Module:7 Industrial applications 7 hours

Water purification methods - zeolites, ion-exchange resins and reverse osmosis;

Fuels and combustion - LCV, HCV, Bomb calorimeter (numerical), anti-knocking agents

Protective coatings for corrosion control: cathodic and anodic protection - PVD technique;

Chemical sensors for environmental monitoring - gas sensors;

Overview of computational methodologies

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 Distribution of water

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 Types of impurities in Water

Natural Water may contain physical, chemical and biological impurities

such as

Physical impurities Chemical Impurities

1. Conductivity
1. Colour -Can be measured by 2. pH
Tintometer (Fe, Mn) 3. Alkalinity
2. Taste 4. TDS – Total dissolved salts
3. Turbidity-Total Suspended solids 5. Hardness-hardness causing ions
4. Odor (Ca2+ and Mg2+)

Biological impurities
1. Microorganism, Bacteria, Viruses
(BOD, COD, DO)

01/03/2025 3
 Hard Water

What is hard water?

Practically speaking, measurement of:

> Calcium (Ca) ions
> Magnesium (Mg) ions

Hardness as calcium carbonate

mg/L (ppm) GPG

Soft 0 -17 0-1.0

Moderately hard (Medium) 60 -120 3.5-7.0
Hard 120 -180 7.0-10.5
Very hard 180 & above 10.5 & over

1 GPG = 17.1 mg/L

GPG = Gram per gallon 1 Gallon = 3.7 liters

01/03/2025 4
Hardness of Water
Hardness in Water is characteristic that prevents the ‘lathering of soap’ thus water which does
not produce lather with soap solution readily, but forms a white curd precipitate is called hard
water.

Type of Hardness 1. Temporary Hardness

1. Temporary (or) Carbonate Temporary Hardness is caused by the presence of dissolved

Hardness
bicarbonate of calcium, magnesium and other heavy metals and
2. Permanent Hardness (or) non- the carbonate of iron. It is mostly destroyed by more boiling of
carbonate Hardness water, when bicarbonates are decomposed yielding insoluble
carbonates.

Ca(HCO3)2 Heat CaCO3 + H2O + CO2

Calcium bicarbonate Calcium Carbonate

Mg(HCO3)2 Heat MgCO3 + H2O + CO2

Magnesium Bicarbonate Magnesium Carbonate

01/03/2025 Calcium/Magnesium Carbonates thus formed being almost 5

insoluble, are deposited as a scale at the bottom of vessel, while
Permanent Hardness

Non Carbonate Hardness is due to the presence of chlorides, sulfates of calcium, Magnesium,
iron and other heavy metals

2C17H35COONa + (H.W)CaCl2 (C17H35COO)2Ca + 2NaCl

Sodium stearate Hardness Calcium stearate
(sodium soap) (Insoluble)

2C17H35COONa + (H.W) MgSO4 (C17H35COO)2Mg + Na2SO4

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)

Without Hardness

C17H35COONa + H2O C17H35COOH + NaOH

Soap Stearic acid

C17H35COOH + C17H35COONa Lather

Stearic acid Soap
01/03/2025 6
External treatment of water – External Conditioning of water

Softening of hard water can be done by the following

methods
1. Lime soda process
2. Zeolite methods
3. Ion exchange resin method
4. Mixed bed deionizer method

Zeolite is a Hydrated Sodium Alumino

Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.
Micro pores
The general chemical structure of
zeolite is given below
Na2O.Al2O3.xSiO2.yH2O (x = 2-10 and y = Granular/Porous Structure of zeolite
2-6)

Why synthetic Zeolite is better than Because they contain more number of pores
natural Zeolite for the softening of of desired size and hence effective
water? purification is possible
01/03/2025 7
 Hard water Ca2+
containing H2O
Ca ions Ca2+

Hardness causing
Ca ion is replaced
by Na ions
Ca2+

Zeolite porous structure

Micro pores
size of
various
01/03/2025 materials 8
Purification of water by a Zeolite softener
Construction of Zeolite Softener

Hard water
in

Hard water
Ca Cl2
spray

NaCl
NaZe Zeolite bed Na Ze
Gravel

Injector

CaCl2
Softened
To sink water
NaCl storage

01/03/2025 9
Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through the
zeolite bed at a specified rate. The hardness causing ions such as Ca 2+, Mg2+ are
retained by the zeolite bed as CaZe and MgZe respectively; while the outgoing water
contains sodium salts. The following reactions takes place during softening process
To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

Hardness

To remove permanent hardness

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4
Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na 2Ze + CaCl2 (MgCl2)

Used 10% brine Regenerated Washings
Zeolite solution Zeolite drained

01/03/2025 10
 Limitations of Zeolite process

1. If the water is turbid ---- then the turbidity causing particles clogs the pores of the
Zeolite and makes it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can not be
regenerated that easily
3. Any acid present in water (acidic water) should be neutralized with soda before
admitting the water to the plant

Advantages of Zeolite process

1. Soft water of 10ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation in the
treated water
4. It does not require more time and more skill

Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3-
and CO32- in the softened water (then it may form NaHCO3 and Na2CO3 which
releases CO2 when the water is boiled and causes corrosion)

01/03/2025 3. It also causes caustic embrittlement when sodium carbonate hydrolyses to give 11
NaOH
Ion-Exchange resin (or) deionization (or) demineralization process

Ion exchange resin

Ion exchange resins are insoluble, cross linked,

long chain organic polymers with a
microporous structure, and the functional
groups attached to the chain is responsible for
the “ion-exchange” properties.

