
It is usually required in very high or very low temp., are generally more corrosion resistant .

Proper designing
Sharp corners and edges should be avoided in a fabrication since these act as
anodes get more easily corroded.
Weld Sharp corner Smooth bend

Poor designs - more corrosion Best design-least corrosion
Bolt joint crevices

Weld joints
Poor design – more corrosion Better design – more corrosion
Weld joint
Best designs – least corrosion

6
Weld rather than rivet. Easy replacement of vulnerable parts Avoid excessive mechl. stress

Electrical insulation
Where different metals are used in combination, galvanic corrosion can be prevented by
electrically insulating them from each other.
The insulation has to break all contact between the metals.

The illustration shows a solution for bolt joints.
Insulating materials (washers, spacers) can be used when two dissimilar metals have to
be put together in a fabrication.
When two dissimilar metals are together, painting or electroplating the anodic metal
will help in reducing corrosion.

b. Use of pure metal:
 Impurity in the metal can create anodic and cathodic parts and hence leads to
electrochemical corrosion.
 Metals like Al, Mg, when used in the purest form become corrosion resistant by
impervious oxide film formation.
 production of pure metals is a very expensive process and metal will lose some of its
mechanical properties during purification.
c. Use of metal alloys:

 Alloying is a very good method for corrosion protection.
 Alloying metals like Fe, Cu etc. with noble metals makes the metal passive and reduces
corrosion.
 Eg. Addition of Ag, Cr, Ni etc. to iron as alloying metals will give corrosion
resistance. (stainless steel) 8
Corrosion control methods: d. Cathodic protection:
d. Cathodic protection:
o Principle is to make the base metal to be protected as cathode by connecting to a highly
anodic metallic plate.
Two methods of cathodic protection are known:

i) Sacrificial anodic protection
ii) Impressed current cathodic protection
i) Sacrificial anodic protection:

 The metallic structure to be protected is connected through a metal wire to a more
anodic metal.
This will induce corrosion at the anodic metal.
 Thus the more anodic metal sacrifices itself and gets corroded protecting the metallic
structure.
 Sacrificial anodes known are Zn, Mg, Al and their alloys.
Applications: protection of
Underground pipelines, ship hulls and other marine devices, Water
heaters, water tanks.
Sacrificial anodic protection
Sacrificial anodic protection - concept

e-
Mg
Mg2+
10
d. Cathodic protection: i) Sacrificial anodic protection
Insulated
Insulated copper wire copper wire
Sacrificial zinc
Soil
Sacrificial
anode
Mg
Underground Sacrificial Zn or Mg
Pipeline (Cathode) Ship hull rod
Sacrificial anodic protection Hot water tank
11
(a) Sacrificial anodic protection method in seawater
In this method, the corroding metal is protected by connecting it with a piece of more anodic metal
(active metal) from the galvanic series.
The active metal behaving as anode gets corroded thereby sacrificing itself.
Metals commonly employed as sacrificial anodes : Mg,

Zn and Al.
Applications: protection of ship-hulls, water tank, etc.
Al on steel
Zn on steel
Sacrificial anodic protection
Zinc is attached to the steel hull of the vessel
Attachment points
Corrosion control methods: d. Cathodic protection:
b) Impressed current cathodic protection:

 Impressed direct current is applied in the opposite direction to the corrosion current to
nullify it.
 Usually, one terminal of a battery is connected with an insoluble anode.

e.g.
 Graphite electrode is immersed in black fill containing coke, gypsum, bentonite and sodium
sulphate for good electrical conductivity.
 The other terminal is connected to the metallic structure to be protected.
 Since the current is impressed on the metallic structure, it acts as cathode and thus gets
protected.
Applications:
 This method is usually used to protect underground water pipe lines, oil pipe lines,
transmission lines, ships etc.
14
Corrosion control; b) Impressed current cathodic protection:
Impressed current cathodic protection

Graphite anode Source for
+ _
impressed DC
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Soil
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
_
::::::::::: Insulated
:::::
::::::::::: copper wire
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
+
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Buried
Pipe
Made
Cathodic
(protected)
Cathodic protection prevents corrosion by converting all of the anodic (active) sites on the metal surface
to cathodic (passive) sites by supplying electrical current (or free electrons) from an alternate source.
Usually this takes the form of galvanic anodes, which are more active than steel. 15
(b) Impressed current cathodic protection system in underground pipeline
e-
An cast iron pipe (anode) connected to an insoluble metal (cathode, lower in the galvanic series:
stainless steel, Pt or graphite).
When an impressed current from a D.C. current source (like battery or rectifier) is applied in the
direction opposite to the corrosion current, the cast iron pipe now behaves as cathode and hence
protected.
Cast iron is a group of iron-carbon alloys with a
The insoluble metal behaves as anode. carbon content greater than 2%
The anode is usually in a “back-fill” (coke or gypsum) so as to increase the electrical contact with the
protected cathode through the surrounding soil.
Applications: large buried oil or water pipes, transmission towers, etc.

