Engineering Chemistry

CHY1701

Dr. Krishnendu Biswas, SAS, #2, I Floor Annex

#1245, krishnendu.biswas@vit.ac.in
 Module 4

Corrosion control methods: Inhibitors – anodic and

cathodic and their action;

Cathodic protection – sacrificial anodic and
impressed current protection methods;

Corrosion protection coatings;

Galvanizing and tinning;

Electroplating-process and typical applications,

Advanced coating processes – Basic concepts of
PVD and CVD.
 Corrosion control
 Surface of the metal to be protected – control

 Corrosion of metal can be reduced by any of the

following methods

 Proper selection, design of metal equipment,

fabrication etc.

 Protective coating
 Metal coatings
 Inorganic and organic coatings

 Cathodic and anodic protection

 Corrosion inhibitors
 Good design – avoid corrosion or if
corrosion occurs – uniform

Important design principles

 Avoid the contact of dissimilar metals in
the presence of a corroding soln.
 larger ‘anodic area’ of metal w.r.t cathode
reduces rate of corrosion.
 Metals closer in galvanic series should be
chosen for fabrication to minimize
differential metal type corrosion.
 Isolation of dissimilar metals by insulation-
fitting. Eg noble metal can be insulated
from less noble metal by plastic washers.
 Equipments - supported on legs – allow
free circulation of air and prevent
formation of stagnant and damp area -
prevent corrosion.
 Uniform flow of corrosion liquid is
desirable.
 Corrosion-resistance of most metals
improved by alloying with suitable elements
– but it should be homogeneous. Eg.
Stainless steel, alloy of Fe Cr and C
 Protective coating
 Protective coating protects the metal from corrosion by
acting as a barrier between the metal and the environment.
 Metal coating – covering base metal with a layer of
protective metal - prevent metal from exposing to
environment.
 Metal coating also provides easier clean ability, aesthetic
look, increase light reflectance, thermal insulating and
electrical properties, wear resistance, oxidation etc.

Metal coating

Anodic metal coating Cathodic metal coating

Metal anodic to base metal is Metal cathodic to base metal is

coated Eg. Zn coating over iron coated Eg. Ni coating over iron
 Anodic metal coating
 Coating anodic metal on base metal
for prevention of corrosion Eg. anodic
coating of Zn or Al on mild steel/iron.
 Zn (coated on base metal) - anode
(corrode)
 Iron (base metal) – cathode
(protected)
 Anodic metal coating - sacrificial
corrosion prevention method
eg. roof sheets, bolts etc.
 Cathodic metal coating
 Coating cathodic metal on base metal for prevention
of corrosion eg. Sn or Cu coating on Fe(base metal).
 Cathodic coating protects the base metal because of
its high corrosion resistance than base metal.
 Cathodic coating – effective – when no defect.
 If there is a defect – coating cause more corrosion
damage than without coating
 Tinning - coating tin over iron or steel

Tin coating (cathodic)

Fe (base metal, anodic)

 Comparison of anodic and cathodic
coating
S. Anodic coating Cathodic coating
No

1 Protects underlying metal Protects underlying metal due

sacrificially to its noble character and
higher corrosion resistance

2 Electrode potential of Electrode potential of coating

coating metal is lower than metal is higher than base
base metal metal

3 If pore or cracks in If pore or cracks in coating,

coating, base metal is not corrosion of base metal
corroded till the coating speeded up
metal is consumed
4 Zn coating over Fe Sn coating over Fe
 Techniques of metal coating
Galvanization and Tinning
 Galvanization - process of coating Fe or steel with thin
coat of Zn to prevent rusting.
 Hot dipping - used for coating low-melting metal (Zn,
Sn, Pb, Al etc.) on Fe, steel and Cu which have
relatively higher m.pt – immersing base metal in bath
of molten coating-metal, eg. Zn on Fe (Galvanizing),
Sn on Fe (Tinning)
 Degreasing - Metal cleaned and degreased by organic
solvent
 Pickling – metal dipped dil. H2SO4 for 10 min at 80
°C to remove rust, scale and impurities.
 Fluxing (ZnCl2 & NH4Cl) – cleans base metal, prevents
oxidation of molten metal and for best adhesion
 Metal dipped – molten Zn at 430-470 °C
 Excess Zn removed from surface of coated metal –
rolling, wiping or air blow techniques.
 Uses of galvanized steel
 Protection of Fe or steel from atmospheric corrosion in the
form roofing sheets, wires, pipes, nails, bolts, screws,
buckets, tubes etc.