01/03/2025 12
Based on the above fact the resins are classified into two types
1. Cation exchange resin (RH+)
2. Anion Exchange resin (ROH-)

Structure of Cation and Anoin exchange resins

Cation exchange resin Anion exchange resin In general the resins
- CH – CH2 – CH – CH2 – CH – CH2 containing acidic
- CH – CH2 – CH – CH2 – CH – CH2 functional groups (-COOH, -
- - SO3H etc) are capable of
exchanging their H+ ions
with other cations, which
SO-3H+ comes in their contact;
SO-3H+ CH2NR+3OH CH2NR+3OH
-CH – CH – CH- -
-CH – CH – CH- - whereas those containing
basic functional groups (-
-CH2 - CH – CH2- -CH2 - NH2, =NH as
CH – CH2-
CH CH hydrochlorides) are
capable of exchanging their
anions (OH-) with other
ions, which comes in their
SO-3H+ SO-3H+ contact.
CH2NR+3OH
-
CH2NR+3OH
-

Draw the structure of sulfonated poly styrene chain then connect each chain through
phenyl group
Purification of water by Ion exchange purifier (or) softener

Hard
water

Gravel
2Cl- 4H+ SO 2-
bed
Cation exchange Resin Anion exchange Resin
4
Ca2+ 2Cl- Mg 2+
SO42-
Injector
4H+
Injector
4OH -

Acid solution for Wastages to

regeneration of sink
Alkaline solution
resin Wastages to
for regeneration
sink of resin
pump

01/03/2025 Soft water 14

Process of softening

Reactions occurring at Cation exchange resin

2 RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+

2 RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+

Reactions occurring at Anion exchange resin

2 ROH- + SO42- (hard water) R2SO42- + 2 OH-

2 ROH- + Cl- (hard water) R2Cl- + 2 OH-
Advanced ion exchange softening-
Precautions
At the end of the process
1. Best applied for additional softening following lime-
H+ + OH- H2O soda softening, or
Softening water that is not too hard to begin with,
say <10 PPM

2. Ion exchange should not be used when the

concentration
of Fe, Mn, or the combination exceeds 0.3 mg/L

3. Ion exchange should not be used on raw or wash

01/03/2025 waters containing (high) dissolved oxygen 15
Regeneration

Regeneration of Cation exchange resin

R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) 2 RH+ + Ca2+ (CaCl2, washings)

Regeneration of Anion exchange resin

R2SO42- + 2OH- (dil. NaOH) 2 ROH- + SO42- (Na2SO4, washings)

Advantages
1. The process can be used to soften highly acidic or alkaline waters
2. It produces water of very low hardness of 2ppm. So the treated waters by
this method can be used in high pressure boilers

Disadvantages
1. The setup is costly and it uses costly chemicals
2. The water should not be turbid and the turbidity level should not be more
than 10ppm
01/03/2025 16
Softening of water by Mixed Bed deionizer

Description and process of mixed bed deionizer

1. It is a single cylindrical chamber containing a mixture of anion and cation exchange resins bed
2. When the hard water is passed through this bed slowly the cations and anioins of the hard
water comes in to contact with the two kind of resins many number of times
3. Hence, it is equivalent to passing the hard water many number of times through a series of
cation and anion exchange resins.
4. The soft water from this method contains less than 1ppm of dissolved salts and hence more
suitable for boilers

Hard water

c a c a Anion exchange
resin
c Mixed bed Mixed
a deionizer a resin bed
a
c a cc Cation exchange
resin

Demineralised
water
01/03/2025 17
 Regeneration of mixed bed deionizer

1. When the bed (resins) are exhausted or cease to soften the water, the mixed bed is back washed
by forcing the water from the bottom in the upward direction
2. Then the light weight anion exchanger move to the top and forms a upper layer above the
heavier cation exchanger
3. Then the anion exchanger is regenerated by passing caustic soda solution (NaOH) from the top
and then rinsed with pure water
4. The lower cation exchanger bed is then washed with dil.H 2SO4 solution and then rinsed.
5. The two beds are then mixed again by forcing compressed air to mix both and the resins are now
ready for use

Low
NaOH
density
resin
H2O

c a c a c a c a c a c a
aa a a a a a
cRegenerated
c Mixed bed c Exhausted a

H2
Back washed
a deionizer a a Mixed bed a
Mixed bed

SO
a

4
deionizer
a a ccccc c
c a cc c a cc c a c c

Back Compressed
wash High air
01/03/2025 water density 18
resin
 Drinking water (or) Municipal water treatment
The drinking water should meet the following requirements (conditions for
good
1. The water should be clear, colorless and odorless
2. It should be free form dissolved gases such as CO2, H2S etc
3. Water should be free from pathogenic microorganisms
4. The hardness should not be high ( not more than 125ppm)
5. The turbidity in drinking water should not exceed 25 ppm
6. The pH of the drinking water must be 7.0 – 8.5
7. The total dissolved salts (TDS) should be 500ppm

Purification steps
1. Screening
2. Aeration
3. Sedimentation and coagulation
4. Filtration
5. Sterilization and disinfection

