Metallic Coatings
Other Inorganic Coatings
Paint Coatings
Other Forms of Organic Coatings
Pre-treatment Before Coating
Metallic Coatings
Methods of application
Dipping
Electroplating
Spraying
Cementation
Diffusion
Method selection considerations
Corrosion resistance that is required, expected
lifetime of component, # of parts being produced,
environmental considerations
Hot Dipping
Immerse metal (usu. Steel) in molten metal
bath (Zn/Al/Al-Zn)
Continuous process: e.g. galvanizing sheet
Batch process: galvanizing fabricated parts,
nuts, bolts, fasteners
Electroplating
Substrate is made cathode
Aqueous electrolyte of depositing metal
4-30 m thick
Zn, Cd, Cr, Cu, Au, Ni, Sn, Ag and alloys Sn-Zn, Zn-Ni, brass,
bronze, gold alloys, nickel alloys
Electroplated Zn more uniform thickness and other
surface characteristics vs. hot dipped- automobile body
sheets
Cr/Ni on steel
-coating is undermined
-coating should have minimum pores
-thick
Zn/Cd on steel
-base metal is cathodically protected
-degree of porosity inconsequential
-thick- longer protection
Area over which sacrificial protection extends
f( solution conductivity)
Cathodic current densities fall off with distance
from anode
Fall off rate is high in distilled/soft water
It is low in seawater
eg. 3mm wide Zn coating defect on steel begins to
show rust in the center in soft water
Several feet wide defect in seawater no rusting!
Zn coatings
Barrier and Galvanic protection
Corrosion products- Zn compounds (carbonate/hydroxides)
White, colorless
Rusting appears sooner with severity of atmosphere
Rural (0.2-3 m/yr) < marine (0.5-8) < industrial atmosphere (2-
16)
Hot dip galvanizing
Metallurgical bonding (diffusion) to steel => Zn-Fe alloys
very adherent
Continuous process thinner coatings
Batch process- thick
0.1-0.2 % Al addition suppresses Fe transport into coating
USE: atmospheric corrosion protection of steel- roofing,
automotive- truck and bus parts, fencing, A/C, farm implements
Electrogalvanized- electrodeposited
Zn alloy coatings too- Zn-Fe, Zn-Co, Zn-Ni
Galvanizing provides good surface for organic
coatings
Extend life of Zn coating
Aqueous envorn at RT
Corro rate is lowest in pH 7-12
Seawater: 0.13 mm thick no rust for ~ 5 yr
Aerated hot water >60C
Reversal of polarity- Zn develops noble characteristics
pitting is possible
Waters high in carbonates & nitrates favor the reversal
Waters high in chlorides & sulphates decrease reversal
Normally
porous Zn(OH)2 product
insulating
Zn is anodic
Reversal
ZnO
electrically semi-conducting
in aerated waters, works as oxygen electrode with
noble potential
Ni Coatings
Usually electroplated
Cu underlayer
To reduce required thickness of (expensive) nickel layer
To facilitate buffing operation, Cu is soft
Ni underlayer is used in automotive industry for
microcracked Cr deposition
Minimum prescribed thickness
For indoor exposures: 0.008-0.013 mm
Outdoor: 0.02-0.04 mm
Thicker coatings for use near sea coast/ industrial environments
Thinner for dry, unpolluted environs.
Chemical industry : 0.025 to 0.25 mm
Fogging: In industrial atmospheres,
reflectivity from Ni sulphate film formation
Coat with very thin 0.0003 mm Cr overlayer
Electroless nickel
For chemical industry
Ni is reduced by hypophosphite at boiling point
Typical solution
NiCl2.6H2O 30g/l; Sodium hypophosphite 10g/l; sodium
hydroxyacetate 50 g/l, pH: 4-6
Deposit is a Ni-(7-9 %) P alloy
Corrosion resistance is comparable to electrolytic Ni
Adv: Uniform coating even on intricate parts
Cadmium coatings
By electrodeposition
Cathodic protection to steel
Lower p.d. between steel/Cd as compared to steel/Zn
it maintains potential of steel
below the critical pot for SCC, and
Above the pot for H cracking
More reliable protection than Zn in moist environ
expensive than Zn
Brighter metallic appearance
Better electrical contact
Better solderability, used in electronic equipment
More resistant to attack by aqueous condensate/salt spray
Coeff. Of friction () is lower than Zn, low torque resistance; use:
fastening hardware & connectors (where frequent dismantling is
required)
Extensively used in aerospace applications
Cd coatings
Resists attack (unlike Zn) by alkalies in aqueous
media
Like Zn it is corroded by dilute acids and aqueous
ammonia
Cd salts (corrosion products) are toxic than Zn
salts
No contact with food products
Galvanised coatings are OK for drinking water only not for
food
Cd plating solutions toxic, waste disposal problem
Cd replacements are being sought
