Metallic Coatings for Corrosion

Prevention

[Link]

Department of Metallurgy and

Materials Science
College of Engineering, Pune
Email:[Link]@[Link]
Tel:+91-20-2550 7264
 Purpose

 Functional
 Aesthetic

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 Metallic coatings
 Zinc,cadmium protect steel by sacrificial
behavior
 Metals such as nickel, tin, silver, copper, and
chromium will be noble to steel
 Corrosion of automobiles

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 Coatings
 Coatings
– Metallic
 Hot-dip
 Electro deposition
 Electroless
 Thermal Spray

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 Hot-dip
 Continuous
– Sheets,
– Wires,
 Batch
– Nuts
– Bolts
– Washers
– Beams,poles

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 Low melting point metals and alloys
 Zn, Al,Mg, and their alloys
 High melting points metals and alloys are
not hot dipped

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 Galvanized coating
 Al content is 0.1 to 0.2%
 Avoids formation of Zn – Fe intermetallics
 Al-Fe intermetallics are formed

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Comparison with aluminum coatings
 Hot dip coatings
 Hot-dip zinc coatings add corrosion
resistance by
– Barrier protection
– Galvanic protection
– Corrosion products act as secondary barrier
 Corrosion of hot-dip galvanized coating is
directly related to its thickness

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Service life (time to 5% rusting of steel surface)
Vs thickness of the coating for various
atmospheres

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 Hot dip coatings
Coatings giving substantial galvanic protection
i Galvanized (Low Al additions <1%) coatings
i Galvanneal coatings
q Hot-dip zinc-coated steel, heat-treated immediately after application
of zinc to promote interdiffusion of zinc and iron
i Galfan (5 wt% Al) coatings
q Corresponds to zinc aluminum eutectic
q Zinc-rich coating without intermetallics at coating/steel interface for
improved formability
i Galvalume (55 wt% Al) coatings
i Zn-Al-Mg coatings
i Superior in corrosion resistance to all above
i Presence of Mg makes corrosion products more stable
i Difficult to produce and not been commercialized till date
 Hot dip coatings
Coatings not giving galvanic protection
i Aluminum
- Type 1 coating (20 – 25 microns)
- Type 2 coating (30 – 50 microns) containing 5-11 %
silicon
- No sacrificial protection except in environments with
high chloride concentrations
i Lead alloy (Terne)
- Dull appearance
- Mainly lead containing 3-15% tin
- Excellent corrosion resistance, formability,
solderability and paintability
Corrosion losses of hot dip coatings in the
industrial environment of Bethlehem
 Problems of hot-dip zinc coating
 White rust formation

 Low corrosion resistance in aggressive

environment

 Poor paintability

 Poor weldability

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 Corrosion prevention
 When white rust formation occurs, the object
should be arranged so that their surfaces dry
rapidly
 To improve further corrosion resistance,
organic painting is done which is suitable for
aggressive environments
 As pure zinc coatings are smooth they have
poor paintability hence to improve it,
phosphating is done
 Galvannealing of these coating provides better
weldability as well as paintability
 Coating life enhancement done through
– Alloying addition
– Organic coating

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 Seven year exposure of galfan and
galvanized steel in a marine atmosphere

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Corrosion performance for thirteen year exposure of
galvanized, aluminum coated and galvalume sheet in
(a) marine atmosphere; (b) an industrial atmosphere

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 Zn-6%Al-3%Mg coated steel sheet is superior in
corrosion resistance to a Zn-0.2%Al and Zn-4.5%Al-
0.1%Mg coated steel sheet

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 Typical applications of continuous hot-dip-coated steel
sheet, wire, and tubing
Coating Product
Sheet Wire
Tubing
Zinc and Roofing, siding, doors, culvert, Nails, staples, guy wires, Electrical
Zn-5Al ductwork, housings, appliances, strand, tension conduit
autobody panels and structural members, rope,
components utility wire, fencing
Zinc-Iron Autobody panels and structural … …
components
Aluminum Mufflers, tail pipes, heat shields, Guy wires, strand, rope, …
type 1 ovens, toasters, flues, chimneys utility wire, fencing
Aluminum Roofing, siding, ductwork, culvert, Guy wires, strand, rope, …
type 2 silo roofs utility wire, fencing