01/03/20256. Storage and distribution 19

Desalination methods:
Reverse Osmosis and Electro Dialysis

Filtration

Adsorption Mechanical

Small particles attached Large particles trapped

to media between media

01/03/2025 20
Osmosis
Diffusion of solvent through a semipermeable membrane from a dilute solution to
concentrated side is called osmosis which happens until an equal concentration of
fluid on both sides of the membrane is achieved

semipermeable membrane

01/03/2025 21
 Reverse Osmosis

Diffusion of solvent through a semipermeable membrane from a

concentrated side to dilute side due to external pressure is called
reverse osmosis

Osmosis

Sea water Soft Water

Solvent< Solute Solvent > Solute
concentration

Reverse Osmosis

01/03/2025 22
 Apparatus for RO
Direction of Osmosis

Direction of Reverse Osmosis

Salt Water
Pure water

H2O Na+ Cl-

Piston H2O
H2O Na+ Cl-
H2O H2O
Na+ Cl- Na+ Cl-
H2O
H2O H2O
H2O
Na+ Cl-

Semi permeable
membrane

Figure: Purification of water by RO Method

Pure H2O
01/03/2025 23
© S. Arockiasamy, VITC
 Reverse osmosis can reduce:
Semipermeable membranes
 Arsenic are fragile:
 Asbestos
 Fluoride Hard water can clog membrane
 Herbicides Chlorine can destroy membrane
 Lead Membrane must be rinsed
 Mercury regularly to prevent scaling
 Nitrate Prefiltration usually required
 Pesticides
 Radium
 Salt
 Colloidal silica

01/03/2025 24
Fuels – solid , liquid, Gas

Definitions
Fuel - Combustible substance (may be solid, liquid of gas) having carbon as
major constituent gives energy while burning.

Reacts with oxygen leading to the formation of the product with the evolution
of heat at a rapid rate.

Fuel + O2 Products + Heat

The energy content of the products is less than the reactants and the excess
energy is liberated as heat energy.

25
Characteristics of a good fuel

 It should have higher calorific value.

 Moderate ignition temperature.
 High suitability.
 Low combustion matter content
 A good fuel should burn with moderate rate of
combustion.

26
Classification of fuels

27
Calorific value of fuels

The calorific value of a fuel can be defined as

"the total quantity of heat liberated when a unit mass (or) volume of the fuel is
burnt completely".

Units of Calorific Value

1. Calorie - Calorie is the amount of heat required to raise the temperature

of one gram of water through one degree centigrade.

2. Kilocalorie (or) kilogram centigrade unit - This is the unit of metric

system and is equal to 1000 calories.

This may be defined as "the quantity of heat required to raise the

temperature of one kilogram of water through one degree centigrade".
Thus 1 kcal = 1000 cal.
28
Units of Calorific Value

3. British thermal unit (B. Th. U.) - This is defined as "the quantity of heat
required to raise the temperature of one pound of water through one
degree Fahrenheit". This is English system unit.
1 B. Th. U. = 252 cal = 0.252 k cal.
1 k cal = 3.968 B. Th. U.

4. Centigrade Heat Unit (C. H. U.) - This is the "quantity of heat required
to raise the temperature of one pound of water through one degree
centigrade".
Thus, 1 k cal = 3.968 B. Th. U. = 2.2 C. H. U.

29
Units in brief
Amount of heat required to raise the temp. of
Calorie : 1g of water through 1oC

Kilocalories : 1Kg of water through 1oC

British Thermal
Unit (B. Th. U) : 1pound of water through 1oF

Centigrade
Thermal Unit (C.T.U) : 1pound of water through 1oC

30
GCV/HCV– Gross / Higher calorific value
• “Amount of heat produced, when unit mass/volume of the fuel is burnt
completely and the products of combustion have been cooled to room
temperature”.

• If the products of combustion are condensed to room temp., the latent heat of
condensation of steam also gets included in the measured heat. Hence higher (or)
gross calorific value
NCV/LCV : Net/Lower Calorific Value

“Amount of heat produced, when unit mass/volume of the fuel is burnt

completely and the products of combustion have been allowed to escape”.
In practice, water vapor are not condensed but allowed to escape. Hence lesser
amount of heat is available.
LCV = HCV – Latent heat of water vapor produced
= HCV – (Mass of hydrogen x 9 x Latent heat of steam)
31
Determination of Calorific Value by Bomb calorimeter

1. Principle 2. Construction
When 1g of a Beckmann’s
solid fuel is thermometer Oxygen
burnt completely valve
in presence of Electrically
air, the heat
operated stirrer
liberated is Electrodes to
measured using which Mg
stainless steel wire is
bomb. Copper
attached
calorimeter

Mg fuse wire Stainless

steel bomb
Weighed pellet Stainless steel
of a fuel sample crucible

3. Working
32
4. Calculation

m = mass of fuel pellet (g)

W = mass of water in the calorimeter (g)
w = water equivalent of calorimeter (g)
t1 = initial temperature of calorimeter
t2 = final temperature of calorimeter
HCV = gross calorific value of fuel.

33
5. Corrections

Fuse wire correction :

Heat liberated during sparking should be subtracted from the total heat obtained.

Acid correction :
Fuels containing Sulphur and Nitrogen if oxidized, the heats of formation of H 2SO4 and HNO3 should
be subtracted (as the acid formations are exothermic reactions).

Cooling correction:
The rate of cooling of the calorimeter from maximum temperature to room temperature is noted.
From this rate of cooling (i.e., dt°/min) and the actual time taken for cooling (t min) then correction (dt × t) is
called cooling correction and is added to the (t2 . t1) term.