Impressed current cathodic protection system in underground pipeline
By imposing a voltage which causes electrons to flow towards the object to be

protected, we make it less anodic and protect it from corrosion damage.
Impressed current cathodic protection system in underground pipeline

Physical Vapor Deposition (PVD) Chemical vapor deposition (CVD)

Physical Vapor Deposition (PVD)
PVD is a process of depositing some material either atom-by-atom or molecule-by-molecule or ion-by-ion on a
solid substrate under vacuum conditions.
PVD is a process used to produce a metal vapour that can be deposited on electrically conductive materials as a
thin, highly adhered pure metal or alloy coating.
The process is carried out in a vacuum chamber at high vacuum (10–6 torr).
Material to be deposited is heated to a high vapor pressure by electron bombardment in "high" vacuum and is
transported by diffusion to be deposited by condensation.
Used to create a very thin layer of material into a substrate and to make as thin films.
PVD only uses physical forces to deposit the layer while CVD uses chemical processes.
Both PVD and CVD are used largely in the production of semiconductors, IC

Applications of PVD coatings
1. PVD is used to apply relatively thick (1mm) coatings of heat resistant materials on jet engine parts.
A special alloy of Chromium, Aluminium and Yttrium are used in this type of coating.
2. PVD is widely used to produce decorative coatings on plastic parts and make them look like
shiny metal. Eg. parts with a PVD coating of aluminum.
3. Applications in Semiconductor devices; heat resistant materials.
4. Used in Surgical/Medical, Coated Cutting tools for metalworking and wear resistance.
,
5. Highly reflective films for decorative displays.

How does PVD process work? PVD processes involved four steps:
1. Evaporation. 2. Transportation, 3. Reaction and 4. Deposition
1. Evaporation:
A target is melted or bombarded by a high energy source such as a
beam of electrons or ions.
The atoms are dislodged from the surface of the target, and get
‘vaporized’.
2. Transportation: Movement of ‘vaporized’ atoms from the target to the

substrate.
3. Reaction:
In order to coat metal oxides, nitrides, carbides, etc, the atoms from
the target will react with an appropriate gas (Reactive gases such as
oxygen, nitrogen and methane) during the transportation stage to form
the metal oxides, nitrides, etc.
In cases where the coating on the substrate should be only the
pure metal, then this step would not be applicable.
4. Deposition: This is the process of coating build-up on the substrate

surface. More the time, higher the coating thickness.
Main types of PVD :
1. Thermal evaporation; 2.Sputtering 3. Ion plating.
All these three processes are performed under vacuum.
PVD-1: Thermal evaporation

Thermal Evaporation method involves the deposition of a thin film on a substrate according to
the following sequence of steps:
1) the target material to be deposited is converted into vapor by physical means;
2) the vapor is transported across a region of low pressure to the substrate;
3) the vapor undergoes condensation on the substrate to form thin film.
2. PVD – Sputtering- bombarding a target material with a charged gas

What is Sputtering?
Sputtering is done by bombarding a target material with a charged gas (typically argon) which
releases atoms from the target and these atoms condense over the nearby substrate to make a
thin film
It all takes place inside a magnetron vacuum chamber under low pressure.
Sputtering process:
1) Inert gaseous ions are generated and directed at a target material;
2) The ions impact the target at very high-speed and sputter (release) the atoms from the target;
3) The sputtered atoms get transported to the substrate through a region of reduced pressure;
4) The sputtered atoms condense on the substrate, forming a thin film.
Materials used: widely used for depositing various metallic films

Aluminum, aluminum alloys, platinum, gold and tungsten, ceramics, metal alloys.
Organic and inorganic compounds on other types of substrates (like silicon wafer used in Pentium
processors.
• Diamond can be coated on any substrate using this sputtering
method using graphitic carbon as a target source.
The magnetron is a high-powered vacuum tube, that works as self-excited microwave oscillator. Crossed
electron and magnetic fields are used in the magnetron ...
2. PVD - Sputtering
Sputtering parameters:
1. The substrate to be coated is connected to a high voltage DC power supply.
2. When the vacuum chamber has been pumped down,

Controlled amount of argon or another gas is introduced to establish a pressure of about 10-2 to 10-3 mmHg.
3. On energizing current supply, a plasma (high-energy particles) is established between the substrate
electrode (anode) and the target material to be evaporated (cathode).
What is a Plasma?
Plasma is created by applying an electric field to an inert gas like Argon, thereby creating free
electrons within the discharge region.
4. The gaseous atoms are ionized and they bombard the material to be coated.
5. The energy of imposing ions cause atoms of the target material to be

sputtered off and they are transported through the plasma to form a coating.
2. PVD - Sputtering
6. Direct current sputtering is used when the target is electrically conductive.
Radio-frequency sputtering, uses a RF power supply is used when the target is a non conductor such as polymer.
Sputtering yield is the number of atoms ejected per incident ion (Ar+).
Sputtering yield depends on 3 factors:
1) target material;
2) mass of the bombarding particles; and
3) Energy of bombarding particles.
Sputtering is done in the energy range between 10 to 5000 eV.
3. PVD – Ion Plating- for very thin films for electrical, optical & wear-resistant applications.
Ion plating is the combination of thermal evaporation and sputtering methods.
1. Metal is evaporated thermally and plasma is established to ionize the evaporating species.
2. Evaporated metal ions bombard the substrate with energy.
3. They physically implant into the substrate to produce an extremely strong coating bond.
4. Sputter and ion plated coatings are used in design for very thin films for electrical, optical and wear-resistant
applications.
5. The wear properties of tools are widely enhanced by hard thin film coatings.
_
+
Applications of PVD coatings
1. PVD is widely used to produce decorative coatings on plastic parts and make
them look like shiny metal. Eg.
Plastic automobile parts with a PVD coating of aluminum.
2. PVD is used to apply relatively thick (1mm) coatings of heat resistant

materials on jet engine parts.
A special alloy of Chromium, Aluminium and Yttrium are used in this type of coating.
2. Used in Surgical/Medical, Coated Cutting tools, Fire arms, etc.
What are the disadvantages of PVD coatings?
1. It is a line-of-sight technique meaning that it is extremely difficult to coat

undercuts and complicated surface features.
2. High capital cost.
3. Some processes operate at high vacuums and temperatures requiring

skilled operators.
4. Process emit large amounts of heat and hence require a cooling system.
5. The rate of coating deposition is usually quite slow.
Advantages of PVD-Sputtering over other PVD methods:

1. Sputtering can be achieved from large-size targets;
2. Film thickness is easily controlled by adjusting the deposition time;
3. Control of the alloy composition and grain structure is more easily accomplished than by thermal
evaporation method.
4. Sputter-cleaning of the substrate can be done;
5) Device damage from X-rays generated by electron beam evaporation is avoided.
Disadvantages of PVD-Sputtering over other PVD methods:

1) High capital expenses are required;
2) The rates of deposition of some materials (such as SiO2) are relatively low;
3) Some materials such as organic solids are easily degraded by ionic bombardment;
4)Sputtering has a greater tendency to introduce impurities in the substrate than deposition by
evaporation because the former operates under a lesser vacuum range than the latter.
Chemical vapor deposition or CVD
CVD is a deposition method involve depositing a solid material from a gaseous phase typically under
vacuum.
CVD is a coating process uses thermally induced chemical reactions at the surface of a heated substrate.
. Used to produce high quality, high-performance, solid materials,
The process is often used in the semiconductor industry to produce thin films.
CVD is a process in which the substrate is exposed to one or more volatile precursors,
which react and/or decompose on the substrate surface to produce the desired thin film deposit.
CVD applications are the preparation of high-temperature materials (tungsten, ceramics, etc.) and
production of solar cells, high-temperature fiber composites
Gallium arsenide is used in some integrated circuits

(ICs) and photovoltaic devices.
Amorphous polysilicon is used in photovoltaic devices.
Certain carbides and nitrides confer wear-resistance.
Chemical vapor deposition or CVD

It is a group of processes that involve depositing a solid material from a gaseous phase.
It is an important technique for surface modification through deposition of films and coatings.
It is similar in some respects to physical vapor deposition (PVD).
PVD differs in that the precursors are solid;
The material to be deposited is being vaporized from the solid target;

The vaporized solid is deposited onto the substrate.
Whereas in CVD, the precursors are introduced to the reaction chamber in the gaseous state.
Used in variety of applications- as wear resistance, corrosion resistance,
high temperature protection etc.
Gallium arsenide- fabrication of semiconductors, integrated circuits, sensors,
Amorphous polysilicon is used in photovoltaic devices
Different Precursors used in CVD?
1. Halides - TiCl4,
2. Hydrides - SiH4, GeH4, AlH3(NMe3)2,
3. Metal Alkyls - AlMe3, Ti(CH2tBu)4,
4. Metal Alkoxides - Ti(OiPr)4, etc
5. Metal Carbonyls - Ni(CO)4, etc
CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the
reactor chamber.
Reactor chamber – Chamber within which deposition takes place.
Substrate loading mechanism – A system for introducing and

removing substrates etc
Energy source – Provide the energy/heat that is required to get the precursors to react/decompose.
Vacuum system – A system for removal of all other gaseous species other than those required for the
reaction/deposition.
Exhaust system – System for removal of volatile by-products from the reaction chamber.
Exhaust treatment systems – In some instances, exhaust gases may not be suitable for release into the
atmosphere and may require treatment or conversion to safe/harmless compounds.
Process control equipment – Gauges, controls etc to monitor process parameters such as pressure,
temperature and time.
Alarms and safety devices would also be included in this category.
Chemical vapor deposition (CVD)

What are the different energy sources used in CVD?
1. Resistive Heating e.g. tube furnaces
2. Radiant Heating e.g. halogen lamps
3. Radio Frequency Heating e.g. induction heating
4. UV-visible light or lasers as a source of photo energy
What are the different Precursors used in CVD?

1. Halides - TiCl4, TaCl5, WF6, etc
2. Hydrides - SiH4, GeH4, AlH3(NMe3)2, etc
3. Metal Alkyls - AlMe3, Ti(CH2tBu)4, etc
4. Metal Alkoxides - Ti(OiPr)4, etc
5. Metal Carbonyls - Ni(CO)4, etc
Essential condition for a precursor to be used in CVD:

Since materials are deposited from the gaseous state during CVD, their precursors must be volatile
and stable enough to be able to be delivered to the reactor.
Coating Characteristics
CVD coatings are typically:
• Fine grained • Impervious • High purity
Harder than similar materials produced using conventional ceramic fabrication processes
CVD coatings are usually only a few microns thick and generally deposited at fairly slow rates,
usually of the order of a few hundred microns per hour.
Materials That Can be Produced by CVD Processes

CVD is an extremely versatile process that can be used to process almost any metallic or ceramic
compound.
Some of these include:

• Metals and alloys
• Carbides
• Nitrides: Silicon nitride is often used as an insulator
• Borides, Oxides
• Intermetallic compounds
Chemical vapor deposition (CVD)
Advantages
1. CVD coatings are typically fine grained and of high purity.
2. Harder than similar materials produced using conventional ceramic fabrication processes.
3. CVD coatings are used to make explosion or shatter resistant glasses.
Disadvantages
1.Separate process and reaction must be developed for each coating.
Some of the gases are toxic and dangerous.
All surfaces in the reaction chamber get coated.
2. But greatest disadvantage is temperature of the substrate should be very high at 700°C.
3. At this temperature, many metals (substrates) soften.
CVD apparatus
CVD Applications
1. As coatings for a variety of applications such as wear resistance, corrosion resistance, high temperature
protection, etc.
2. In the fabrication of semiconductors, integrated circuits, sensors, etc.
3. In the production of optical fibers for telecommunications.
4.To produce ceramic matrix composites such as carbon-carbon, carbon-silicon carbide (SiC) and SiC-SiC
composites.
5. CVD can be used to produce a synthetic diamond by creating the circumstances necessary for carbon atoms in
a gas to settle on a substrate in crystalline form.
Gallium arsenide is used in some integrated circuits (ICs) and photovoltaic devices.
Amorphous polysilicon is used in photovoltaic devices.
Certain carbides and nitrides confer wear-resistance.

