Module 4 - Corrosion Protection
Module 4 - Corrosion Protection
Corrosion Control
Topics:
Corrosion protection
• Cathodic protection – sacrificial anodic and impressed
current cathodic protection (ICCP)
• Advanced protective coatings: Anodic and cathodic coating
• Electroplating and Electroless plating
• Vapor Deposition – Physical Vapor Deposition (PVD) and
Chemical Vapor Deposition (CVD).
• Alloying for corrosion protection –
• Basic concepts of Eutectic composition and Eutectic mixtures
- Selected examples – Ferrous and non-ferrous alloys.
Control of Corrosion
a) Proper designing
b) Proper selection of metal or alloy
c) Cathodic protection (Sacrificial and Impressed
current cathodic protection)
d) Corrosion inhibitors (Anodic & Cathodic
inhibitors)
e) Changing the environment
f) Protective coatings (Galvanizing & Tinning)
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Design Aspects for corrosion protection
• Avoid sharp corners and sharp edges
• While working with dissimilar metals, larger anodic area and lesser cathodic
area are necessary
N2 H4 + O2 N2 + 2 H2O
o Neutralisation of acidic environment containing H2S, SO2, HCl, CO2 etc., can
be done by introducing alkaline neutralisers like ammonia gas, lime,
naphthionic soaps, caustic etc., (Used in refinery to protect the
equipment).
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Cathodic Protection
Principle: Metal to be protected is forced to behave as cathode
Two methods of cathodic protection known are :
i) Sacrificial anodic protection
ii) Impressed current cathodic protection (ICCP)
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Sacrificial anodic protection
Sacrificial anodic protection - concept
e-
Mg
Mg2+
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Corrosion control
ii) Impressed current cathodic protection:
https://www.youtube.com/watch?v=QYd9ENn1nP0
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
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lines, oil pipe lines, transmission lines, ships etc.
Impressed current cathodic protection
Impressed current cathodic protection - concept
Corrosion current of equal magnitude but opposite in direction applied to nullify corrosion current
e-
DC Source
/Rectifier
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Coating Techniques
Methods of metallic coatings:
a) Hot dipping
b) Metal cladding
c) Electroplating
d) Electrolessplating
e) PVD
f) CVD
a) Hot dipping:
i) Galvanizing: Dipping the base metal iron in molten zinc metal solution
ii) Tinning : Dipping the base metal iron in molten tin metal solution.
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Protective coatings
Metallic coatings:
a) Anodic coatings
b) Cathodic coatings
a) Anodic coatings (Using sacrificial anodic coating):
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.
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Protective coatings
Cathodic coatings:
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https://youtu.be/NuU0JOwp31g
Eg. Tin coated steel containers for storage of food stuff such
as Fruit pulp etc.
Surface preparation before coating
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.
a) Mechanical cleaning:
o Useful for removing loose scales and rust.
o Hammering, wire brushing, grinding, pneumatic blasting, polishing are the methods
commonly used.
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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.
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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.
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Electroplating
https://www.youtube.com/watch?v=qI6YY634MOA
• Base metal such as Fe, Cu and Al and their alloys are electroplated
with Au and Ag to increase commercial and decorative value.
• When current density is low, it forms well formed deposit. Because electron
transfer is slow compared with surface diffusion and the adatoms finds the most
favourable position.
• As the applied voltage is increased, the current density rises till it reaches a
limiting value. Surface diffusion is slowed down compared to electron transfer as
the current density is increased. Due to this reason, the adatoms may not reach
the most favourable positions.
• Organic Additives:
• Levellers – To facilitate even deposition. Levellers occupy those regions to
reduce electron transfer there. e.g., sodium allyl sulphonate
• Brighteners: to produce microscopically fine deposits. Enhances the ability
to reflect light. Glossy, shiny and bright appearance e.g., coumarin,
thiourea
• Structure modifiers or stress relievers: Electrodeposits are internally
stressed and develops microcracking of of deposits. e.g. Sachharin
• Wetting agents: facilitate H2 gas evolution and entrapment is prevent
which may make it brittle and forms blisters. e.g., sodium lauryl sulphate
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.
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.
o 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 to get uniform and adherent
deposition. 24
Important Factors of electroplating
o Additives to electrolytic bath
Additives to electrolyte are added in small quantities to get
strong adherent deposition.