34
Equation after Corrections

Specific heat capacity of water = 4.184 J/g. 35

 Calculation of calorific value- problems

1. Problem : When 1g of a fuel on complete combustion in slight excess of oxygen, increased

the temperature of the water in a calorimeter containing 1Kg of water to 3oC (t2-t1). Calculate
the HCV of the fuel. The water equivalent of the calorimeter is 120g.

36
2. Problem : When 2g of a pre-analyzed sample containing 92%C, 5%H and 3% ash is burnt in
a bomb calorimeter containing 700g of water the following results are obtained
Rise in temperature = 2.5oC; The water equivalent = 1000g
Cooling correction = 0.04oC
Fuse wire correction = 10 cal
Acid correction = 50 cal.
Calculate the HCV and LCV?

HCV = (W+w)(T2-T1 + cooling correction) – (Acid +Fuse wire correction)

cal/g
m

LCV
KNOCKING

Knocking !!!
Knocking !!!

Noise !!!

38
Knocking
• It is a kind of explosion due to rapid rise of pressure in an internal combustion (IC)
engine.
• Gasoline and air (1:17) mixture is compressed and ignited by a spark where
oxidation of HC takes place.
• Products of oxidation drives the piston down in cylinder, if combustion is uniform and
regular.
• Sudden oxidation takes place and mixture detonates resulting an explosive sound
called knocking which leads to loss of power.
• Compression ratio = Gaseous vol. in the cylinder at the end of suction stroke / volume
at the end of compression stroke
• Compression ratio depends on the nature of constituents of the fuel. Efficiency of IC
engine increases with compression ratio

39
Knocking Exhaust

Spark
Fuel + Air

V2
V1

Compression Ratio (CR)= (V1/V2) ~ 1

V1 = Gaseous vol. in the cylinder at the end of suction stroke
V2 = Volume at the end of compression stroke

40
 Exhaust

Spark
Exhaust Fuel + Air

Spark
Fuel + Air

V2
V2
V1 V2’
V1

SUCTION
COMPRESSION

Compression Ratio (CR)= (V1/V2) ~ 1

V1 = Gaseous vol. in the cylinder at the end of suction stroke
V2 = Volume at the end of compression stroke

41
Knocking effect !!!

42
• Knocking tendency depends on the chemical structure of fuel, which decreases
in the following order.
• Straight chain paraffins > Branched chain paraffins > Cycloparaffins >
Olefins > Aromatics
• Knocking results in loss of efficiency of the engine
• Knocking characteristics of a combustion engine fuel (petrol) – octane number
• Antiknock quality of a fuel is expressed as octane number

B.P C-atoms Uses

Uncondensed gases < 30oC C1-C4 LPG fuels
Gasoline/Petrol 40-120 C5-C9 Fuel for IC engines
Naptha/S.Spirit 120-180 C9-C10 Solvent in paints
Kerosene oil 180-250 C10-C16 Fuel for stove & jet
Diesel oil 250-320 C15-C18 Diesel engine fuels
Heavy oil 320-400 C17-C30 Fuels for ships
43
Fuel Additives to Reduce Knocking

Chemical additives are used to raise the octane number of gasoline. Low exposure to lead : Subtle
and insidious neurotoxic
The most effective antiknock agents are lead alkyls; effects such as Low IQ and
(i) Tetraethyl lead (TEL), (C2H5)4Pb was introduced in 1923 antisocial behavior
(ii) Tetramethyl lead (TML), (CH3)4Pb was introduced in 1960

In 1959 a manganese antiknock compound known as

Methylcyclopentadienyl manganese tricarbonyl (MMT) was introduced to
supplement TEL (used in Canada since 1978).

About 1970 low-lead and unleaded gasoline were introduced over toxicological concerns with lead
alkyls (TEL contains 64% by weight lead).

Alcohols such as ethanol and methanol have high knock resistance.

Since 1970 another alcohol methyl tertiary butyl ether (MTBE) has been
added to gasoline to increase octane number.

44
Octane number

It is defined as the % of isooctane in a mixture of n-heptane and isooctane which has the same
knocking characteristics of the petrol under the same set of conditions.

Isooctane – best antiknocking properties

and assigned O.N of 100

n-heptane – poor antiknocking property and assigned O.N. of 0

CH3-CH2-CH2-CH2-CH2-CH2-CH3  n-heptane (O.N = 0)

Most effective antiknock agent is tetraethyl lead (TEL) along

with ethylene dibromide which prevents deposition of lead by forming volatile lead halides
Others are tetramethyl lead, tertiary butyl acetate, diethyl telluride
Greater the octane number, greater is the resistance of knocking 45
 Diesel knock
• Long ignition delay leads to accumulation of more vapors in the engine and
when ignited an explosion results as the combined effect of temperature and
pressure. This is responsible for diesel knock.
• Diesel knock can be reduced by the addition of pre-ignition dopes such as ethyl
nitrite, iso-amyl nitrate and acetone peroxide
Cetane number
• There is a delay period between the injection of diesel fuel and its ignition. If this delay period is
large, too much fuel accumulates in the cylinder and burn very rapidly and causes diesel knock.
• Increasing delay period occurs in the series : CH3-(CH2)14-CH3
n-hexadecane (C.N = 100)
n-paraffin < Olefins < naphthenes < isoparaffins < aromatics
CH3
Order is the reverse for gasoline antiknock quality.
• n-hexadecane ; Cetane number = 100 2-methyl naphthalene
(C.N. = 0)
• α – methyl naphthalene ; Cetane number = 0
• A given fuel matches in quality with the blend having 40/60 blend of cetane and methyl naphthalene, it is
assigned a cetane number 40
• Cetane number of diesel can be improved by adding pre-ignition dopes such as amyl/butyl nitrite,
carbamates, ditertiary butyl peroxide and metal organic compounds. 46
corrosion
Objectives
1. What is corrosion – Definition
2. Why most of the metals undergoes corrosion but not Au, Ag
and Pt
3. What is the need for learning corrosion- Link to Water
chemistry
4. Types or Broad classification of Corrosion

Chemical (or) Dry Electrochemical (or) Wet

corrosion Corrosion

47
arket watch on Corrosion
Definition
Corrosion is defined as the gradual destruction or deterioration of metals or alloys by the
chemical or electrochemical reaction with its environment.

