For Sake of Reading

Control of Corrosion
Corrosion can be controlled by:
a) Proper designing
b) Use of pure metals, alloys
c) Cathodic protection
d) Changing the environment
e) Use of inhibitors
f) Application of protective coatings
Prof. Dr. F. Nawaz Khan, VIT

UNIVERSITY 52
Corrosion control
a. Proper designing:
o Proper selection of metal or alloy or design will play an important
part in corrosion control.
o To the extent possible, contact of dissimilar metals far apart from

each other in the electrochemical series should be avoided.
o Metals which are close in potentials in the electrochemical series are

preferable.
o While working with dissimilar metals, larger anodic area and lesser
cathodic area are necessary to minimize corrosion.
o Insulating materials (washers, spacers) can be used when two

dissimilar metals have to be put together in a fabrication.
o When two dissimilar metals are together, painting or electroplating

the anodic metal will help in reducing corrosion.
o Sharp corners and edges should be avoided in a fabrication since

these act as anodes getProf.
more easily corroded.
Dr. F. Nawaz Khan, VIT
UNIVERSITY 53
Corrosion control
Weld Sharp corner Smooth bend

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

Weld joints
Poor design – more corrosion Better design – lesscorrosion
Weld joint
Best designs
Prof. Dr. F.–Nawaz
leastKhan,
corrosion
VIT
UNIVERSITY 54
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Corrosion control
b. Use of pure metal:
o Impurity in the metal can create anodic and cathodic parts and
hence leads to electrochemical corrosion.
o Metals like Mg, Al when used in the purest form become corrosion
resistant by impervious oxide film formation.
o But 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:

o Alloying is a very good method for corrosion protection.
o Alloying metals like Fe, Cu etc. with noble metals makes the metal
passive and reduces corrosion.
o Eg. Addition of Cr, Ni etc. to iron as alloying metals will give
corrosion resistance. (stainless steel)
UNIVERSITY 58
Corrosion control
d. Cathodic protection:
o Principle is to make the base metal to be protected as
cathode by connecting to a highly anodic metallic plate.
o Two methods of cathodic protection are known:
i) Sacrificial anodic protection
ii) Impressed current cathodic protection
i) Sacrificial anodic protection:

o The metallic structure to be protected is connected through a
metal wire to a more anodic metal.
o This will induce corrosion at the anodic metal.
o Thus the more anodic metal sacrifices itself and gets corroded
protecting the metallic structure.
o Sacrificial anodes known are Zn, Mg, Al and their alloys.
o Applications are: protection of underground pipelines, ship hulls
and other marine devices, water tanks.
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Sacrificial anodic protection
Sacrificial anodic protection - concept
e-
Mg
Mg2+

UNIVERSITY 60
Cathodic Protection - Preventing Corrosion
To protect underground
pipelines, a sacrificial
anode is added.
The water pipe is turned

into the cathode and an
active metal is used as the
sacrificial anode.
Magnesium is used as the

sacrificial anode, since it is
more easily
oxidized than the
iron water pipe.

UNIVERSITY 61
Corrosion control
Insulated
Insulated copper
copper wire
wire
Sacrificial zinc
Soil
Sacrificial
anode
Mg
Underground Sacrificial Zn or Mg
Pipeline (Cathode) Ship hull rod
Sacrificial
Prof. Dr. F.anodic protection
Nawaz Khan, VIT
Hot water tank
UNIVERSITY 62
Zinc is attached to the steel hull of the vessel

UNIVERSITY 63
Aluminium anodes mounted on a steel jacket
structure – using galvanic corrosion for
corrosion control! Called cathodic protection
(aka sacrificial anode)
UNIVERSITY 64
 Use of sacrificial anodes – Zinc, lead, etc.
 Used on small structures
 Anodes welded or bolted to fixtures
 Need regular checks for wastage
 Recently aluminium oxides have become more popular due to
better performance to weightUNIVERSITY 65
Sacrificial Anodes
This field is located in Viosca Knoll, block 786, southeast of New Orleans. It lies in
water depths of approximately 1754 feet (535 meters). Petronius is the largest free-
standing structure in the world. Texaco's choice was Galvotec-CW-III Aluminum
Sacrificial Anodes for their Petronius cathodic protection
system. http://www.galvotec.com/img/texaco.jpg
UNIVERSITY 66 66
Corrosion control
ii) Impressed current cathodic protection:
o Impressed direct current is applied in the opposite direction to the

corrosion current to nullify it.
o 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.
o The other terminal is connected to the metallic structure to be

protected.
o Since the current is impressed on the metallic structure, it acts as

cathode and thus gets protected.
o This method is usually used to protect underground water pipe

lines, oil pipe lines, transmission lines, ships etc.
UNIVERSITY 67
Impressed current cathodic protection
Impressed current cathodic protection - concept
e-