Zn-55 Al Roofing, siding, ductwork, culvert, … …

mufflers, tailpipes, heat shields,
ovens, toasters, flues, chimneys,
silo roofs
Lead-tin Fuel tanks, radiator components, … Fuel lines,
valve covers, air-filter housings hydrauli
c lines
ELECTROPLATING
 Electroplating
 Application of metal coating on metallic
/conducting surface by electrochemical process
 Component to be plated is cathode
 Anode is metal to be deposited
 Electrolyte
 Cathode : M+(aq) + e = M(s)
 Anode : M(s) = M+(aq) + e
 Direct Current

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 Purpose
 Appearance
 Protection
 Special
surface properties
 Engg/mechanical properties

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 Ingredients of plating bath
 To provide source of metal
 To form complexes with ion of deposited
metal
 To provide conductivity
 Stabilize solution against hydrolysis
 To act as buffer to stabilize pH
 Modify physical form of deposit
 Help in dissolving anode

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 Copper plating
 Alkaline bath
– Composition (g/L): Copper cynide-45,sodium
cyanide - 68, Rochelle salt- 45 – 75, Potassium
hydroxide- 8-15,
– Operating condition : Temperature – 55 to
70⁰C,
– Voltage – 6 V,
– Anode – Copper,
– Current density- 2 to 5 A/dm2

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 Acid plating bath
 Acid bath:
 Composition (g/L): Copper sulfate -
200,Sulfuric acid – 45-75
Operating condition : Temperature – 20 to 50⁰C,
– Voltage – 6 V,
– Anode – Copper,
– Current density- 2 to 10 A/dm2

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 Ni Plating
– Watts solution :
– Composition (g/L): Nickel sulfate -225-400,
Nickel chloride – 30- 60, boric acid – 30 -45,
– Operating condition : Temperature – 45 to
65⁰C,
– Voltage – 6 V,
– Anode – Nickel,
– Current density- 3 to 11 A/dm2
– Used for getting high hardness , wear &
corrosion resistance

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 Applications of electroplated
coatings
 Sn, Cr for steel strip in food packaging
and other containers
 Galvanized: steel strips, sheets,
stampings, forging, wire, and screw
machine products
 Zn, Cd: fasteners and other hardware
 Cr: gun bores
 Electroplating
i Copper plating
 Performs a lubricating function in deep drawing and
wire drawing operations
 Promotes adhesion of rubber bonded to steel

 Used where improved lubricity and wear resistance

against steel are desired (bushings etc)

 Heat transfer, electronic circuits

i Cadmium plating
 Used for marine environments, (Components of

repeated use)
i Tin plating
 Provides good ductility and corrosion resistance to

steel
 Extensively used in food preservation containers
Problems of electroplated coatings
 Hydrogen embrittlement of steels is a major
problem in all types of cyanide zinc plating
 Corrosion is rapid in industrial and marine
locations
 Zinc plated steel is not used for equipment that
is continuously immersed in aqueous solutions
 It must not be used in contact with foods and
beverages because of dangerous health effects
 Cadmium is highly toxic and it has been
banned in many industries

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 Remedial measures
 When no embrittlement whatsoever can
be tolerated, mechanically deposited zinc
is the preferred alternative
 Corrosion resistance is enhanced by
organic paintings for general outdoor
service
 Zinc alloy plating has developed to give
higher performance
 Tin coating used foods and beverages
cans

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Cont…
 Cadmium is highly toxic and it is
replaced by zinc and its alloy plating
 Zinc-iron (15-25%) plating has good
weldability and ductility
 Zinc–cobalt (0.6 to 2%) plating has
better abrasion and corrosion resistance
 Zinc-nickel (5-15%) gives highest
corrosion resistance of all the
electroplated zinc alloys