Consequences of Corrosion
1. Due to formation of corrosion product over the machinery, the efficiency of the machine gets
lost.
2. The products are contaminated due to corrosion.
3. The corroded equipment must be replaced frequently.
4. Plant failure due to corrosion.
5. Corrosion releases toxic products, health hazard, etc.
Stress corrosion cracking - pictures

> If the tensile stress is more than or equal to yield

stress crack occurs on the surface a metal

Examples :
1. steel undergoes caustic embrittlement in caustic
solution

De-stress

50
 Factors Affecting the rate of corrosion

Nature of the metal Nature of the environment

1. Position of the metal in EMF series 1. Temperature

2. Purity of the metal 2. Humidity
3. Relative area of Anode and Cathode 3. pH of the corrosive medium
4. Physical state (Stress) on the metal
5. Solubility of corrosion product
6. Nature of the metal oxide (corrosion
product) formed

51
Control of corrosion

1. Materials selection
2. Alteration of the Environment
3. Proper Design of articles – Avoid Crevice
and sharp bends
4. Cathodic protection methods:
a) Sacrificial Anodic Protection
b) Impressed Current Cathodic
Protection method
5. Corrosion Inhibitors:
a) Anodic inhibitors
b) Cathodic inhibitors
c) Vapour phase inhibitors
6. Metallic coating:

a) Electroplating and electro-less plating

b) Physical vapour deposition
c) Chemical vapour deposition

52
Cathodic Protection methods

1. The principle involved in cathodic protection is to force the

metal to be protected to behave like a cathode.
2. Since, there will not be any anodic area on the metal,
corrosion does not occur.

There are two types of cathodic protection

(a) Sacrificial anodic protection method
(b) Impressed current cathodic protection method.
a) SACRIFICIAL ANODIC PROTECTION METHOD

In this method, the metallic structure to be protected is made cathode

by connecting it with more active metal (anodic metal).
So that all the corrosion will concentrate only on the active metal
The artificially made anode thus gradually gets corroded protecting
the original metallic structure
Hence this process is otherwise known as sacrificial anodic protection.

e- Flow

Fe Zn

Underground pipeline Sacrificial anode

Examples of sacrificial anode:
• This method is used for the protection of ships and boats.
• Sheets of zinc and magnesium are hung around the hull of the ship
• Zinc and magnesium being anodic to iron get corroded.
• Since they are sacrificed in the process of saving iron (anode), they are called sacrificial anodes

Insulated copper wire

Sacrificial Zn or Applications of Sacrificial Anode

Ship hull Mg
• Protection of underground pipelines and cables from soil
corrosion.
• Magnesium rods are inserted in to domestic water boilers or
tanks to prevent the formation of rusty water.
• Calcium metal slag's are employed to minimize engine corrosion.
b) IMPRESSED CURRENT CATHODIC PROTECTION

1. In this method, an impressed current is applied in the opposite direction to nullify the
corrosion current and convert the corroding metal from anode to cathode
2. This can be done by connecting negative terminal of the battery to the metallic
structure to be protected
3. Positive terminal of battery is connected to an inert anode. Inert anode used for this
purpose is graphite (or) platinised titanium

4. The anode is surrounded by ‘backfill’ (containing mixture of gypsum, coke,

- + breeze, sodium sulphate) to improve the electrical contact between the
Cathode
DC
Anode
anode and the surrounding soil.

APPLICATION OF IMPRESSED CURRENT PROTECTION

This type of cathodic protection is applied to

open water-box coolers,

Back
fill water tanks,

Underground Graphite buried oil and water pipes,

pipeline anode
condensers,

marine piers,

Transmission line towers, etc.,

Comparison of sacrificial anode and impressed current cathodic method

Sacrificial anodic method Impressed current method

 No external power supply is  External power supply must be

necessary present
 This method requires periodical  Here anodes are stable and do

replacement of sacrificial anode not disintegrate

 Investment is low  Investment is more

 Soil corrosion effects are not  Soil corrosion effects are taken

taken in to account in to account

 This is most economical method  This method is well suited for

especially when short-term large structures and long term

protection is required. operations
Protective coatings/Metallic coatings

58
 Protective coatings

Thick film coating Thin film coating

methods methods
Electroplating Physical &
Galvanising Chemical vapour
Tinning deposition.

Metal cladding –
Definition, Process and
applications

59
Sample (or) substrate Preparation

> Mechanical cleaning :– To remove loose scale and rust,

using hammer, wire-brushing, grinding and polishing.
> Sandblasting :– To clean large surface areas in order to
produce enough roughness for good adherence of
protective coating, using sand with air stream at 25-100
atm.
> Solvent Cleaning :– To remove oil, grease, rust using organic
solvents like alcohol, xylene, toluene, hydrocarbons
followed by cleaning hot water or steam.