UNIVERSITY 68
Corrosion control
Graphite anode + Source for
_
impressed DC
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Soil
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
_
::::::::::: Insulated
:::::
::::::::::: copper wire
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
+
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Buried
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Pipe
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Made
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
Cathodic
(protected)
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
:::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::
ImpressedProf.
current cathodic protection
Dr. F. Nawaz Khan, VIT
UNIVERSITY 69
Mg
Magnesium Anode
Impressed current
Early anodes made from scrap steel but most modern ICCP
systems use lead silver alloy, titanium or niobium

UNIVERSITY 70
f. Corrosion inhibitors
o Corrosion can be reduced by using corrosion inhibitor, which is a
substance when added in small quantities to the aqueous
corrosive environment, effectively decreases the corrosion of a
metal.
o Inhibitors are divided as anodic inhibitors and cathodic inhibitors.
o Anodic inhibitors are the substances which reduce the corrosion

occurring at anode by forming sparingly soluble salts with the
metal ions produced. Eg. tungstates, chromates, phosphates etc.
o Metal surface adsorbs metal ions to form a protective layer to

reduce the corrosion rate. Even though the corrosion control is
highly effective, local corrosion may occur in case of exposure of
even small area.

UNIVERSITY 71
o Cathodic inhibitors are mainly added to reduce the diffusion of

hydrated H+ ions to the cathode. The H+ ions formed are
combining to form hydrogen gas, which is evolved
2H+(aq) + 2e- → H2(g)
o The formation of H2 gas can be controlled by increasing the

overvoltage of hydrogen evolution.
o Organic inhibitors like amines, mercaptans, heterocyclic nitrogen

compounds, substituted urea, thioureas, heavy metal soaps
reduce the diffusion of H+ ion considerably.
o These inhibitors get adsorbed on the metal surfaces and form an

adherent film of metals at the cathodic area thereby increase the
hydrogen overvoltage considerably.

UNIVERSITY 72
o However, in neutral solution, the cathodic reaction is
H2O + ½ O2 + 2e- → 2OH-
o Hence, the corrosion can be controlled either by removing

oxygen from the corroding environment or by reducing its
diffusion to the cathodic areas.
o The oxygen can be eliminated by adding reducing agents

like Na2SO3 or by deaeration. The diffusion of oxide ion is
reduced by using inhibitors like Mg, Zn or Ni salts.
o These react with hydroxyl ions forming corresponding

insoluble hydroxides, which are deposited on the cathode
forming impermeable self barrier.

UNIVERSITY 73
Passivity
o Any metal exhibiting lower rate of corrosion than normal in a
certain environment is said to be passive.
o Fe, Cr, Ni, Ti and their alloys exhibit passive character.
o Eg. i) Iron dipped in conc. HNO3 becomes passive.

ii) Stainless steel immersed in conc. HNO3 (for one hour)
becomes passive.
o This passivity is attained because of the formation of a passive film

on the surface of the metal in the environment.
o Passivity is not a permanent property and depends on the

environmental conditions.

UNIVERSITY 74
Protective coatings
o Protective coating provide a physical barrier between the
metal and the environment .
o They not only give corrosion protection but also add to
the decorative value of the article.
o Coatings are broadly divided as:
a) Inorganic coatings : metallic and chemical conversion
coatings
b) Organic coatings : paints, varnishes, enamels, lacquers
o Protective coatings are classified as:

i) metallic coatings
ii) chemical conversion coatings
iii) organic coatings and linings
iv) ceramic protective coatings
UNIVERSITY 75
Protective coatings
o 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.
UNIVERSITY 76
Protective coatings
a) Mechanical cleaning:
o Useful for removing loose scales and rust.
o Hammering, wire brushing, grinding, blasting, polishing are the
methods commonly used.
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.
o This will produce enough roughness for good adherence of the
protective coating.
o 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.
o Hot water cleaning is followed after solvent cleaning is done.
UNIVERSITY 77
Protective coatings
d) Alkali cleaning:
o Cleaning of the base metal with sodium hydroxide, trisodium
phosphate, sodium silicate, 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.
e) Acid pickling and etching:

o Base metal is dipped inside the acid solution at higher
temperature for long periods of time.
o This treatment ensures cleaning of the base metal surface free
from all kinds of impurities including oils, greases, rust etc.,
o H2SO4, HCl, HF, H3PO4, HNO3 are the acids commonly used for
pickling and etching.

UNIVERSITY 78
Protective coatings
Metallic coatings:
a) Anodic coatings
b) Cathodic coatings
a) Anodic coatings:
o Anodic coatings are given on cathodic metals using metals which
are more anodic.
o Zinc, aluminium, cadmium coatings on iron are anodic coatings.
o If the coating breaks, then a galvanic couple is set up and
corrosion rate gets enhanced.
o During this process, the anodic coating gets disintegrated but it
protects the cathodic base metal.
o Hence, the anodic metal sacrifices itself to protect the base
metal.
o This type of coating is known as galvanisation.

UNIVERSITY 79
Anodic coating
Corroding environment  Iron can be protected
from corrosion by
Exposed part (cathode)
Zinc
coating it with zinc metal
Zinc coating
coating
flow of electrons
- a metal that will oxidize
Unexposed area first, instead of the iron
Steel
 Note that E°oxidation

of zinc is greater
than that of iron. Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 80
Protective coatings
Cathodic coatings:
o Cathodic coatings are given on anodic metals using metals which
are more cathodic.
o Coating of tin, chromium, nickel on iron surface are cathodic

coatings.
o If there is a discontinuity in the coating, then galvanic couple will

form with base metal as anode and the coated metal as cathode.
o Then the process of corrosion will start by the base metal ions
going into solution and the metal deteriorating.
o To avoid this, the article is checked and re-plated periodically so

that there is no discontinuity in the coating.

UNIVERSITY 81
Corroding environment
Cathodic coating
Exposed part (anode)
Tin Tin
coating coating
flow of electrons
Unexposed area
Steel

UNIVERSITY 82
Protective coatings
Methods of metallic coatings:
a) Hot dipping
b) Metal cladding
c) Electroplating
d) cementation
e) Vacuum metalizing
f) Metal spraying
a) Hot dipping:
Two types of hot dipping techniques are known.
i) Galvanizing: Dipping the base metal iron in molten zinc metal

solution.
i) Tinning : Dipping the base metal iron in molten tin metal
solution.
UNIVERSITY 83
Protective coatings
a) Hot dipping:
i) Hot dipping:
o Iron or steel part is dipped in molten zinc bath to get a thin coat of zinc.
o Before hot dipping, the steel or iron part is cleaned by acid pickling in dilute
H2SO4 at 60-90oC for 15-20 minutes.
o The base metal is then dipped in molten zinc bath maintained at 415-430oC
(M.P. of Zn is 419oC).
o The surface of zinc bath is covered with NH4Cl flux to prevent oxide formation.
o The coated part is then passed through a set of rollers to get the correct
thickness of coating and then annealed at 225oC and cooled slowly.
o Galvanizing is used for protecting iron in the form of sheets, wires, nails, bolts
and screws.
o Galvanised iron articles are not suitable for storing food items since some of
the zinc compounds are poisonous.
UNIVERSITY 84
Schematic diagram of hot dipping
Drying Ammonium Pairs of Galvanized

Iron chamber chloride flux hot rollers sheet
sheet
Hot air
Annealing
water chamber
Dil. H2SO4 Molten zinc Excess zinc

Washing removed
at 60-90oC at 425-430oC
bath
Galvanizing a sheet of iron

UNIVERSITY 85
Protective coatings
ii) Tinning:
o Tinning is s a process of coating tin over steel sheets, iron sheets
by dipping the sheets in molten tin bath.
o Before tinning, the sheets are pickled in dilute H2SO4 to remove
surface impurities.
o Tin bath is covered with a flux of ZnCl2 to prevent oxidation.
o After tinning, the sheet is passed through palm oil to protect the
tin coating from immediate oxidation.
o The sheets are passed through a set of rollers to achieve required
thickness of tinning.
o (Set up is similar to hot dipping.)