What is the difference between PVD and CVD?
PVD is similar to chemical vapor deposition (CVD) except that the raw
materials/precursors, i.e. the material that is going to be deposited starts out in solid
form in PVD.
Whereas in CVD, the precursors are introduced to the reaction chamber in the gaseous
state.
What are the differences between PVD/CVD and electroplating?

PVD/CVD is a high cost process because of vacuum chamber/heating
requirements, and are normally batch processes whereas
Electroplating is low-cost and is a continuous process.

Factors that enhance corrosion!
Factors that enhance corrosion and

Choice of parameters to mitigate corrosion

Factors influencing corrosion
Metal corrosion is a slow process of destruction of metal objects, after
chemical reactions that occur on the surface of metals, alloys, under the
action of the environment.
Corrosion process is influenced by a number of internal and external factors.
Nature of the metal
 Position in the galvanic series
 Over voltage
 Relative areas of cathode and anode
 Purity of the metal
 Physical state of the metal
 Nature of surface film
 Passive character of the metal
 Solubility of corrosion product
 Volatility of the corrosion product
Nature of the corroding environment:
 Temperature
 Humidity in environment
 Presence of impurities in the atmosphere
 Presence of suspended solids in the environment Effect of pH
 Effect of pH, Nature of ions present
 Formation of oxygen concentration cell
 Flow velocity of process stream
Factors influencing corrosion depend on:
a) Nature of the metal and b) Nature of the corroding environment
(a) Nature of the metal (9 different factors):

i) Position in the galvanic series:
When two dissimilar metals are in contact, the more anodic metal
(Higher up in the series) will corrode.
The extent of corrosion depends on how far apart are the two metals
in the galvanic series.
ii) Over voltage:
o. When a metal (eg. Zn) is dipped in 1 N sulphuric acid, the initial rate of
corrosion is quite slow since hydrogen evolution takes place on Zn at 0.7V.
o. If a few drops of CuSO4 are added, the hydrogen over voltage comes down to
0.33V and corrosion rate increases.
o. Reduction in hydrogen over voltage increases the rate of corrosion.

iii)Relative areas of cathode and anode:
When two dissimilar metals are in contact, the rate of corrosion is
directly proportional to the ratio of cathodic part to anodic part.
If anodic area is small, the corrosion is rapid.
iv) Purity of the metal:

Purer the metal, lesser is the rate of corrosion.
Due to impurities, local galvanic cells are formed and anode gets corroded.
v) Physical state of the metal:

The rate of corrosion will depend on the physical state of the metal
grain size, orientation of crystals, stress etc.
vi) Nature of surface film: (Pilling-Bedworth rule):
Corrosion depends on the nature of surface film i.e. the oxide film is stable or unstable
or volatile or porous or non-porous will decide the rate of corrosion of the metal.
Ratio (R): ~  1 ; i.e., V[MOx]  V[M] : Protective oxide
Ratio (R):  1 ; i.e., V V : Non protective oxide
vii) Passive character of the metal:
Some metals eg. Ti, Al, Cr, Ni and Co are passive, hence show resistance
to corrosion.
They form highly protective oxide layers on their surfaces which gives
the metal passive character and protects it from further corrosion.
viii) Solubility of corrosion product:

If the corrosion product is soluble in the environment in which the metal
is working, then the corrosion will proceed faster.
If the corrosion product is insoluble in the environment, then the

corrosion is very slow since the corrosion product becomes a protective
layer on the metallic surface. Eg.PbSO4.
ix) Volatility of the corrosion product:

If the corrosion product is volatile, it evaporates as soon as it is formed
exposing fresh metal for corrosion and hence the corrosion becomes
very rapid and the metal will disappear over a period of time (MoO3,
SnCl4).
b)Nature of the corroding environment:

i) Temperature: As temp. increases, the rate of corrosion also increases.
ii) Humidity in environment:
“Critical humidity” is the relative humidity above which metallic corrosion rate
increases sharply.
It depends on the nature of the metal and the corrosion product.
In marine environment, humidity is higher and gases like CO2/O2 furnish water
to the electrolyte (salt) to set up a electrochemical cell resulting in corrosion.
iii) Presence of impurities in the atmosphere:

Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 which are present in
the industrial areas provide conductive environment for enhancing the
chemical (dry-type) corrosion.
In marine environment, the Cl- ion responsible for enhanced rate of wet
corrosion.
iii) Presence of suspended solids in the environment:

Particles like NaCl or Ammonium sulphate together with moisture act as
conductive electrolyte and enhance the rate of electrochemical corrosion.
b)Nature of the corroding environment:
v. Effect of pH: Acid medium facilitates corrosion than neutral/basic media.
For Zn: Zinc corrodes rapidly in acidic solutions but the rate of corrosion
is low in alkaline medium.
Reason: the zinc oxide film is destroyed at acidic pH.
For Al: Aluminum corrodes less in acidic solutions but the rate of
corrosion is very high in alkaline medium.
Reason: Aluminum oxide film is destroyed at alkaline pH.
Fe at pH = 5: case 1: Corrosion rate of Fe in O2 free water is very slow (H2

evolution type of corrosion).
Fe at pH = 5: case 2: Corrosion rate of Fe in the presence of O2 is enhanced
(O2 absorption type of corrosion).
Reason: The oxide film, though forms a protective film, is damaged at
acidic pH and hence a small area of anode is created, thereby the rate
of corrosion is high.
vi) Nature of ions present:
Anions like silicates form insoluble salts and inhibit corrosion.
But, H+Cl- present in the atmosphere destroy the protective oxide
film and enhance rate of corrosion.
b) Nature of the corroding environment
Vii)Formation of oxygen concentration cell:

If one part of the metal is exposed to higher levels of oxygen, it becomes
cathode and the other part which is exposed to lesser levels of oxygen will
become anode.
This is called oxygen concentration cell which promotes
corrosion by anodic oxidation/dissolution.
2 H2O + O2 + 4e-4 OH- (Cathodic reaction-higher O2)
This OH- will move to the cathode-anode interface where Fe2+

reacts to form Fe(OH)2 which later converts into rust (Fe2O3.3H2O).
Buried pipelines, cables, experience this kind of electrochemical corrosion.
Viii) Flow velocity of process stream:
Corrosion is a diffusion controlled process.
Increase in flow velocity of the corrosion medium (liquid in a boiler) enhances

diffusion rate, thereby increasing the corrosion rate.
Therefore, optimization of flow velocity may decrease corrosion rate.

Lithium ions Battery

The 2019 Nobel Prize in Chemistry awarded to trio for

development of lithium-ion batteries
The prize went to:
•John B. Goodenough of the University of Texas.
•M. Stanley Whittingham of the State University of New York at Binghamton.
•Akira Yoshino of Asahi Kasei Corporation and Meijo University in Japan.
John B. Goodenough M. Stanley Whittingham Akira Yoshino
The 2019 Nobel Prize in Chemistry was awarded to John B. Goodenough, left, M. Stanley
Whittingham, centre, and Akira Yoshino
Goodenough, who at 97 becomes the oldest winner of a Nobel Prize, doubled the lithium battery's potential in the
following decade and Yoshino eliminated pure lithium from the battery, making it much safer to use.
(II) Advanced Secondary batteries: 2. Lithium ions Battery
Lithium ions Batteries have the highest energy density of all batteries.
Lithium Primary Batteries-

Lithium ion Batteries- Intro
In the 1980s progress was made in the use of Li as an anode material with MnO2,
• Liquid SO2 or thionyl chlorides as the cathode, and hexaflurophosphate dissolved in propylene carbonate as
a typical organic electrolyte.
• Li cells are generally properly sealed against contact with air and moisture.
• The main attractions of lithium as an anode material is
• It is the most electronegative metal in the electrochemical series.
• It has very low density, Lightest metal but gives the
• Largest amount of electrical energy per unit weight.
 It can provide the highest number of electrons per gram when it is oxidized
• But Li cannot be used with the traditional aqueous electrolytes
• Due to the very vigorous corrosive reaction bet. Li and water with flammable hydrogen as the
product.
Lithium ion Batteries-
 The anode material is layered carbon or graphite and Lithium with binder
 The battery consists of a anode of Lithium, dissolved as ions, into a carbon.
• Lithium has greatest electrochemical potential, lightest weight of all metals.
Cathodic material used as
Lithium cobalt oxide,/ Lithium manganese dioxide/Lithium nickel dioxide.
• Overcharging would convert Lithium-X dioxide to metallic lithium, with risk of explosion.
Lithium ion batteries: Anode materials, Electrolyte:
Anode materials:
Cathode materials
The most common compounds used for cathode materials are
LiCoO2, LiNiO2 and LiMn2O4.
LiCoO2 has the best performance but is very high in cost, is toxic and
has a limited lithium content range over which it is stable.
LiNiO2 is more stable, however the nickel ions can disorder.
LiMn2O4 is generally the best value for money, and
It is also better for the environment.
Electrolyte:
 Since lithium reacts violently with water and the cell voltage is so high that
the water would decompose.
 Non-aqueous electrolyte must be used.
Lithium ion Batteries- Chemistry and Construction

• Anode here is lithium ions in the carbon material
e.g. carbon, which can store and exchange lithium ions.
• A lithium ion-accepting material, for example CoO2,

is then used as the cathode material,
• Lithium ions are exchanged back and forth between the

two electrodes during discharging and charging.
• These are called intercalation electrodes.
• This type of battery is known as a “rocking chair battery”

as the ions simply “rock” back and forth between the two
electrodes.
• The lithium ion moves from the anode to the cathode during
discharge and from the cathode to the anode when charging.
Lithium ion Batteries- Chemistry and Construction

Anode: lithium adsorbed over the carbon material
Cathode: lithium in between the layered CoO2
The following reactions take place during discharging and charging:
• At the anode: Li(0)C6 Li+ + 6C + e-
• At the cathode: Li+ + Co(IV)O2 +e- Li(I)Co(III)O2
• Overall: LiC6 + CoO2 LiCoO2 + 6C

Chemistry and Construction:
• Anode here is a non-metallic compound, e.g. carbon, which can store and exchange
lithium ions.
• A lithium ion-accepting material, for example MnO2 or CoO2, is then used as the
cathode material, and
• Lithium ions are exchanged back and forth between the two electrodes (carbon,
graphite) during discharging and charging. Hence, these electrodes are called
intercalation electrodes.
• This type of battery is known as a “rocking chair battery” as the ions simply “rock”
back and forth between the two electrodes.
Lithium ion Cells

Charging Discharging
Anode: Lithium ions in the carbon material

Cathode: Lithium ions in the layered material (lithium compound (LiCoO2)
Anode : Li1-XCoO2+ CnLix  LiCoO2 + Cn Cathode: LiCoO2+ Cn  Li1-XCoO2 + CnLix
The lithium ion moves from the anode to the cathode during discharge and
from the cathode to the anode when charging.
Applications: Laptops, cellular phones, electric vehicles

