Corrosion control

Cathodic protection:
• Principle is to make the base metal to be protected as cathode by connecting to a
highly anodic metallic plate.
• Two methods of cathodic protection are known:
i) Sacrificial anodic protection
ii) Impressed current cathodic protection
i) Sacrificial anodic protection:
• The metallic structure to be protected is connected through a
metal wire to a more anodic metal.
• This will induce corrosion at the anodic metal.
• Thus the more anodic metal sacrifices itself and gets corroded
protecting the metallic structure.
• Sacrificial anodes known are Zn, Mg, Al and their alloys.
• Applications are: protection of underground pipelines, ship hulls
and other marine devices, water tanks.
 Corrosion control
ii) Impressed current cathodic protection:

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

corrosion current to nullify it.
 Usually, one terminal of a battery is connected with an insoluble
anode e.g. graphite electrode is immersed in black fill containing
 coke, gypsum, bentonite and sodium sulphate for good electrical
conductivity.
 The other terminal is connected to the metallic structure to be
protected.
 Since the current is impressed on the metallic structure, it acts as
cathode and thus gets protected.
 This method is usually used to protect underground water pipe
lines, oil pipe lines, transmission lines, ships etc.
 Corrosion Inhibitor
• 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.

• Inhibitors are mainly anodic inhibitors and cathodic inhibitors.

Anodic inhibitors

• 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.

• 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.
 Cathodic inhibitors
• 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)

• The formation of H2 gas can be controlled by increasing the overvoltage of

hydrogen evolution.

• Organic inhibitors like amines, mercaptans, heterocyclic nitrogen compounds, substituted ureas, thio
ureas, heavy metal soaps reduce the diffusion of H + ion considerably.

• These inhibitors are being adsorbed at the metal surfaces and form an
adherent film of metals at the cathodic area thereby increase the hydrogen
overvoltage considerably.
 Cathodic Inhibitors

• However, in neutral solution, the cathodic reaction is

• H2O + ½ O2 + 2e- → 2OH-

• Hence, the corrosion can be controlled either by removing oxygen from

the corroding environment or by reducing its diffusion to the cathodic
areas.

• 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.

• These react with hydroxyl ions forming corresponding

insoluble hydroxides, which are deposited on the cathode forming
impermeable self barrier.
Electrodeposition is the process that exploits the creation
of solid materials directly from electrochemical reactions
in liquid compositions with substrate materials.

It is also known as Electroplating.

An electrochemical process where

metal ions are transferred from a solution and are
deposited as a thin layer onto surface of a cathode.
 Electroplating can enhance;

Chemical properties---increase corrosion resistance

Physical properties---increase thickness of part

Mechanical properties---increase tensile strength & hardness

Limitations
Typically restricted to electrically conductive substrate materials

Difficulties in the preparation of desired templates.

Additional high temperature annealing steps are expensive and unsuitable

for polymer substrates
 Experimental Setup

Copper Cathode is reduced Nickel Anode is oxidized

(accepts electrons) (gives us electrons)

Ni2+ ions within solution become attracted

to Copper cathode
A three-electrode electrochemical cell (a reference electrode, a specially designed
cathode, and an anode or counter electrode)

Accessories for applying controlled current at a certain voltage (dc or Ac power supply
or potential stat)

The template can be made of either nonmetallic or metallic materials

The surface morphology of the deposits depends on the surface structure and chemical
composition of the cathode substrate as well as other electrochemical parameters.
 Thermodynamic and Kinetics of
Electrodeposition
The nucleation of nanostructures on the electrode substrate is influenced by the
crystal structure of the substrate, specific free surface energy, adhesion energy, lattice
orientation of the electrode surface, and crystallographic lattice mismatch at the
nucleus-substrate interface boundary.

The final size distribution of the electrodeposits strongly depends on the kinetics of
the nucleation and growth:

Instantaneous nucleation: all the nuclei form instantaneously on the electrode

substrate, and subsequently grow with the time of electrodeposition.

Progressive nucleation: the number of nuclei that are formed is a function of time of
electrodeposition. These nuclei gradually grow and overlap, and therefore, the
progressive nucleation process exhibits zones of reduced nucleation rate around the
growing stable nuclei.
Active template-assisted electrodeposition:

The formation of nanostructures results from growth of the

nuclei that invariably nucleate at the holes and defects of
the electrode substrate.

Subsequent growth of these nuclei at the template yields

the desired surface morphology of the nanostructures,
which can therefore be synthesized by choosing the
appropriate surface of the electrode
 Electroless Plating
• Electroless plating: Substrate is placed in a
more complex chemical solution, in which
deposition happens spontaneously on any
surface which forms a sufficiently high
electrochemical potential with the solution.
No external electrical potential and contact to
the substrate are required, but more difficult
to control the thickness and uniformity of the
deposits.
A drastic increase in the reduction rate of nickel and copper ions after the induction
period is due to simultaneous appearance of new and growth of the earlier formed
metal particles. Absolute quantity of the particles formed per unit volume of the
solution and their accumulation rate are considerably higher for the reduction of
nickel ions by hydrazine borane and boron hydride as compared to dimethylamine
borane or in case of copper ions being reduced by boron hydride as compared to
formaldehyde
Electroless Plating Electroplating
 Physical Vapour Deposition
(PVD)
“depositing material by atom by atom or molecule by molecule or
ion by ion”

Types
• Thermal evaporation
• Sputtering
dc (direct current sputtering)
RF (radio frequency)
• Ion plating
 PVD – Thermal Evaporation