UNIVERSITY 86
Protective coatings
Rollers
Tin
plated
sheet
Acid pickling bath

Molten tin
Fig.: Tinning of sheet
Tank
87
corrosion.

UNIVERSITY
Electroplating
o It is a process by which a coating metal is deposited 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
c) chemical resistance
d) surface hardness
e) appearance
o Both ferrous and non-ferrous metals are plated with Ni, Cr, Cu, Zn,
Pb, Al, Ag, Au, Sn etc.
o Electroplating is mainly used in automobile, aircraft, refrigerator,
chemical and electrical appliances etc.
On non metals to increase the strength (wood, plastics, glass etc), for
decorative purposes, for surface conductivity
Electroplating

UNIVERSITY 89
Important Factors of electroplating
o Cleaning of the article is essential for strong adherence of
the electroplating:
- Scraping, grinding, sand blasting, wire brushing, solvent cleaning
and acid pickling are used for surface cleaning.
- A well cleaned and properly pre treated surface of any material to

be electroplated is necessary for obtaining the coating of long life.
o Concentration of the electrolyte is another important factor:
-Low concentration of metal ions will give uniform coherent

deposition.
-To maintain low conc. of metal ions, complexing agents are added
to the electrolyte. CN-, sulphamate, hydroxide
In plating Cu on Fe, CN- is added so that Cu2+ is complexed with CN-
to avoid Fe + Cu2+ giving Fe2+ and Cu
This also produces smooth and adherent deposit
UNIVERSITY 90
Important Factors of electroplating
o Thickness of the deposition should be optimised to get a
strong and adherent deposition:
- For corrosion protection multiple coatings are given to get

impervious coating without any discontinuity.
- For decorative purpose, thin coating is given.
 Current density
 - Current density is the current per unit area of the article being
plated (amps cm-2).
 - The C.D should be maintained at optimal level (low) to get
uniform and adherent deposition
At low current density diffusion is faster than the electron transfer so
smooth and uniform deposit
 Additives to electrolytic bath (Adherence)

- Additives to electrolyte are added in small quantities to get
strong adherent deposition.
- Commonly used additives Prof.are
Dr. F. gelatin,
Nawaz Khan,glue,
VIT glycine, boric acid
etc. and brighteners for bright plating.
UNIVERSITY 91
Choice of the electrolyte:
Good conductor, highly soluble, do not undergo hydrolysis,
oxidation, reduction, sufficient throwing power
Sometimes single, sometimes mixture of electrolytes
In copper plating, CuSO4 and H2SO4 is used
Brighteners Aromatic sulphonates or sulphones, and compounds

like thiourea, coumarin used to produce microscopic fine deposits
which reflect the light
Throwing power
Ability of the electrolytic cell to give a deposit of uniform thickness
over the entire cathode area, max throwing power attained when
cathode is regular shape, if irregular then agitating the solution to
minimize local electrolytic resistance
Electroplating
o pH of the bath:
- For a good electrodeposit, the pH of the bath must be properly
maintained (using buffers). For most plating baths, pH ranges
from 4 to 8.
pH lower than the optimum value means stronger hydrogen
evolutions, resulting in burnt deposit, at higher pH hydroxides
deposits
o Method of Electroplating:
- Method depends upon the type of metal to be electroplated, the

size and type of article to be electroplated.
- its main objectives and economics are also considered.

UNIVERSITY 93
Plating bath solution
o It is a highly conducting salt solution of the metal which is to be
plated.
o However, non-participating electrolytes are added to the bath

solution to increase the conductivity and the throwing power.
o The level of the plating bath should cover completely the cathode
and sufficient area of anode.
o Heating if required is provided by heating coils or hot gases.
o Air sparger or nitrogen sparger is employed to introduce convection

current in the plating bath solution.
o It should possess sufficient throwing power. Hence mixture of two

or more electrolytes is used for preparing electrolytic bath.
o It should be good conductor and highly soluble.
o It should not undergo hydrolysis, oxidation, reduction and other