Commonly used additives are gelatin, glue, glycine, boric acid
etc. and brighteners for bright plating.
o pH of the bath:
For a good electrodeposit, the pH of the bath must be properly
maintained. For most plating baths, pH ranges from 4 to 8.
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.
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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.
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Electroplating
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Electroplating with Nickel on Copper
Metal ions reduced to the metal wth the help of reducing agents.
Once a metal is formed, it gets plated over a catalytic surface.
Applications:
1. This process is widely used to produce decorative coatings on plastic parts those are
resembling shiny metal.
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.
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PVD: – 1. Thermal Evaporation Method
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PVD: 2 – Sputtering Method
Sputtering is a process whereby particles are ejected from a solid target material due to
bombardment of the target by energetic particles.
Sputtering is done either using DC voltage (DC sputtering) for metals or using AC voltage
(RF sputtering) for dielectric materials and polymers.
The gas atoms are ionized and they
bombard the material to be coated.
• 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.
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Sputtering offers the following advantages over other PVD methods used in VLSI
fabrication:
1) Sputtering can be achieved from large-size targets, simplifying the deposition of thins
with unifrom thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and simply
adjusting the deposition time;
3) Control of the alloy composition, as well as other film properties such as step
coverage and grain structure, is more easily accomplished than by deposition through
evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be done;
5) Device damage from X-rays generated by electron beam evaporation is avoided.
5. Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications.
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Applications
1. This process is widely used to produce decorative coatings on
plastic parts those are resembling shiny metal.
PVD differs in that the precursors are solid, with the material to be
deposited being vaporised 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.
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CVD Apparatus
A CVD apparatus will consist of several basic components:
Gas delivery system – For the supply of precursors to the reactor chamber
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
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in this category
Advantages of CVD over PVD:
One of the primary advantages is that CVD films are generally quite conformal, i.e.,
that the film thickness on the sidewalls of features is comparable to the thickness on
the top.
Another advantage of CVD is that, in addition to the wide variety of materials that
can be deposited,
. they can be deposited with very high purity.
This results from the relative ease with which impurities are removed from gaseous
precursors using distillation techniques.
Other advantages include relatively high deposition rates, and the fact that CVD often
doesn’t require as high a vacuum as PVD processes
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CVD also has a number of disadvantages:
2. CVD precursors can also be highly toxic (Ni(CO)4 ), explosive (B2H6), or corrosive (SiCl4).
3. The byproducts of CVD reactions can also be hazardous (CO, H2, or HF).
4. Some of these precursors, especially the metal-organic precursors, can also be quite
costly.
5. The other major disadvantage is the fact that the films are usually deposited at
elevated temperatures. This puts some restrictions on the kind of substrates that can
be coated.
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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. used largely in the production of semiconductors
5. Thin-film coatings are key to the manufacture of many electronic devices. They
involve the application of dopant, sealant and other microelectronic paste.
6. Thermal evaporation is a low cost process, but all these processes are normally
batch processes because of vacuum chamber requirements.
7. CVD is also used to produce synthetic diamonds.
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Additional Figures
Based on the concepts discussed already
Sacrificial Anodes
• Galvanization of Steel
• Dip steel sheet in molten zinc. Get a pretty thin coating.
• Zinc will be anode. Steel exposed by crack is the cathode.
Since we have a huge anode having to be served by a
small cathode, corrosion rate will be slow.
Larger Area
Large area
(Zinc)
anode (zinc)
An example of a unfavorable area ratio. Bad deal: huge cathode, tiny anode
An example of a favorable area ratio. Bad deal: huge cathode, tiny anode
Another Example
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Aluminium anodes mounted on a steel jacket structure –
using galvanic corrosion for corrosion control! Called
cathodic protection (aka sacrificial anode)
Sacrificial Anode for a Pipeline
Passivation of the anode
• We have two examples already. Stainless and aluminum.
• A thin oxide layer forms on the surface and isolates the metal from the
environment.
• Zn, Mg, Cu and Ti are also capable of passivation under normal
conditions of operation.
• Steel will also passivate in the presence of an alkaline environment, such
as rebar in concrete.
• Corrosion inhibitors. Some of these, such as the chromates, are capable
of coating a steel and passivating it.
• Coatings, paints, etc.
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.
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