(II) Advanced Secondary batteries: Lithium-TiS2 battery
Backup batteries
Anode: Li (s)
Cathode: TiS2-Titanium disulfide
Electrolyte: Poly-2-vinylpyridine (P2VP) solid electrolyte
Electrochemical reaction during discharge
Anode half – cell reaction : Oxidation: Li (s) ↔ Li+ + e−
Cathode half – cell reaction : Reduction: Ti(II)S2 (s) + e− ↔ TiS2-
Therefore, the net cell reaction is: Li (s) + TiS2 (s) ↔ Li+ + TiS2-
Characteristics: P2VP is a solid organic charge transfer complex which permits

transfer of ions but not the transfer of electrons;
Cell voltage is 3 V; TiS2/Li battery is thermodynamically stable;
Li is light weight; all the constituents of the battery are solid and hence no risk of leakage
from the battery;
Can be made in a variety of shapes and sizes.
Lithium-TiS2 battery- devices, as backup batteries
Lithium-TiS 2 battery
Applications:
Used in portable consumer electronic devices, as backup batteries in

computers and communication equipment,
Lithium batteries can easily support the brief, heavy current demands of
devices such as digital cameras, and
They maintain a higher voltage for a longer period than alkaline cells;
Self-discharge is less than half compared to Ni-Cd batteries.
Lithium ion batteries: Advantages & Disadvantages:
Advantages:
2.5 to 1.7 non-linear output voltage;
lighter weight than lead-acid battery;
low cost of sulphur;
high energy density; used in electric cars.
The lithium-sulfur cell can get an electric car 400 miles for a single charge.
Disadvantages:
This battery must be operated at high temperatures as S and Li must be in
their molten states for the operation of cell reaction.
Since sulphur lacks electro-conductivity, the carbon coating on the sulfur then
provides the electro-conductivity that was missing from pure sulfur;
Intermediary polysulfides are soluble in the electrolytes which causes

irreversible loss of active sulfur material.
Lithium Polymer batteries are better than Lithium ion batteries
Exploded laptop
• Li-ion batteries use organic solvents to suspend the lithium ions.
• In situations where the structure of the battery is compromised, that solvent
can ignite and vent from the pressurized battery.
• The result is a dangerous explosion
• The main advantage of Li-poly batteries that has been discussed in the press
recently is their reluctance to explode under duress .
• Lithium Polymer batteries used in Power bank.
The safety Issues
Difference between a lithium ion battery and a lithium polymer battery?

The difference between a lithium ion battery and a lithium polymer battery
Li-ion battery has a liquid electrolyte
Li-ion battery using a liquid lithium-salt electrolyte ( LiPF6) suspended in an organic solvent
( Ethelene Carbonate /Dimethyl Carbonate /Diethelene Carbonate ),
• Li-ion polymer batteries has the solid polymer electrolyte ,

The polymer may be a solid or semi-solid
The battery uses a solid polymer electrolyte (SPE) such as

• Poly-Carbon Monofluride
• poly(ethylene oxide) (PEO),
• poly(acrylonitrile) (PAN),
• poly(methyl methacrylate) (PMMA) or poly(vinylidene ...
Lithium Polymer Batteries
Lithium Polymer batteries used in Power bank.

Electrolyte used is a Polymer- Poly-Carbon Monofluride
Lithium Polymer Batteries: Lithium salt movement in solid polymer medium

Lithium Polymer Batteries are better than Lithium ion batteries.

Lithium Polymer Batteries - battery of the future.
Modules: 3 & 4: Corrosion & Corrosion Control
Galvanic
Differential aeration
corrosion corrosion:
Stress corrosion cracking
Galvanic corrosion: Stress corrosion cracking
Pitting corrosion
Modules: 3, 4,: Corrosion and Corrosion control methods
Module: 3;Corrosion: 6hrs

Corrosion Types– dry and wet corrosion;
Detrimental effects to buildings, machines, devices & decorative art forms.
Forms of corrosion:
Differential aeration, pitting, Galvanic and stress corrosion cracking.
Factors that enhance corrosion and choice of parameters to mitigate
corrosion.
Module: 4 Corrosion control: 4hrs

Corrosion Protection:
Cathodic protection –
Sacrificial anodic and impressed current protection methods;
Advanced Protective coatings:

Electroplating and Electroless plating, PVD and CVD.
Alloying for corrosion protection –

Basic concepts of Eutectic composition and Eutectic mixtures.
Selected examples – Ferrous and non-ferrous alloys.
Iron Ores, Different Metals

Nature:
Magnetite (Fe3O4, 72.4% Fe),
Hematite (Fe2O3, 69.9% Fe),
Hematite
Magnetite
Different Metals
In nature, most metals exists as compounds

(as their oxides, carbonates, chlorides,
silicates, etc). (except noble compds. Au, Pt,
etc)
These metallic compounds are
thermodynamically more stable.
Corrosion Corrosion
Corrosion is defined as the gradual destruction or deterioration of metals or alloys by
the chemical or electrochemical reaction with its environment.
or
Any process of deterioration and consequent loss of solid metallic material,
through an unwanted chemical or electrochemical attack by its environment.
It is a surface phenomenon- Deterioration of the metal starts at

the surface. It is an Oxidation reaction.
The most familiar example of corrosion is rusting of iron, when exposed to atmospheric
conditions.
The corrosion product formed is Fe3O4 (Fe2O3.FeO) which is a complex oxide
( red colored scale).
Corrosion degrades the useful properties of materials and structures including

strength, appearance and permeability to liquids and gases.
Chemical or electrochemical attack from the environment on a solid metal resulting in its
deterioration (or destruction or disintegration) starting at the surface of the metal is called
“CORROSION”. - Thus corrosion is a “reverse extraction of metals”.
Effects of Corrosion
Corrosion degrades the useful properties of materials and structures including
strength, appearance and permeability to liquids and gases.
Detrimental effects to buildings, machines, devices & decorative art forms.
Oxygen, H2S, sulphur dioxide, nitrogen,
Corrosion Types
Types of Corrosion
I. Dry Corrosion 2. Wet Corrosion 3. Other types