 Zn get dissolved in dil. acids to form highly toxic

compounds – galvanized utensils cannot be used for
preparing and storing foodstuffs, especially acidic ones
 Tinning
 Tinning - coating tin over iron or steel

 Pickling

 Fluxing

 Metal quickly dipped in molten Sn

 To avoid oxidation, hot Sn-coated metal, is treated with

palm oil.

 Rollers remove any excess of tin and produce thin film of

uniform thickness.

 Due to non-toxic nature of Sn, Sn-coated metals used in

food storage cans, cooking utensils and refrigeration
equipments etc.
 Metal cladding
 Metal cladding – pasting dense,
homogenous layer of corrosion
resistant metal (Ag, Ni, Pb, Cu
etc) firmly and permanently over
base metal surface (Al, Cu etc.)
on one or both sides

 Sandwiching the base metal

between two thin layers of
coating metal by Hot-rolling,
under action of heat and pressure
- bond firmly.

 Cladding - widely used in

aircraft industry of ‘alclad’
sheeting - plate of duralumin
(Al-Cu) is sandwiched between
two layers of 99.5 pure Al.
 Electroplating
 Electroplating – coating
metal, deposited on the base
metal by passing a D.C
through an electrolyte
solution containing the
soluble salt of the coating
metal.
 Eg. Electroplating of Fe with
Sn (tinning) and Fe with Zn
(galvanizing)
 Cathode - object to be plated
 Anode - metal to be
deposited (it replenish the
metal ion in the solution)
 Electrolyte – soluble salt of
coating metal
 Au, Ag, Cr, Ni etc. can
electroplated on base metal.
Objectives
 To increase hardness, resistance against corrosion, chemical
attack etc.
 To increase decorative and commercial values of metals
Uses of electroplating
 In electronic industries for making printed circuit boards,
semiconductor lead-out connection
 In manufacture of jewelry, iron box, etc.
 Thickness of the deposit – for decorative purpose thin
coating and for corrosion resistance thick coating
Factors affecting
 Cleanness of metal surface (clean surface - strong
adherence)
 Concentration of electrolyte (moderate conc. preferred for
uniform coating)
 Current density (should be low for uniform controlled
deposition)
 Additives (ensure strong adherence eg. H3BO3, gelatin etc.)
 pH of the electrolytic bath (more favorable pH 4.0 – 8.0)
 Increase in concentration of Electrolyte : increases plating
 Increase in amount of current : increases plating. There is
more energy for ions to move towards electrodes.
 Time : longer time, even if current is same can allow more
ions to pass through.
 Surface area of anode is greater, it enhances plating.
 Distance between electrodes : if distance between electrodes
is smaller, ions need less energy to flow from anode to
cathode.
For electroplating of Cu on metal surface,
 Electrolyte: (3-5%)H2SO4 / (15-30%) CuSO4
 Anode: Pure Cu metal or Graphite (inert)
 Cathode: Metal to be coated
 Additive: Boric acid or gelatin

Ionization reaction of electrolyte is observed,

CuSO4  Cu2+ + SO42-
On passing current,
Cu2+ + 2e-  Cu (at cathode)
For electroplating of Ni on metal surface
 Electrolyte: Nickel sulfate (NiSO4·6H2O) + Nickel
chloride (NiCl2·6H2O)
 Anode: Pure Ni metal
 Cathode: Metal to be coated
 Additive: Boric acid

For electroplating of Au on metal surface

 Electrolyte: Gold cyanide([Au(CN)2]-)
 Anode: Pure Au metal
 Cathode: Metal to be coated