60
Sample Preparation (contd..)

Alkali Cleaning : To remove old paints that are soluble in

alkaline medium using chemicals like NaOH, Na3PO4 etc. After
cleaning, the metal is washed with 1% chromic acid solution.

Acid pickling and etching: Base metal is dipped inside acid

solution at a higher tempt for a long duration. Acids used are
HCl, H2SO4, H3PO4, HNO3, under dilute conditions.

Piranha (H2SO4 + H2O2)

61
Metallic coatings

Anodic coating – Galvanization:

It is produced by anodic coating metals (Zn, Al, Cd) on the
surface of base metal (Fe) based on the relative negative
electrode potential.

Crac
k
Zn
Eoznfilm
=-
Steel (or) Fe EoFe = - 0.76V
0.44V

62
Cathodic coating:
It is produced by cathodic coating metals (Sn, Cr, Ni) on Fe surface
based on the relative positive electrode potential of coat metal.

Crac
k
Sn
film
E Sn = -
o

Steel (or) Fe EoFe = - 0.14V

0.44V

63
Methods of application of thick metallic coating

(A) Galvanizing
1. Hot dipping
(B) Tinning
2. Metal cladding
3. Electroplating – Cu, Ni, Au, Ag
4. Cementation
5. Vacuum metalizing
6. Metal spraying 1. Hot Dipping

> It is one of the common method of applying metallic coating

on the surface of base metals.
> Hot dipping is a process of coating the base metal by
immersing it in the molten liquid of the metal to be coated.
Examples: Galvanizing and Tinning
64
(A) Galvanizing
Fe or steel is coated with a thin coat of Zn by immersing in molten Zn to prevent
rusting.

1. Fe or steel base metal is cleaned by acid pickling using dil. H2SO4 (60-900C) for
15-20 min.

2. Base metal dipped in molten Zn (4300C) and then passed through rollers to
correct the thickness of the film.
3. NH4Cl flux used to protect the surface of molten Zn from oxide formation.
4. Annealed at 250 0C and cooled slowly
5. Coating of Iron pipes, screws, bolts, wires, etc.

6. Poisonous for utensils that store food stuffs

65
Galvanization process
Galvanised steel structure

NH4Cl flux to
avoid ZnO
formation

Hot air Galvanized

Steel sheet Steel
Pair of Hot Sheet
rollers

Annealing
chamber
250oC

Hot air

Washing Molten Zn at Excess Zn

Dil. H2SO4 at Collector
bath 425 – 430oC
60 – 90oC

m.p of Zn = 419oC
66
(B) Tinning:
In this process tin is coated over mild steel sheets immersed in molten tin
(Sn).

• The sheet is subject to acid pickling and passed through a bath of molten tin
covered with a metallurgical flux of ZnCl2 , which forms ZnOCl2 and clean the
surface of the base metal.

• After coating, the sheet is passed through palm oil to protect from oxidation
• Finally the sheet is passed to roller to get uniform thickness.

• It is used for the coating of steel, Cu and brass sheets that store food stuffs.

67
Process of Tinning

ZnCl2 flux
to avoid Tinned
SnO Steel
Steel formation Sheet
sheet

Hot
rollers

Dil. H2SO4
at 60 – Palm
90oC Molten Sn
oil
Acid
Pickling m.p of Sn =
232oC 68
Thin-Film Coatings
• PVD Coating (Physical Vapor Deposition)
• CVD Coating (Chemical Vapor Deposition)

lead frame gold wire

bonding pad

chips connecting pin 69

Deposition techniques

70
Physical vapour
deposition

In PVD, materials are first evaporated and then condensed to form a solid material on the target at
higher temperatures.

The primary PVD methods include

1. Thermal evaporation,
2. Sputtering – ion plating and ion beam implantation
3. Arc vapour deposition

Deposition
process
1. Clean the substrate or object to be coated with solvent and acid pickling then
dry the substrate by hot air blower
2. Clean the chamber, load the substrate in to the PVD chamber at the substrate
holder also place the source metal to be coated inside the chamber
3. Pass H2 if required in order to provide reducing atmosphere
4. Heat the source metal (beyond melting point), sublimed vapour condensed on
the substrate surface which is kept at room temperature 71
3 major types Physical vapour
deposition
1. Thermal Evaporation
There are two types of thermal evaporation: pulsed laser deposition and electron beam deposition. Both processes use
energy to evaporate a metal material (such as Titanium, Zirconium, Chromium, Aluminum, or Copper) into a vacuum. The
vacuum then allows vapor articles to travel to the relatively cooler production parts where it will once again condense and
crystallize into a thin, hardened, metal state. This PVD type is most commonly used in computer industry microfabrication or
for products such as film packaging.
2. Sputter Deposition
Two types of sputter deposition are currently used in manufacturing applications: ion beam sputtering and magnetron
sputtering. In the former, an ion beam directs a high electric field toward the surface of the material to be vaporized. This causes
the metal vapor gases to ionize after which momentum transfer directs those ions toward the target production part. In
magnetron sputtering, positively charged ions are accelerated by an electrical field and then superimposed onto the target
parts. This process is commonly used in the medical industry for manufacturing lab products and optical films.
3. Arc Vapor Deposition
This process uses a low-voltage arc to evaporate metal source material into vaporized metal particles. These evaporated metal
atoms combine with reactive gas molecules in a plasma state that once again condense on relatively cooler production parts in
close proximity. Production parts spin on a multi-axis rack carousel to produce an evenly distributed lifetime coating in colors
that include hues of black, bronze, gold, graphite, nickel, blue, purple, and “rainbow” combinations of more than one color.