Tin Coatings
Tin is active to steel in most food products
Galvanic + barrier protection
On the outside of a can, Sn is cathodic to Fe
barrier protection
On the inside, Sn is always anodic cathodic
protection
Potential reversal occurs from complexing of stannous
ions, Sn2+ by food products => aSn2+
potential of Sn becomes more active
Tin salts are non-toxic, tasteless, colorless
Tinplate (low C-steel strip coated with tin) food/beverages
containers- millions of tons of tinplate
Electrodeposited more uniform and thin than hot-dipped
tinplate is heated Sn melts=> FeSn2 form, then passivated in
chromic acid/sodium dichromate
Can-makers tinplate has 5 layers
Steel sheet 200-300 m
FeSn2 layer 0.08 m
Tin layer, 0.3 m
Passive film 0.002 m
Oil film 0.002 m
Galvanic protection is lost in presence of dissolved O
Faster tin corrosion aSn2+ increases
not complexed enough corrosion of Fe at pores in the coating
food should not be retained in tinplated cans after opening
Sn has high hydrogen overpotential H+ reduction is
insignificant
Inorganic Coatings
Glass coatings (alkali borosilicates)
Vitreous enamels (porcelain enamels)/glass linings
Fused on metals
Powdered glass is applied on pickled steel (Cu, brass, Al too) surface
Heated in a furnace to glass softening T (750-850C)
powder melts, flows, and then hardens to a smooth, durable vitreous coating
Several coats may be applied
Decorative
Corrosion protection
Resist strong acids, mild alkalies
excellent barrier to water/Oxygen- pore free coatings are must
Weakness: Susceptible to mechanical damage, cracking by thermal
shock
Crazing : network of cracks
Repair- tamping Au/Ta foil into cracks
Gasoline pump casings, advertising signs, decorative building panels,
plumbing fixtures, appliances etc
Aeroplane exhaust tubes- high T gases
Long life in soils, too
Portland Cement coatings
Low cost
CTE ~ steel
Ease of application/repair
Centrifugal interior of pipings
Trowelling, spraying
5- 25 mm thick- may be reinforced with wire mesh
8-10 days cure is required
Use:
Cast iron, steel water pipes- water & soils sides
Interior of hot/cold water tanks, oil tanks
protects against seawater, mine waters
Limitations:
Damage from mechanical/ thermal shocks
Sulphate rich waters attack the cement
Chemical conversion coatings
In-situ chemical reaction with metal surface
Phosphate coatings (steel)
Parkerizing/Bonderizing
Brush/spray the cold/hot Mn or Zn acid orthophosphate (eg.
ZnH2PO4 + H3PO4) solution
Sometimes accelerators (Cu2+, NO3-) are added
Reaction product porous metal phosphate firmly bonded
to steel surface
Useful as a base for paints- good adherence
Decreases the tendency for corrosion to undercut the
paint film at scratches
Auto bodies- first & most important layer is ~3 m
phosphate coating thinnest yet it anchors
subsequent layers
Oxide coatings on Al (anodizing)
Room T anodic oxidation in suitable electrolyte (e.g. Dilute H2SO4) at >100
A/m2.
Al2O3 coat: 0.0025- 0.025 mm thick
Must be hydrated to improve protection
(sealing) to close the porous Al oxide
Vinyl, coal-tar epoxy, Frequent wetting by fresh water: condensation, splash, spray,
epoxy, chlorinated frequent immersion
rubber
Vinyl, coal-tar epoxy, Frequent wetting by salt water
epoxy, Zn rich
Vinyl Chemical exposure: acidic pH < 5
E
R
I
follows Ohms law at all V and I
R is independent of frequency
AC I and V signals though a resistor are in phase
In reality, ideal resistors rarely exist
some other complex circuit elements that do not
fulfill all of the above conditions => Impedance
Like resistor an impedance is a measure of resistance
to the flow of current in a circuit
Electrochemical Impedance
small
excitation
signal
Purturbation (excitation) v(t ) Vm sin( t )
signal
v is potential at time t
Vm is the amplitude
2f
is the radial frequency, rad/s
f is in Hz
In (pseudo) linear system,
response signal i(t) is shifted i(t ) I m sin( t )
in phase by
Z ( ) Z m (cos j sin )
Log
Fitting of EIS data
1 1 1
parallel: ....
Z Z1 Z 2
Application of perturbation- centered on
free corrosion potential
cathodic protection potential
Modeling of Impedance Spectra
EIS spectrum
software packages to fit the spectra to
analogous circuits
Uncoated
Bode plots for AISI 1010 steel exposed v. low z (Rcp & Cc are absent, only Rp is
for 2 h to aerated 0.5 N NaCl present)
Rp is low => C. Rate
Drawbacks
Complex & expensive instrumentation
Difficulty in quantitative measurements at low
Occasional problems with data interpretation