For electroplating of Ag on metal surface

 Electrolyte: Silver Nitrate (AgNO3) + Pot. Cyanide
(KCN)
 Anode: Pure Ag metal
 Cathode: Metal to be coated
Methods of cleaning before electroplating
 Solvent cleaning – To remove oil, grease, rust using organic
solvents like alcohol, xylene, acetone, chlorinated
hydrocarbons followed by cleaning with steam and hot
water.
 Alkali cleaning – To remove old paints, chemicals like
NaOH, Na3PO4 etc. can be used. After cleaning, the metal is
washed with 1% chromic acid solution.
 Mechanical cleaning – To remove loose scale and rust, using
hammer, wire-brushing, grinding and polishing.
 Acid pickling and etching – Metal is dipped in acid solution
at a higher temp. for a long duration. Acids used are HCl,
H2SO4, H3PO4, HNO3, under dilute conditions.
 Flame cleaning – Heating metal surface with a hot flame to
remove moisture and loosely adhering scales.
 Sandblasting (sand with air stream of 25-100 atm is
used.) - To clean large surface areas and to produce enough
roughness for good adherence of protective coating.
 Cathodic protection
 Principle: Forcing the metal to be
protected to behave as cathode -
prevent corrosion.
 Sacrificial anodic protection
 Impressed current cathodic
protection
Sacrificial anodic protection
 Metal structure to be protected is
connected through a piece of wire
to more anodic metal.
 Metal structure and anode must be
in contact with the
electrolyte(moist soil and water).
 All corrosion concentrated at more
active anodic metal and cathodic
metal is protected. fi
 Zn, Mg, Al – can be used as
sacrificial anode.
 It is employed in protection of
– Buried pipelines
– Underground cables
– Marine structures
– Ship-hulls
– Water-tanks etc.
Advantages of sacrificial anodic protection
– No external power is required
– Easy to install and anodes can be readily
added
– Minimum maintenance and uniform
distribution of current
– Effective use of protective current
Oil rigs use blocks of Al at the
Limitations foot of every Fe pillar to
 Limited driving potential and current prevent corrosion
output
 Poorly coated structure may require many
anodes
 Can be ineffective in high-resistivity
environment
 Installation can be expensive if installed
after construction.
 Impressed current cathodic protection
 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.
 Connecting negative terminal of the
battery to the metallic structure to be
protected.
 Positive terminal of battery is connected
to an inert anode like graphite or
platinised titanium.
 Corrosion metal become cathodic and
corrosion prevented.
 Impressed current is obtained from DC
source.
 Anode buried in backfill containing
mixture of gypsum, coke, sodium sulphate
to increase electrical contact between
itself and surrounding soil.
It is employed in protection of
 Water tanks, buried water or oil pipes,
marine piers, laid-up ships etc.
Advantages
 Can be designed for a wide range of voltage and
current.
 Large areas can be protected by single installation. But
require periodic inspection and maintenance.
 This method is useful for protection of large structure
for long-term operation.