Low Temperature Arc Vapour Deposition is a favorite form of PVD coating because it is the most environmentally friendly
method, and it results in a very thin (0.25 to 4.0 microns) hard metallic coating that is available in a wide variety of colors. PVD
finish has a transparent quality that allows underlying chrome or polish to shine through. Matte and brushed metal finishes
also receive PVD to lock in these desired physical appearances for a lifetime of corrosion, chemical, and scratch resistance. PVD
can also be used on lower-cost or lighter weight base materials (including plastic and aluminum) and provide superior aesthetic
looks, abrasion, and corrosion resistance.
Deposition of thin film by Physical Vapour Deposition
(PVD)

PVD Chamber

Substrate
TiN film
N2
View Port

Heater

Suction valve
H2 = 50 sccm (provides N2 Ti Metal
reducing atmosphere) (and) source 2000oC
N2 = 15 sccm
H2
To vacuum pump

01/03/2025 09:45 AM
Nanotechnology
73 73
Chemical Vapour deposition
process
CVD is a technique in which a stable thin film (<1000nm) is formed on by the
chemical reaction of a reactant gas (or) a vapourised chemical compound on the
surface of a heated substrate in a chamber.
The reactive/complex molecule in the vapour state impinges on the hot substrate,
decomposes and forms a thin film. These reactions are promoted by resistance, RF
or infrared radiation heating

150C
Ni(CO)4 Ni + 4CO

Requirements for a CVD process

1. Vacumised chamber (10-3 mbar) connected to a rotary pump
2. Complex chamber with heating facility
3. Vapour transport SS tubes ( quarter inch)
4. Substrate holder inside the chamber withy heater (flat heater – 900 oC)
5. High Temperature valve to control the flow rate of complex vapour

74
ION IMPLANTATION - A PVD TECHNIQUE

Ion implantation is a materials engineering process by which

ions of a material can be implanted into another solid
(substrate), thereby changing the physical properties of the
solid (substrate).

Effect of ion Implantation on the target

The ions introduce both a chemical change in the target, in that they can be a different element than
the target

Induce a nuclear transmutation and a structural change, in that the crystal structure of the target can
be damaged or even destroyed by the energetic collision cascades.

75
Block
Diagram Two key parameters control the implant
profile

Energies of 1 – 10 keV is
used to penetrate only
few nanometers of the
surface and goes up to Accelerato
MeV to shallow junctions r-
Accelerate
d in an
electric
field
Magnets- select only
the species of interest
Ion
source-
Ionize the
substrat
atom= I *
Dose t/ qi *A e

Target
chambe
Example: 1µA to 30mA current is
r used then the dose will be 1011 to
1016 atoms/cm2 76
Applications/Advantages

1. Semiconductor device fabrication – doping od P, As and B

2. In metal finishing, as well as various applications in materials
science research to modify the surface- Drill bit.
3. The number of ions to be implanated on the surface of the
substrate can be controlled accurately

77
Chemical sensors for environmental monitoring - gas sensors
Chemical sensors are those devices that detect and convert chemical information (such as concentration, pressure,
activity of particles) into an electrical signal to obtain qualitative or quantitative time- and spatial-resolved information
about specific chemical components.
Global chemical
sensors market
was valued
at US$ 18.87 bn
in 2018 and is
anticipated to
reach US$ 29.27
bn by
2027. Analysts
predict that the
global market
will expand at a
CAGR of 5.0%
from 2019 to
2027.
Classification of Chemical Sensors

There are two main types of chemical sensors:

photochemical and electrochemical.
The former rely on changes in light or color properties
such as fluorescence or luminescence. Photochemical
sensors are commonly used for colorimetric assays such
as pregnancy strip tests or enzyme-linked immunosorbent
assays (ELISAs). Photochemical detection requires
equipment to measure the color change at the end point,
which can limit its use in wearable devices for self-
monitoring. However, there is increasing attention being
paid to the development of smartphones as a platform to
measure color from photochemical reactions

Electrochemical sensors function as both the receptor and

the transducer, thus facilitating continuous monitoring. The
signal from electrochemical sensors takes the form of
electrical outputs arising from chemical reactions: for
instance, differences in hydrogen ion activity can be
transduced into electrical potential (potentiometry), current
(amperometry), conductivity (conductometry), resistance
(resistometry), or voltage (volammetry)
Classification of Chemical Sensors
• Chemical sensors are measurement
devices that convert a chemical or physical
property of a specific analyte into a
measurable signal, whose magnitude is
normally proportional to the concentration
of the analyte.
• A chemical sensor typically contains two
main components: a receptor and a
transducer. The receptor transforms
chemical information about a sample into
a form of energy. The transducer then
transforms the energy into some form of
analytical signal.
• The chemical sensor is an analyser that
responds to a particular analyte in a
selective and reversible way and
transforms input chemical quantity,
ranging from the concentration of a
specific sample component to a total
composition analysis, into an analytically
electrical signal.
How it works?

•Different Types of Sensors

• Temperature Sensor
• Proximity Sensors
• Infrared Sensor (IR Sensor)
• Ultrasonic Sensor
• Light Sensor
• Smoke and Gas Sensors
• Alcohol Sensor
• Touch Sensor
• Color Sensor
• Humidity Sensor
• Tilt Sensor
Gas sensors

▪ Gas sensor is a subclass of chemical sensors.