#. Corrosion by gases #. Galvanic or bimetallic
(with less water) #. water line corrosion
corrosion.
8
Types of corrosion
a) Dry corrosion - Corrosion by atmospheric gases

(absence of moisture or with less water):
Dry corrosion is due to the attack of metal surfaces by the
atmospheric gases --O2, H2S, SO2, N2 & inorganic liquids.
Types:
(i) Corrosion by oxidation;
(ii) Corrosion by gases other than O2
(iii) Corrosion by liquid metals;
b) Wet or Electrochemical corrosion; water line corrosion

Most of the corrosion processes are electrochemical in nature.
Types:
(i) Evolution of hydrogen-type corrosion;
(ii) Absorption of oxygen-type corrosion;
iii) concentration cell corrosion (or water line corrosion)
(v) pitting corrosion;
(vi) Stress corrosion.
Galvanic or bimetallic corrosion;

Types of corrosion: a. Dry or Chemical corrosion
a) Dry or Chemical corrosion
(i) Corrosion by oxidation;
(ii) Corrosion by gases other than O2
(iii) Corrosion by liquid metals;
a. Dry or Chemical corrosion; (i) Corrosion by oxidation
It occurs when O2 present in the atmosphere attacks the metal at low or

high temperatures (usually in the absence of moisture), thereby forming
an oxide layer on the surface of the metal.
Fe  Fe2+ + 2 e- (oxidation)
½ O2 + 2e-  O2- (reduction) Oxidation corrosion results in the
Fe + ½ O2  Fe2+ + O2- (total reaction) formation of an metal-oxide film
(MO)
which may be porous/non-porous.
Mechanism Fe2+ Outward diffusion of metal ions through

2+
the
scale (faster, due to small size of Fe )
Atmospheric oxygen Fe  Fe2+ + 2e- (oxidation)
(air) O2 Metal (M)
2e-
½ O2 + 2e-  O2- (reduction) O2- Inward diffusion of oxide ions (MO) through
the scale (slower, due to larger size of O2-)
Prof ASN
I. Dry Corrosion
O2 gas attach on the surface and leads to corrosion
Corrosion Surface
A. Stable B. Unstable C. Volatile 4. Porous

Metal oxide (MOx) MOx-Unstable<M-stable) (MOx)-evaporate (MOx)-pores O2
Metal (M) Metal (M) Metal (M) Metal (M)

*MOx as protective layer *Not easy to corrode! *M-expose lot/corrosion *M-expose lot/corrosion
Al, Sn, Pb, Cu, Au & Ag MoO3 Li, Na, K, Mg, Te2O3
Ni and Cr
*MOx is unstable *MOx is volatile
*Metal is stable. *Allow free metal *MOx is porous
*Passive surface *Metal not corrode *Metal to attach O2 *More O2 exposure
*Protecting the metal *Special case! • Continuous
•*Severe corrosion
*Corrosion Resistive film corrosion 11
• Fresh surface exposed for
further attack
(i) Corrosion by oxidation: Types of oxide layers formed: 4 types
i) Stable oxide layer:
o It is a fine grain of metal-oxide layer which is stable, non-porous and
adheres strongly to the pure metallic surface.
o E.g. Oxides of Al, Pb, Cu, Ni and Cr which form stable, non-porous and
tightly adhering metal-oxide films (<300 Å or 30 nm thick) to the pure metallic
surface thereby preventing further oxidation corrosion.
ii) Unstable oxide layer:

o Oxide layers produced on noble metal surfaces (Au, Pt, Ag, etc) immediately
decompose back into the metal and oxygen. thereby preventing oxidation corrosion.
Metal + Oxygen Metallic oxide
Unstable
Exposed surface
metal oxide
O2 in air Metal oxide

decomposes
metal metal metal + O2
immediately
iii) Volatile oxide layer:
o The metal-oxide layer which evaporate rapidly as soon as they are formed,
thereby exposing the underlying metal surface for further corrosion. E.g.
MoO3 is volatile.
Exposed surface volatile metal oxide Fresh surface exposed for

further attack
Metal oxide
O2 in air volatilizes
metal
metal metal
iv) Porous oxide layer:

o These oxide layers have minute pores or cracks through which the
atmospheric oxygen diffuse and contact the pure metal surface, thereby
further corrosion is promoted. Li, Na, K, Mg
Exposed surface Porous metal oxide
metal O2 in air Further attack through

metal pores & cracks continues
Pilling-Bedworth rule:
o An oxide is protective or non-porous
o If the volume of metal-oxide is equal to or greater than the volume of the
metal getting corroded;
o Then the oxide film is non-porous and protects the metal from
further corrosion.
o Cu, Al, Ni, Cr form tightly adhering, non-porous oxide layers

resulting in rapid decrease in the rate of oxidation to zero.
An oxide is non-protective or porous