Limitations
 May increase the corrosion of adjacent pipeline or an
adjacent metal structure because of stray (leaked)
currents.
 Require periodic inspection and maintenance costs
 Chemical reactions occurring at the surface of the
protected structure may cause problem.
 Overprotection can cause coating damage.
 Require external power, resulting in monthly power
costs.
Sacrificial anodic Impressed current
method method
No external power External power supply
supply is necessary must be present.
This method requires Here anodes are stable
periodical and do not
replacement of disintegrate.
sacrificial anode.
Investment is low. Investment is more.
Soil corrosion effects are Soil corrosion effects are
not taken in to taken in to account.
account.
This is most economical This method is well
method especially suited for large
when short-term structures and long
protection is required. term operations.
 Anodic protection
 Principle of anodic protection: Metal to be protected from
corrosion is made ‘more anodic’. An external impressed DC is
applied to anode part, which makes it more anodic. A protective
oxide film formed which protects the surface from further
corrosion.
 A potentiostat maintains metal at constant potential w.r.t
reference electrode (calomel). potentiostat has 3 terminals. One is
connected to structure to be protected, other to auxiliary cathode
(Pt), and third to a reference electrode.
 This technique is only applicable to metals which exhibit active-
passive behavior eg, Ti, Al, Ni, stainless steel, Cr etc., (and these
metals cannot afford cathodic protection since these readily get
passivated).
 Limitations: This method is applicable for only those metals which
passivate.
 During anodic protection corrosion does take place but at a very
slow rate (i.e corrosion rate is not zero)
 Applications: Stainless steel containers used for transporting
corrosive chemicals (eg. conc. acids) are protected from corrosion.
 Corrosion inhibitors
 Corrosion inhibitors are substance which when added in
requisite quantities to the medium reduces rate of corrosion
of metals.
 Anodic and Cathodic
Anodic Corrosion inhibitors
 Chromates (CrO42-), phosphates (PO43-), tungstates (WO42-
), borates (BO33-), silicates (SiO44-), molybdates (MoO42-)
Mechanism
 Anode – corrosion or dissolution of metal
 Anodic inhibitors react with newly born metal ion and form
a sparingly soluble metal salts (eg. phospates, chromates
etc.).
 Metal salts formed get adsorbed on the anode surface,
forming a protective film – reduces rate of corrosion.
 Caution: Sufficient amount of anodic inhibitors should be
used – uncovered anode aggravates the corrosion due to
small anodic area and large cathode surface area.
Cathodic Corrosion inhibitors
 If reaction at cathode is controlled - possible to inhibit corrosion
 In acidic solution, main cathodic reaction is evolution of hydrogen.
 To decrease the rate of corrosion, either
a) rate of diffusion of H+ ion should be decreased or
b) H2 overvoltage should be increased.
 Decreasing the rate of diffusion of H+ ion – converting smaller H+
into bulkier cation by reacting with organic inhibitor, amines,
mercaptans, heterocyclic nitrogen, substituted urea etc., which are
capable of being adsorbed at metal surface.
 In neutral solution DO gets reduced to form OH- at cathodic area
 Corrosion can be controlled either eliminating O2 or by forming
impermeable film over cathode.
 Addition of inhibitor like Mg, Zn or Ni salts reacts with OH- and
form insoluble hydroxide, which deposit on cathode forming
protective layer.
 Deposition of thin film of Sb or As over cathodic surface –
increases considerably the H2 overvoltage.
 Inorganic coating
 Coating inorganic material over base metal for prevention of
corrosion.
 Inorganic coating - chemical or electrochemical techniques.
 Formation of passive oxide film (O2-)
 Phosphate coating (PO42-)
Passive oxide film
Anodization - formation of protective oxide film by making the base
metal as anode in electrochemical process. Eg. anodization of Al
 Al made as anode of the cell in oxidizing electrolyte (H2SO4,
(COOH)2, H2CrO3)
Experimental conditions for anodization of Al
 H2SO4 – 190-200 g/L of water
 Current density (1-25 amps/cm2); Voltage (10-28 V)
 Temperature – 15-23°C
 Time – 30-50 min
 Anodized material used for making soapboxes, tiffin carriers,
utensils, window frames etc.
Phosphate coating
 Coating thin film of metal phosphate (Zn/Mn phosphate) on base
metal.
 Phosphate coating - offer complete resistance to corrosion
 Phosphate coating done mainly on Fe, steel and Zn.
 Phosphating done by immersion, spraying, brushing or
electrochemical process.
 Phosphating serves as good point of adhesion for paints, lacquers
enamels etc.
 Phosphating bath - H3PO4, Zn/Mn phosphate soln.
 Accelerators such as Cu salts, H2O2, nitrates etc. enhances rate of
deposition.
 pH of phosphating bath maintained at 1.8-3.2,temp.35°C
 Phosphate coating produced by chemical reaction of base metal
with metal phosphates in aq. H3PO4.
 Phosphate coated materials used in automobile industry, nuts and
bolts, construction materials etc.
 Organic coating
 A method to prevent corrosion of metal – paints,
varnishes, lacquers and enamels
 Organic coating – introducing inert organic barrier
between metal surface and environment to prevent
corrosion and decoration.
 Paint – mixture of one or more pigments in an organic
medium consisting of oil. Important constituents of
paints a) pigments, b) medium (drying oils, c) thinner,
d) fillers and e) plasticizers.
 Varnishes – solution of natural (resin, shellac etc.) or
synthetic gums (phenol-formaldehyde, chlorinated
rubbers etc.) in medium (linseed oil).
 Lacquers – a mixture of cellulose derivative, organic
solvent, synthetic resin, plasticizers and diluents.
 Enamels – Pigmented varnishes and pigmented
lacquers.
Thin-Film Coatings (µm)
 Classifications of thin-films based on
their applications
Thin-film property Typical applications
category

Optical Reflective/anti-reflective coatings

Interference filters, Decoration (colour, luster),
Memory discs (CDs), Waveguides

Electrical Insulation, conduction, Semiconductor devices,

Piezoelectric drivers

Magnetic Memory discs/devices

Chemical Barriers to diffusion or alloying
Protecting against corrosion or oxidation
Gas/liquid sensors

Mechanical Tribological (wear resistant) coatings

Hardness, Adhesion, Micromechanics
Thermal Barrier layers, Heat sinks
 Physical Vapor Deposition (PVD)

 PVD is a process to produce a metal vapor that can be

deposited on 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).