▪ Gas sensor measures the concentration of gas in its vicinity.
▪ Gas sensor interacts with a gas to measure its concentration.
▪ Each gas has a unique breakdown voltage i.e. the electric field at which it is ionized.
Sensor identifies gases by measuring these voltages.
▪ The concentration of the gas can be determined by measuring the current discharge in
the device.
▪ Types of gas sensors:
▪ Electrochemical gas sensor
▪ Contact combustion gas sensor
▪ Optical gas sensor
▪ Polymer gas sensor
▪ Semiconductor gas sensor

https://www.figaro.co.jp/en/movie/
IR absorption type CO2 gas sensor

▪ CO2 absorbs infrared light therefore CO2 sensor consists of a tube containing an infrared source at
one end and an infrared detector at the other end.
▪ The infrared detector detects the infrared light which is not absorbed by CO2 between source and
detector.
▪ Infrared radiation which is not being absorbed by CO2 produces heat so the temperature will
increase.
▪ The infrared detector measures the temperature.
▪ A voltage is produced due to the temperature increase in the infrared sensor.
▪ We can read amplified voltage into the data logger.
 Solid electrolyte-type CO2 sensors
• Low-cost, high-sensitivity, high-selectivity and simple-element structure.
• NASICON is the active element. Formula Na1+xZr2SixP3-xO12 (1.8 < x < 2.4)
• A commercial NASICON with a nominal-composition is Na3Zr2Si2PO12
• Binary carbonate systems such as Na2CO3-BaCO3, Na2CO3-CaCO3, Li2CO3-BaCO3, and Li2CO3-CaCO3
are also used as active elements (as auxiliary constituents).
• The NASICON layer was screen-printed with a paste on the alumina substrate. The Pt electrodes
were also screen-printed on the designated regions before and after the deposition of the
NASICON layer.
• The assembly was sintered at 900°C, 1000°C, and 1100°C for 4 hours in air, respectively. After this,
a series of auxiliary phases (Na2CO3-CaCO3) was screen-printed on the Pt sensing electrode.
• The EMF response to CO2 content as a function of the CO2 concentration is calculated. Greater the
CO2 concentration greater the EMF recorded.
Hydrogen gas sensor

▪ Mostly palladium is used to detect hydrogen because palladium selectively

absorbs hydrogen gas and forms the chemical palladium hydride.
▪ Types of hydrogen gas sensor:
▪ Electrochemical
▪ Thin film sensor
▪ Thick film sensor
▪ Chemochromic hydrogen sensors
▪ Diode based Schottky sensor
▪ Optical fiber hydrogen sensors
▪ Nanoparticle-based hydrogen microsensors
NOx gas sensor – Metal oxide type

• WO3 is known as the most promising NOx gas-sensing material

• Other materials: ZnO, SnO2, In2O3, TiO2, etc.
• These sensing materials are oxygen-deficient nonstoichiometric compounds
• The conductivity of these n-type semiconductors, such as WO3 and In2O3, is estimated based on the
electron created by the surplus metal.
• When sensing materials are exposed to oxidizing gases at temperature ranging from 200ºC to 300ºC,
the concentration of electrons is decreased due to the reaction between the electron and the gas.
• Consequently, the conductivity decreases and the resistance increases.
• As NOx is also an oxidizing gas, the concentration of electrons is decreased due to the reaction
between the electrons in the sensing materials and NOx gas, as shown in the following equations:
Carbon monoxide gas sensor

• CO is a colourless, tasteless and odourless gas produced by incomplete combustion of

carbon-containing materials. It is often referred to as the "silent killer" because it is
virtually undetectable by humans.
• Types of CO sensors:

▪ Semiconductor sensor
▪ Electrochemical sensor
▪ Biomimetic type
▪ Opto-chemical type (Widely used)
Opto-chemical type CO sensor

• The detector consists of a pad of a coloured chemical which changes colour upon reaction with carbon monoxide.
They only provide a qualitative warning of the gas however. The main advantage of these detectors is that they are
the lowest cost, but the downside is that they also offer the lowest level of protection.
• One reaction used for carbon monoxide detection is potassium disulphitopalladate (II) catalytic oxidation.

CO + K2Pd(SO3)2 ⟶ Pd + CO2 + SO2 + K2SO3

• As reaction progresses, atomic palladium release causes the color to change from yellow to brown to black.
Biomimetic and electrochemical type CO sensor
• A biomimetic sensor works in a fashion similar to haemoglobin which darkens in the presence of CO proportional to
the amount of carbon monoxide in the surrounding environment.
• It uses cyclodextrins, a chromophore, and a number of metal salts. This can either be seen directly or connected to an
infrared source of photons such as an IR LED and then monitored using a photodiode.
• The electrochemical detector uses the principle of a fuel cell to generate an electrical current when the gas to be
detected undergoes a chemical reaction.
• The generated current is precisely related to the amount of carbon monoxide in the immediate environment close to
the sensor.
• Essentially, the electrochemical cell consists of a container, two electrodes, connection wires and an electrolyte,
typically sulfuric acid. Carbon monoxide is oxidized at one electrode to carbon dioxide while oxygen is consumed at the
other electrode.
• Advantages of electrochemical cell over other technologies: highly accurate and linear output to carbon monoxide
concentration, requires minimal power as it is operated at room temperature, and has a long lifetime.