If the volume of the metal-oxide is less than the volume of the metal
getting corroded, it will promote further corrosion of the metal”.
o Li, Na, K, Mg form porous oxide layers and hence the rate of
oxidation continues non-stop.
Prof ASN
Pilling-Bedworth Rule
Condition-1: An oxide is protective or non-
porous if the volume of metal-oxide is equal MOx V[MOx]
to or greater than the volume of the metal
from which it is formed. M
V[M]
Volume of V[MOx]
Ratio (R) = ~ 1 ; i.e., V[MOx]  V[M] : Protective oxide
Volume of V[M]
Condition-II: An oxide is non-protective or
porous if the volume of the metal-oxide is MOx Porous
less than the volume of the metal from V[MOx]
which it is formed.
M
V[M]
Volume of V[MOx]
Ratio (R) = <1 ; i.e., V[MOx] V[M] : Non protective oxide
Volume of V[M]
Corrosion system 15
•Briefly explain the effect of metal oxide volume and the metal surface area on further
•corrosion. What type of oxide is formed on the metal (M) and justify its impact on
Dry or Chemical corrosion: ii) Corrosion by gases other than O2: Cl2 , H2S,
ii) Corrosion by gases other than O2: Cl2 , H2S,
o The extent of corrosion depends on the chemical affinity between the metal
and the gas involved.
o Dry Chlorine reacts with Ag and forms the protective or non-porous layer
(2Ag + Cl2  2 AgCl), thereby preventing the metal from further attack.
o The film formed is non-protective or porous (Sn + 2Cl2  SnCl4, volatile),

thereby exposing the underlying fresh metal surface for further attack.
Fe + H2S  FeS + 2H (atomic hydrogen) in which H2S gas attacks steel at high
temperature and make them brittle (hydrogen embrittlement) by forming FeS as
porous scales.
Dry or Chemical corrosion: (iii) Corrosion by liquid metals:
(iii) Corrosion by liquid metals:
Liquid metal (Hg) flowing at high temperature over the solid metal
or alloy can result in either the:
a) Dissolution of the solid metal by the liquid metal (Gold can be

corroded by mercury) or
b) Internal penetration of the liquid metal into the solid metal.

Such corrosion is found in devices used in nuclear plants.
Passivity:
Definition:
Passivity or passivation is the phenomenon in which a metal or an alloy
exhibits a much higher corrosion-resistance than expected from its position
in the electrochemical series.
Reason of passivity formation:

Passivity is due to the formation of a highly protective,
Very thin (~30 nm thick) and quite invisible film on the surface of the metal or
an alloy, which makes it more noble.
Characteristics of the passive film:

The film is insoluble, non-porous and self-healing in nature.
When broken, it will repair itself on re-exposure in the presence of oxygen.
Examples: Ti, Al, Cr, and Stainless steel containing Cr.

Advanced protective coatings: Electroplating techniques

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Advanced protective coatings: Electroplating techniques

Uploaded by

Copyright:

Available Formats

Advanced protective coatings: Electroplating

Dr. A.A.NAPOLEON, M. Pharm., Ph.D.

Coatings are broadly divided as

Protective coatings are classified as

o Mechanical cleaning, sandblasting, solvent cleaning, alkali cleaning, acid

o Useful for removing loose scales and rust.

o Hammering, wire brushing, grinding, polishing are the methods commonly

protective coatings Methods

a. Anodic coatings: Zn, Al, Cd = anode; Fe = Cathode (more noble)

Iron surface can be protected from corrosion by depositing a thin layer of

The anodic metal sacrifices itself to protect the base metal.

Since corrosion occurs at Zn, it behaves as Anode.

Copper/brass can be protected by coating it with a thin layer of tin.

Tinning of brass utensils is a very common practice in our country.

1. Cathodic protection of iron is successful only when there is no pit or crack

Galvanizing Process: Coating iron or steel sheets , rods, screws

Galvanized metal sheets

Then this metal is dipped in a molten zinc bath maintained at 430'c.

Tinning Process: Not for Examination, Only for understanding

Metal Cladding Not for Examination, Only for understanding

o Electroplating is done for improving

o Mainly used in automobile, aircraft, refrigerator & electrical appliances etc.

Electroplating or Electro-deposition- depositing a thin layer of metal

(a) On Metals: To increase the corrosion/chemical/wear Copper plating on aluminium

Electroplating copper can be extremely valuable in applications in the

products used in the aerospace and defense industries.

2. Adherence: Weak adherence leads to the peeling-off of the coating.

4. Decorative value: Should be

5. Temperature: Plating temperature: 35 to 60oC.

8. Composition of the electrolytic bath:

b) Complexing agents: Avoid the passivation of anodes so that they are

(c) Organic additives:

9. Choice of the electrolyte: Should be a

Should not undergo hydrolysis, oxidation, reduction and other chemical

It should possess sufficient covering power.

No single electrolyte satisfies all the above requirement.

Usually a mixture of electrolytes are used.

1. Solvent Cleaning: using solvents like toluene, acetone, CCl4, xylene.

This treatment provides a metal surface which can be readily wetted by

What is the importance of cleaning the metallic articles before electro-

6.Sand-blasting: Process consists of introducing sand into an air stream under

Plating bath solution: components:

3. Heating arrangement: Heating is provided by

6. Provision of Filters: In large plating operations, pumps and filters are

7. Pretreatment of cathodic surface:

(b) Acid pickling using dil. H2SO4;

(c) Polishing: using silicon carbide wheels followed by sand blasting

(d) Rinsing in water followed by drying.

Electroplating- Silver coating on Spoon

Electroplating with Nickel coating on Copper

Copper Cathode is reduced Nickel Anode is oxidized

Ni2+ ions within solution become attracted

Metallic pillar and outside

Dr. A.A.NAPOLEON, M. Pharm., Ph.D.

(b) Wet or Electrochemical corrosion

Wet corrosion occurs under the following conditions,

At the anode: M Mn+ + ne- (oxidation)

The important conditions/characteristics for electrochemical

(a) The formation of anodic and cathodic areas

(b) Presence of an electrolyte

(c) Corrosion of anodic part only

the cathodic areas.

Wet or Electrochemical corrosion occurs in the