• Metal to be coated is placed in a boat or crucible

• Electron beam is directed into the crucible to melt the evaporant

• Evaporant forms a atomic cloud that coats all surfaces in the line of sight of
the boat or crucible
 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.
Applications of Vacuum-deposited Materials
• Single and multilayer films and coatings
• Nanolayered materials
• Optical films for transmission and reflection
• Decorative films
• Decorative and wear-resistant (decorative/functional) coatings
• Permeation barriers for moisture and gases
• Corrosion-resistant films
• Electrically insulating layers for microelectronics
• Coating of engine turbine blades
• Coating of high strength steels to avoid hydrogen embrittlement
• Diffusion barrier layers for semiconductor metallization
• Magnetic films for recording media
• Transparent electrical conductors and antistatic coatings
• Wear and erosion-resistant (hard) coatings (tool coatings)
• Dry film lubricants
• Composite and phase-dispersed films and coatings
• Nanocomposite materials
• Thin-walled freestanding structures and foils
 Plasma Sputtering
plasma is a “state of matter similar to gas in which a certain portion
of the particles are ionized”

• The main principle is to build a vaccum chamber and fill with Argon

• By adding a high voltage, the argon will arc to plasma state

• The argon ion (Ar+) will move toward to cathode with high speed and
sputter the target material (use target as cathode).

• The target atom or molecular will be hit to substrate surface and condense as a film.

• Instead of heat melting in evaporation method, the plasma Ar+ ion hit and sputter
the target is the main mechanism in plasma sputtering method.

• The target atom is knocked out by Ar+ ion, the knock force is so big and can
accelerate target atom a high speed. With such velocity, the target atom can hit and
attach to substrate surface deeply.

• The film density is good than evaporation.

Plasma CVD
Gases are dissociated by r.f. or dc glow discharge and atoms deposited on
the substrate.

Direct current sputtering is used when the target is electrically conductive.

Radio-frequency sputtering, which uses a RF power supply is used when the target is a
non conductor such as polymer.

DC = 1000 volts
Vacuum = 10-3 Pa
 PVD – Ion Plating
 Ion plating is an atomistic deposition process that utilizes continuous or periodic
bombardment of the substrate and depositing atoms of film material by atomic-
sized energetic particles.

 The bombardment prior to deposition sputter cleans the surface.

 Bombardment during deposition is used to obtain good adhesion, densify the

depositing material, aid in chemical reactions, modify residual stress, and
otherwise modify the structure, morphology, and properties of the depositing film
or coating.

 It is important, for best results, that the bombardment be continuous between the
cleaning and the deposition portions of the process in order to maintain an
atomically clean interface.
 PVD – Ion Plating
1. A third variation of the PVD process is ion plating.

2. Metal is evaporated thermally and plasma is established to ionize the

evaporating species

3. Evaporant ions bombard the substrate with energy

4. They physically implant into the substrate to produce an extremely

strong coating bond.

5. Sputter and ion plated coatings are used in design for very thin films for
electrical, optical and wear-resistant applications.

6. The wear properties of tools are widely enhanced by hard thin film
coatings.
PVD applications
 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 polish 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.
 Chemical vapour deposition
Chemical vapour deposition or CVD is a generic name for a group of
processes that involve depositing a solid material from a gaseous phase

PVD differs in that the precursors are solid, with the material to be
deposited being vaporized from a solid target and deposited onto the
substrate
Precursor gases (often diluted in carrier gases) are delivered into the
reaction chamber at approximately ambient temperatures. As they pass over
or come into contact with a heated substrate, they react or decompose
forming a solid phase which and are deposited onto the substrate. The
substrate temperature is critical and can influence what reactions will take
place.
Examples Ni(CO) for the deposition of Ni
4

SiH4(g) + O2(g) ---> SiO2(s) + 2H2(g) [oxidation] @ 450 ºC

use to deposit: Al2O3, TiO2, Ta2O5, SnO2, ZnO, . .

WF6(g) + 3H2(g) <===> W(s) + 6HF(g) [reduction] @ 300 ºC

use to deposit: Al, Ti, Sn, Ta, Nb, Cr, Mo, Fe, B, Si, Ge,,
Chemical Vapour Deposition
CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the reactor chamber

Reactor chamber – Chamber within which deposition takes place

Substrate loading mechanism – A system for introducing and removing
substrates, mandrels etc

Energy source – Provide the energy/heat that is required to get the

precursors to react/decompose.

Vacuum system – A system for removal of all other gaseous species other
than those required for the reaction/deposition.

Exhaust system – System for removal of volatile by-products from the

reaction chamber.

Exhaust treatment systems – In some instances, exhaust gases may not be

suitable for release into the atmosphere and may require treatment or
conversion to safe/harmless compounds.

Process control equipment – Gauges, controls etc to monitor process

parameters such as pressure, temperature and time. Alarms and safety
devices would also be included in this category
 Chemical Vapour Deposition
• Nickel deposition by CVD method finds application on glass containers
to make explosion or shatter resistant glasses.

• All surfaces in the reaction chamber get coated.

Advantages:
• high growth rates possible
• can deposit materials which are hard to evaporate
• good reproducibility
• can grow epitaxial films (high quality crystal growth)

Disadvantages:
• high temperatures (may soften tool steel > 700º)
• complex processes
• toxic and corrosive gasses
 CVD Applications
1. A newer process known as plasma assisted chemical vapor deposition.
This process is used to apply 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.