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 Pollution prevention
 Replace Cd with Zn
 Use trivalent Chrome instead of hexavalent
Chrome
 Ozone depleting solvents chloroflurocarbon
and trichloroethane are not used

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 Electro less Ni Plating
 Deposition without use of electric current
 Autocatalytic chemical reduction of Ni ion
by hypophosphite, aminoborane
 Corrosion & wear resistance
 Uniformity is better
 Solderable
 Chemicals are costly
 Brittle coating, slower plating rate

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 Composition (g/L)
 Nickel sulfate-21
 Reducing agent–Sodium hypophosphite-24,
 Lactic acid – 28,
 Lead – 1 ppm, propionic acid-2
 Operating condition : Temperature – 85 to 95⁰C,
 Plating rate-25 µm/h
 aminoboranes,sodium borohydride
hydrazine

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 Electro less Cu Plating
 Copper sulfate/Copper chloride/nitrate
 Reducing agent-Formaldehyde,dimethylene
borane, hypophosphite, sucrose, glucose
 Operating condition : Temperature – 20⁰C,
 Plating rate-0.6 µm/h
 PCB, Decorative plating on plastics

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 Sheet lead is used to line tanks hold ing
corrosive liquids, such as acids, which
would eat through other metals.
 Pure aluminum is used mostly as cladding
material on aluminum alloys or as
protecting coating for other metals.

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 Tin is used in the production of tinplate
(steel coated with tin) used for food
packaging,
 Tin is used as an alloy in metallic coatings.
 Nickel plating is used

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 Applications include vacuum deposition of
thin films and coatings used in the
manufacturing of electronic devices,
integrated circuits and optical products.

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 Cr is used in plating to produce a hard,
beautiful surface and to prevent corrosion.
 in fabrication of plated products for
decoration or increased wear resistance
 Gold and Silver plating is used

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What should be the product shape?
Almost all shapes can be electroplated

Selected applications are:

Piston rings, Micrometers, Bushings,
Crankshaft, Cutting tool, Gun
barrel, Hydraulic cylinder etc.

Parts with sharp cornered grooves, bosses

and undercut are difficult to plate
 Sources of Hydrogen
 Steel making process, fabrication or
service
 H+ plate out during electroplating.
 H+ absorption during acid pickling.
 Furnace atmospheres of H2 or cracked
NH3 during heat treatment of steel.
 Hydrogen pickup during welding.
Service Environments
 Summary
 Most of the Automobile components are prone
to corrosion
 Control measures are
– Removal/taming environment
– Metallic coatings
– Conversion coatings
– Inhibitors
 Thank You

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 Electroplated cadmium coatings represent approximately 9% of
cadmium total use. Cadmium coatings have good lubricity, are easy to
solder and possess other properties which are essential for reliable
service life of many engineering components.
 Cadmium is normally applied by electrodeposition from cyanide or
acid solutions in barrels or vats. Cadmium can also be applied by
mechanical plating, vacuum deposition and metal spraying, but
generally only electroplated Cadmium is of commercial importance.
 electroplating of Cadmium became widely used as a protective coating
on iron and steel.

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 aluminum is its self forming microscopically thin surface layer of
aluminum oxide. This layer is so thin that it is measured in atomic
units. The air-formed film on new aluminum surfaces is about 2.5 nm
thick, while the film on aluminum that is several years old may be 10
or more nm thick. The film is composed of two parts:
 A thin, inner barrier layer
 A much thicker bulk outer layer which is more permeable than the
inner barrier layer
 Chemically, the film is a hydrated form of aluminum oxide. The
corrosion resistance of aluminum depends upon this protective oxide
film. which is stable in aqueous media when the pH is between about
4.0 and 8.5. The oxide film is naturally self-renewing and accidental
abrasion or other mechanical damage of the surface film is rapidly
repaired. The conditions that promote corrosion of aluminum and its
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alloys, therefore, must be those that continuously abrade the film