 Single or multi-layer coatings can be applied during the

same process cycle.

 Additionally the metal vapor can be reacted with various

gases to deposit Oxides, Nitrides, Carbides or Carbonitrides.

The coating method involves purely physical processes such as

high temperature vacuum evaporation or plasma sputter
bombardment rather than involving a chemical reaction at
the surface to be coated.
 The parts to be coated are first cleaned. The cleaning process
varies depending on the level of quality from the electroplater,
substrate material and geometry.
 The parts are loaded into the vacuum chamber on custom fixtures
designed to optimize the chamber load size and ensure coating
uniformity.
 The vacuum chamber is evacuated to 10-6 torr (high vacuum) to
remove any contaminants in the system.
 The vacuum chamber is backfilled with an inert gas argon and
ionized, resulting in a glow discharge (plasma). This is the gas
cleaning stage and prepares the parts for the initial metal
deposition.
The process involved four steps:
• Evaporation.
• Transportation.
• Reaction.
• Deposition.
During this stage, a target, consisting of the material to be deposited is
bombarded by a high energy source such as a beam of electrons or ions. This
dislodges atoms from the surface of the target, ‘vaporising’ them.

This process simply consists of the movement of ‘vaporised’ atoms from

the target to the substrate to be coated and will generally be a straight
line affair.

In some cases coatings will consist of metal oxides, nitrides, carbides and
other such materials. In these cases, the target will consist of the metal. The
atoms of metal will then react with the appropriate gas during the
transport stage. For the above examples, the reactive gases may be oxygen,
nitrogen, acetylene or methane.

This is the process of coating build up on the substrate surface.

Depending on the actual process, some reactions between target materials
and the reactive gases may also take place at the substrate surface
simultaneously with the deposition process.
 Physical Vapor Deposition (PVD)

PVD Chamber

Substrate
Ni film

Heater

N2 Suction valve
(or) Ni Source
2000oC
H2
To vacuum pump
 Titanium Nitride coated punches
Aluminium Chromium
Titanium Nitride coated

Aluminium Titanium Nitride coated

 Different types of PVD coating

• Cathodic Arc Deposition: In which an electric arc is used to

vaporize material from a cathode target. The vaporized
material condenses on a substrate, forming a thin film.

• Evaporative deposition: In which the material to be

deposited is heated to a high vapor pressure by electrically
resistive heating in "low" vacuum.

• Sputter deposition: In which a glow plasma discharge

(usually localized around the "target" by a magnet)
bombards the material sputtering away as a vapor.

• Pulsed laser deposition high-power pulsed laser beam strike

a target of the material that is to be deposited - vaporized
from the target (in a plasma plume) - deposits it as a thin
film on a substrate (such as a silicon wafer facing the target
- ultra high vacuum or in the presence of a background gas,
such as oxygen which is commonly used when depositing
oxides to fully oxygenate the deposited films.
 Cathodic Arc deposition

 In the cathodic arc deposition process, a pulsed or continuous high

current-density, low voltage electric current is passed between
two separate electrodes (cathode and anode) under low pressure
vacuum, vaporizing the cathode material while simultaneously
ionizing the vapour, forming a plasma.
 The high current density (usually 104-106 Amp/cm2) causes arc
erosion by vaporization and melting while ejecting molten solid
particles from the cathode surface, with a high percentage of the
vaporized species being ionized with elevated energy (50-150eV)
and some multiply charged.
 For example, in the case of TiN, as the vaporized titanium
(cathode target) passes through the arc, it becomes ionized
forming a plasma.
 The plasma is directed towards the substrate’s surface, and in the
presence of nitrogen, forms a TiN coating.
 Similarly, TiAl, TiSi, TiCr, etc. targets can be used to produce
TiAlN, TiSiN, TiCrN, etc., or using acetylene, carbides can be
formed.
Advantages of cathodic arc processes:

 High level of atom ionization in the plasma : As a result of

the high level of energy produced by this process, materials
can be co-evaporated at the same rate, thus producing
stoichiometric compounds.
 Better adhesion can be achieved as a result of the
intermixed reaction zone
 Low-processing temperatures allow for the coating of heat-
sensitive substrates/components
 Multilayered coatings and functionally graded compositions
can easily be produced.