chemical changes. Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 94
Physical vapor deposition (PVD)
 The physical vapor deposition technique is based on the
formation of vapor of the material to be deposited as a thin
film.
 The material in solid form is either heated until
evaporation (thermal evaporation) or sputtered by ions
(sputtering).
 In the last case, ions are generated by a plasma discharge
usually within an inert gas (argon).
 It is also possible to bombard the sample with an ion beam
from an external ion source.
 This allows to vary the energy and intensity of ions
reaching the target surface.
Physical Vapour Deposition
o This is a process of depositing some material by atom by atom or
molecule by molecule or ion by ion.
Applications:
1. This process is widely used to produce decorative coatings on plastic
parts those are resembling shiny metal.
2. Many automobile parts are plastic with a PVD coating of aluminium.
3. A lacquer coating is applied over the decorative coating to provide

corrosion protection.
4. This process is also used to apply relatively thick (1mm) coatings of

heat resistant materials on jet engine parts, A special alloy of
chromium, aluminium and yttrium is used for this type of coating.
UNIVERSITY 96
PVD – Thermal Evaporation

UNIVERSITY 97
PVD - Sputtering
1. High technology coatings such as ceramics, metal alloys and organic and
inorganic compounds are applied by sputtering.
2. The substance to be coated is connected to a high voltage dc power supply.
3. When the vacuum chamber has been pumped down, a controlled amount of
argon or another gas is introduced to establish a pressure of about 10-2 to 10-3
torr.
4. On energizing current supply, plasma is established between the work and the
material to be coated.
5. The gas atoms are ionized, and they bombard the material to be coated.
6. The energy of impinging ions cause atoms of the target material to be

sputtered off, and they are transported through the plasma to form a coating.
7. Direct current sputtering is used when the target is electrically conductive.
8. Radio-frequency sputtering, which uses a RF power supply is used when the

target is a non conductor such as polymer.
UNIVERSITY 98
Sputtering
The substrate is placed in a vacuum chamber with the source material,

named a target, and an inert gas (such as argon) is introduced at low
pressure. A gas plasma is struck using an RF power source, causing the
gas to become ionized. The ions are accelerated towards the surface of
the target, causing atoms of the source material to break off from the
target in vapor form and condense on all surfaces including the substrate.
99
PVD – Ion plantation
1. A third variation of the PVD process is ion plating, which involves
the evaporation.
2. They physically implant into the substrate to produce an extremely

strong coating bond.
3. Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications.
4. The wear properties of tools are widely enhanced by hard thin film
coatings.
5. Sputtered coating processes produce microscopic modules of

diameter of several micrometers and they are called macros.
6. These macros are undesirable for metal to metal sliding systems.
7. On the other hand they are usually beneficial to cutting tools.

UNIVERSITY 100
Applications of PVD

UNIVERSITY 101
Evaporation and sputtering: comparison
Evaporation Sputtering
Rate Thousand atomic layers per second One atomic layer per second
(e.g. 0.5 µm/min for Al)
Choice of materials Limited Almost unlimited
Purity Better (no gas inclusions, very high Possibility of incorporating
vacuum) impurities (low-medium vacuum
range)
Substrate heating Very low Unless magnetron is used
substrate heating can be
substantial
Surface damage Very low, with e-beam x-ray Ionic bombardment damage
damage is possible
In-situ cleaning Not an option Easily done with a sputter etch
Alloy compositions, Little or no control Alloy composition can be tightly
stochiometry controlled
X-ray damage Only with e-beam evaporation Radiation and particle damage is
possible
Changes in source Easy Expensive
material
Decomposition of High Low
material
Scaling-up Difficult Good
Uniformity Difficult Easy over large areas
Capital Equipment Low cost More expensive
Number of depositions Only one deposition per charge Many depositions can be carried
out per target
Thickness control Not easy to control Several controls possible
Adhesion Often poor Excellent
Shadowing effect Large Small
Film properties (e.g. Difficult to control Control by bias, pressure,
grain size and step substrate heat
coverage) Prof. Dr. F. Nawaz Khan, VIT
UNIVERSITY 102
What is CVD Process?
 Chemical Vapor Deposition is the formation of a non-volatile solid
film on a substrate by the reaction of vapor phase chemicals
(reactants) that contain the required constituents.
 The reactant gases are introduced into a reaction chamber and are
decomposed and reacted at a heated surface to form the thin film.