Disadvantages of cathodic arc processes:

 Coating complex geometries can be difficult due to line-of-

site process
 Evaporative deposition
 In evaporation the substrate is placed inside a vacuum chamber,
in which a block (source) of the target material to be deposited is
also located.
 The source (target) material is then heated to the point where it
starts to boil and evaporate.
 The vacuum is required to allow the molecules to evaporate freely
in the chamber, and they subsequently condense on all surfaces.
There are two popular evaporation technologies, which are e-
beam evaporation and resistive evaporation each referring to the
heating method.
 Sputtering
 Coating can be done for both
conductive (dc) and non-conductive
(RF sputtering) materials
 DC sputtering – the target and
substrate to be coated are connected
to high voltage dc power supply.
 Vacuum chamber is filled with
controlled amount of argon gas to
establish a pressure of 10-1 torr.
 The supplied direct current
energizes the chamber creating a
plasma between the target and the
material to be coated (substrate).
 The argon atoms get ionized and
accelerated to bombard on the target
(workpiece) resulting in the
sputtering of atoms, which are
transported and coated on the
substrate (substance)
Pulsed laser deposition
 Chemical Vapor Deposition
 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.
 Deposited films range from metals to semiconductors
to insulators.
 Many different films can be deposited: elements and
compounds, crystalline, polycrystalline, and amorphous.
Most films can be deposited from several different
precursor systems.
 High temperatures and low pressures are the most
common process conditions, but are not necessary.
 All CVD involves using an energy source to break
reactant gases into reactive species for deposition.
 In a typical CVD process, reactant gases (often diluted in a
carrier gas) at room temperature enter the reaction
chamber.
 The gas mixture is heated as it approaches the deposition
surface, heated using radiation or placed upon a heated
substrate.
 Depending on the process and operating conditions, the
reactant gases may undergo homogeneous chemical
reactions in the vapor phase before striking the surface.
 Near the surface thermal, momentum, and chemical
concentration boundary layers form as the gas stream
heats, slows down due to viscous drag, and the chemical
composition changes.
 Heterogeneous reactions of the source gases or reactive
intermediate species (formed from homogeneous pyrolysis)
occur at the deposition surface forming the deposited
material.
 Gaseous reaction by-products are then transported out of
the reaction chamber.
 Contd…

1. Transport reactants via forced convection to reaction

region
2. Transport reactants via diffusion to wafer surface
3. Adsorb reactants on surface
4. Surface processes: chemical decomposition, surface
migration, site incorporation, etc.
5. Desorption from surface
6. Transport byproducts through boundary layer
7. Transport byproducts away from deposition region
Contd…
 Deposition by Chemical Vapour Deposition (CVD)

H2 = 50 mm Hg CVD Chamber
N2 = 15 mm Hg

Ni film
HTV

Substrate
Pre
Vap Heater

N2 Suction valve
Solid
complex
(or)
H2
400oC To vacuum pump
 Typical precursor materials

Halides - TiCl4, TaCl5, WF6, etc

Hydrides - SiH4, GeH4, AlH3(NMe3)2, NH3, etc.

Metal Organic Compounds:

Metal Alkyls - AlMe3, Ti(CH2t-Bu)4, etc

Metal Alkoxides – Ti (OiPr )4, etc
Metal Dialkylamides - Ti(NMe2)4, etc
Metal Diketonates – Cu (acac)2, etc
Metal Carbonyls - Ni(CO)4, etc

Others – include a range of other metal organic

compounds, complexes and ligands.
 CVD Reaction Types
Pyrolysis
Chemical decomposition or change induced by heat
Polycrystalline silicon is deposited from silane (SiH4),
using the following reaction:
SiH4 → Si(s) + 2 H2 (g) (650 deg C)
Ni(CO)4 (g) → Ni(s) + 4CO(g) (180 deg C)
Reduction
SiCl4 (g) + 2H2 (g) → Si(s) + 4HCl(g)
MoF6(g) + 3H2 (g) → Mo(s) + 6HF(g)
Disproportionation:
2GeI2 → Ge(s) + GeI4 (g)
Oxidation:
SiH4(g) + O2(g) → SiO2(s) + 2H2(g)