UNIVERSITY 103
CVD vs. PVD
 Chemical Vapor Deposition (CVD) relies
on chemical reactions between reactants
in the gas phase and/or on the substrate
surface.
 Physical Vapor Deposition (PVD) is a
thermal evaporation driven or energy
driven process.

UNIVERSITY 104
Applications of CVD

UNIVERSITY 105
Chemical vapour deposition

UNIVERSITY 106
Chemical vapour deposition
Advantages and Disadvantages:
• This coating finds application on glass containers to make
explosion or shatter resistant glasses.
• The main advantage of CVD process over PVD is that it is

not line of sight.
• All surfaces in the reaction chamber get coated.
• Separate process and reaction must be developed for each

coating. Some of the gases are toxic and dangerous.
• But greatest disadvantage is temperature should be very

high at 700°C. At this temperature, many metals soften.
UNIVERSITY 107
Plasma Enhanced (PE)CVD
As the thermal budget gets more constrained while more layers are
added for multi-layer metallization, we want to come down with the
temperature for the oxide ( or other) CVD processes. One way for doing
this is to supply the necessary energy for the chemical reaction by
ionizing the gas, thus forming a plasma. UNIVERSITY
108
Applications of CVD
1. A newer process known as plasma assisted chemical vapour
deposition. This process is used to apply diamond and diamond
like carbon coatings.
2. Silicon carbide barrier coatings are applied on plastic films and

semiconductors.
3. Chemical Vapour Deposition is used to produce bulk shapes of
high purity silicon carbide. Reactants are deposited on a
chamber wall to a thickness in terms of millimeters.
4. Thin-film coatings are key to the manufacture of many electronic

devices. They involve the application of dopant, sealant and
other microelectronic paste.
5. Thermal evaporation is a low cost process, but all these

processes are normally batch processes because of vacuum
chamber requirements.
UNIVERSITY 109
CVD Used in Semiconductors
Temperature
Layer Reaction equations (ºC)
SiO2 LTO SiH4 + O2 -> SiO2 + 2H2 400-450

TEOS Si(OC2H5)4 -> SiO2 + gas.RP 650-700
HTO SiCl2H2 + N2O -> SiO2 + 2N2 + 2HCl 850-900
SiH4 + CO2 H2 -> SiO2 + gas.RP 850-950
Si3N4 3SiH2Cl2 + 4NH3 -> Si3N4 + 6HCl + 6H2 700-900
Polysilicon SiH4 -> Si + 2H2 600-650
selective 2WF6 + 3Si -> 2W + 3SiF4 300

Tungsten
blanket WF6 + SiH4 -> W + SiF4 + 2HF + H2 400-450
UNIVERSITY 110
Metal cladding:
Metal cladding is sandwiching the base metal

between two thin layers of coating metal by hot
rolling process to give strong bonding between the
two.
More cathodic metals are used to clad base metal;

Eg. Cu, Ni, Ag, Pt, Ti.
Duraluminium sandwiched between aluminium

sheets and hot rolled gives “Alkad” which is free
from stress

UNIVERSITY 111
UNIVERSITY 112
Alloying for corrosion protection
Basic concepts of Eutectic composition and

Eutectic mixtures
Selected examples – Ferrous and non-ferrous

alloys
Significance of Alloying
 The alloy coatings bring quality, reliability and
durability for process vessel linings and pipe linings.
 along with the surface protection of components and
equipment against extreme conditions such as high
temperature, higher abrasion or high acidity
surroundings.
Examples
 Nickel alloys are known for resistance to extreme corrosion
and high temperature requirements.
 Copper-nickel alloys are used for anti-fouling resistance.
 Nickel-titanium alloys exhibit shape memory.
 Iron-nickel alloys show low thermal expansion.

Basic concepts of Eutectic composition
Eutectic mixture.
 A mixture of two or more substances which melts at
the lowest freezing point of any mixture of the
components.
 This temperature is the eutectic point. The liquid
melt has the same composition as the solid.
 Eutectic alloys have two or more materials and have a eutectic
composition.
 The melting point of the eutectic alloy is lower than that of the
components (eutectic = easy to melt in Greek).
 When a well-mixed eutectic alloy melts, it does so at a single
and sharp temperature.
 Conversely, when a non-eutectic alloy solidifies, its components
solidify at different temperatures, exhibiting a plastic melting
range.
Initially, the alloy is a liquid at the
eutectic composition
α and β are two different metals.