Compound Formation
SiCl4 (g) + CH4(g) → SiC(s) + 4HCl(g)
In every case, CVD processes must
 Provide a volatile precursor containing the constituents of the film
 Transport that precursor to the deposition surface
 Encourage surface reactions that form the film
 To be done rapidly, reproducibly, and uniformly for industrial
applications.
Advantages
 high growth rates possible
 can deposit materials which are hard to evaporate
 good reproducibility
 can grow epitaxial films
Disadvantages
 high temperatures
 complex processes
 toxic and corrosive by-product gasses
 Metal-Organic Chemical Vapor Deposition
(MOCVD)
• Metal organic precursors
Ga(CH3)3 + AsH3 →→ 3CH4 + GaAs
(Trimethyl gallium gas)(Arsine gas) (Methane) (substrate)
• Ultra pure gases are injected into
a reactor to deposit a very thin
layer of atoms onto
a semiconductor wafer.
• Surface reaction of organic
compounds or metalorganics and
hydrides containing the
required chemical elements -
crystalline growth
• Dopants are introduced in
precisely controlled amounts
• This technique allow crystals to
be deposited on a substrate one
monolayer at a time with great
precision.
• This technique is also very useful
for artificial crystal structures
such as “superlattices” and
“quantum wells”.
• Useful for lab experiments & for
mass production
 Electroless Plating
• Depositing without any applied current – autocatalytic
plating
• Deposition of metal from salt solution on a catalytically
active substrate surface using a chemical reducing agent.
• Etching the surface – acid treatment
• Non-conducting surfaces – treated with SnCl2 and PdCl2 –
form a thing layer of Pd by reduction.
Advantages
• Electrical contact and power not needed
• Insulators and semi-conductors can also be plated
• More compact and highly adherent deposits
• Complex shapes can be plated due to more throwing power.
Electroless plating of Cu
• Salt : CuSO4. 5H2O, 5 g/dm3 ; Reducing agent :
formaldehyde
• Buffer: NaOH 12g + Rochelle salt 14 g/dm3, pH = 11
• Complexing agent – EDTA: 5 g/dm3; Temperature – 298 K

2HCHO + 4OH-  CHO- +2H2O + H2 + 2e-

 Phase rule
• Phase rule : F = C – P + 2 ; F = degrees of freedom, C =
components, P = Number of phases.
• For two component system - reduced phase rule : P + F = C + 1
 Eutectic composition
• Lead – Silver system – (non – ferrous alloy)
Application :
Pattinson’s process -
Molten liquid
with Ag (0.1%) at x
slowly let to cool
down and at y solid
Pb starts to crystallize
out, it follows the
curve YC with
enrichment of Ag.
Finally reaching the
eutectic point where
Ag is 2.6 %
a) Area ACB – homogeneous single phase of molten liquid exists ; P = 1, C=
2, F = 2
b) MP curves – AC : melting temperature of Ag in Pb; BC : Melting
temperatures of Pb in Ag. AC and BC curves indicate two phase
equilibrium i.e solid lead and silver – molten liquid respectively.
P = 2, C = 2, F = 1 (T or C)
c) Eutectic of Pb and Ag – C denotes the eutectic point - all three phases
co-exist; P = 3, C = 2, F = 0 - invariant
• Iron – Carbon system – (ferrous alloy)

C = Peritectic point
D = Eutectic point – pearlite phase
E = eutectic point – Ldedbuirte phase and
M = Cementite phase at 6.7 % of carbon
Classification of ferrous alloys:
Iron: less than 0.008% C in a-ferrite at room T.
Steels: 0.008 – 2.14% wt C, a-ferrite + Fe3C at room T

Cast Iron: 2.14 – 6.7% wt C (usually < 4.5 %)

Cementite: 6.67 % C

Eutectic composition: 4.3 wt % C (coming under cast iron)

Cementite: 6.67 wt % C and 93.3 % Fe is metastable and remain
indefinitely at room T but once heated to 650 to 700 °C decomposes to a-
Fe & C.

For the storage purpose of iron cementite can be a best alloy to store and
on the basis of requirement it can be utilised for alloying mostly for
mechanical strengthening.
End of module 4