Solidification starts at the nucleation sites Nucleation sites grow
• Finally the entire alloy

becomes solid.
• Therefore, as the
composition changes by
diffusion (a slow
process), it is important
that alloys be allowed to
cool at equilibrium (i.e.
slowly) if they are to be
of exactly eutectic
composition.
Ferrous Metals
 Ferrous Metals mostly contain Iron.
 They have small amounts of other metals or
elements added, to give the required
properties.
 Ferrous Metals are magnetic and give little
resistance to corrosion.
Some examples of the ferrous metals are:

 Vehicle scrap metal
 Demolition Site scrap metal
 Metal offcuts from manufacturing industries
Phase
Diagram
of
Fe-
Carbon
System
Non-Ferrous Alloys
Some examples of Non-Ferrous Metals are:
• Aluminum Alloys
• Copper Alloys
• Magnesium Alloys
• Beryllium Alloys
• Nickel and Cobalt Alloys
• Titanium Alloys
• Refractory and Precious Metals
 Large amount of alloying elements to
produce strong and stable phases at high
temperatures.
 Heat resistance, creep resistance, and
corrosion resistance up to 1000 oC even
though the melting point similar to that of
steel.
 Applications: Vanes and blades for turbines
and other jet engine parts, chemical reaction
vessels, heat treatment equipment, heat
exchangers.

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Control of Corrosion

Corrosion can be controlled by:

Prof. Dr. F. Nawaz Khan, VIT

o To the extent possible, contact of dissimilar metals far apart from

o Metals which are close in potentials in the electrochemical series are

o Insulating materials (washers, spacers) can be used when two

o When two dissimilar metals are together, painting or electroplating

o Sharp corners and edges should be avoided in a fabrication since

Weld Sharp corner Smooth bend

Bolt joint crevices

c. Use of metal alloys:

i) Sacrificial anodic protection:

Prof. Dr. F. Nawaz Khan, VIT

The water pipe is turned

Magnesium is used as the

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

o Impressed direct current is applied in the opposite direction to the

o Usually, one terminal of a battery is connected with an insoluble

o The other terminal is connected to the metallic structure to be

o Since the current is impressed on the metallic structure, it acts as

o This method is usually used to protect underground water pipe

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

o Anodic inhibitors are the substances which reduce the corrosion

o Metal surface adsorbs metal ions to form a protective layer to

Prof. Dr. F. Nawaz Khan, VIT

o Cathodic inhibitors are mainly added to reduce the diffusion of

2H+(aq) + 2e- → H2(g)

o The formation of H2 gas can be controlled by increasing the

o Organic inhibitors like amines, mercaptans, heterocyclic nitrogen

o These inhibitors get adsorbed on the metal surfaces and form an

Prof. Dr. F. Nawaz Khan, VIT

o Hence, the corrosion can be controlled either by removing

o The oxygen can be eliminated by adding reducing agents

o These react with hydroxyl ions forming corresponding

Prof. Dr. F. Nawaz Khan, VIT

o Fe, Cr, Ni, Ti and their alloys exhibit passive character.

o Eg. i) Iron dipped in conc. HNO3 becomes passive.

o This passivity is attained because of the formation of a passive film

o Passivity is not a permanent property and depends on the

Prof. Dr. F. Nawaz Khan, VIT

o Protective coatings are classified as:

o Surface preparation is a process to remove rust, oxide scales, oil,

o Hence, mechanical and electrical methods are used to prepare the

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

e) Acid pickling and etching:

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

 Note that E°oxidation

o Coating of tin, chromium, nickel on iron surface are cathodic

o If there is a discontinuity in the coating, then galvanic couple will

o To avoid this, the article is checked and re-plated periodically so

Prof. Dr. F. Nawaz Khan, VIT

Exposed part (anode)

Prof. Dr. F. Nawaz Khan, VIT

Two types of hot dipping techniques are known.

i) Galvanizing: Dipping the base metal iron in molten zinc metal

Drying Ammonium Pairs of Galvanized

Dil. H2SO4 Molten zinc Excess zinc

Galvanizing a sheet of iron

Prof. Dr. F. Nawaz Khan, VIT