Vous êtes sur la page 1sur 48

Corrosion Protection by Coatings

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

Electroless plating: chemical reduction of metal-salt solutions,


precipitated metal forms a adherent layer eg. Electroless Ni
Cementation
Tumbling the work in a mix (metal powder+flux) at
high T
Powder metal diffuses into base metal
Eg. Al, Zn
Thermal Spraying
A gun simultaneously melts and propels small
droplets
Feedstock: powder, rod, wire, liquid
Flame-powder spraying
Flame-wire spraying
Plasma spraying- 12,000C, powder feedstock
Coating characteristics:
Porosity (can be filled with thermoplastic resins for
Corr Resist.) , any thickness, adherent, can be applied
on fabricated structures
Classification of coatings
All coatings provide barrier protection
Barrier between corrosive environ & metal
Coatings can get damaged during shipment/use
Galvanic action at the base of the scratch-
performance
Noble coatings
Only barrier protection
Ni, Ag, Cu, Pb, Cr
Sacrificial coatings
Barrier protection
Cathodic protection
Current flow at defects in noble/sacrificial coatings

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

Hot dilute chromate solution


hydrated aluminum oxide (boehmite) has a greater
seal provides better protection
volume than the aluminum oxide
Oxide coating may be dyed for
Steam/hot water exposure for several minutes
colors

Anodized coats provide good base for paints on Al


Chromate coatings
On Zn
Immerse in acidified sodium dichromate solution (200
g/l) for few sec at RT, rinse, dry
Zn chromate surface- slight yellow
Protects against spotting/staining by condensed
moisture
Atmospheric corrosion resistance
For Zn-Al coatings and Cd coatings, too
Organic Coatings
Physical barrier between the substrate and the corrosive
environment
May also serve as a reservoir for inhibiting compounds
Liquid-applied organic coatings
Suitable for atmospheric corrosion protection & mild corrosive
conditions
Liquid
Solvent
Carries the dissolved/suspended resin & inert pigment particles
Solvent evaporation cures the coating
Industrial coatings are further cured by baking below ~300C
Resin
Provides the chemical & corrosion resistance
Pigment
Decreases permeability, provides opacity & colour => shields the cured resin
from degrading UV exposure
May possess corrosion inhibition function
Minor additives
Improve coating flow, emulsification, uniformity, reduce pigment settling
Painting system Conditions
(suggested)

Unpainted Structural steel embedded in concrete, or protected by fire-


proofing membrane in dry interiors

Latex or 1 coat Interior- dry, very mild

Oil base Exterior: normally dry, life >6 years

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

Zn-rich Chemical exposure: pH 5-10

Epoxy Chemical exposure: mild organic solvents, aliphatic hydrocarbons

None suitable Chemical exposure: severe- oxidizing chemicals, strong organic


solvents, high T exposures
Zn bearing coatings
Zn powder as a filler
Binder one of the organic resins
Paints with Zn pigments- 80 wt % pigment out of which 20 wt % is Zn
oxide
Zn/ZnO combination inhibits atmospheric rusting in primers/finish coats
Excellent coverage, adhesion & abrasion resistance
Less galvanic protection
Good for rural & mild industrial atmosphere
Zn-rich coatings- 92-95 wt % metal Zn when dried, with no oxide
Good galvanic protection
Zn seals coating defects with Zn corrosion products
& at defects provides galvanic protection
undercutting at paint/metal interface is suppressed- Unique
characteristic!
To ensure electrical conductivity surface preparation is critical
Remove all surface oxides/organics
Zn is added immediately before spraying to minimise settling
Popular in aggressive atmospheres
Zn rich primers are used under automotive topcoats (topcoats provide
decorative finish)
Marine structures, ship hulls, ship superstructures, highway bridges, sewage &
water treatment plants, many other
Not suitable at pH<5 or >10 => Zn readily dissolves
Exposure tests for evaluation
Accelerated lab tests
field exposure tests - too long for
development programs/quality control
Accelerated lab test to simulate same
mechanism of degradation as in
service/field
Salt fog test
Accelerated atmospheric exposure test
Spray of salt-laden water in closed high
humidity chamber
Conditions approach oxygen saturation,
and continuous immersion as the spray
condenses on specimens
Coatings are usually scribed to create a
well defined defect and attack at the
scratch is observed
Alternate immersion cycles
To enhance undercutting
50-75 % reduction in time required for equivalent undercutting as
compared to continuous salt-fog tests
0.25 h immersion in 5% NaCl, air saturated
1.25 h drying at room temperature, ambient humidity
22.5 h exposure at 48C & 90% relative humidity
Accelerated Lab test ranking may not conform with the
field tests
Final qualification of coated product is by service
testing in the field
Coupons/panels exposed in atmosphere or in process streams
Periodic examination
Degradation and failure of coatings
Penetration by reactant species water, oxygen,
SO2, other electrolytes
Cathodic disbondment (salt fog test):
Attributed to formation of OH- from reduction rxn
O2 + 2H2O + 4e 4OH- (1)
Coatings: macroscopic & microscopic defects
Pinholes, voids, mechanical scapes, scratches
Allow access of the environ to base metal
Anodic rxn Fe Fe2+ + 2e at the defect
Coupled to nearby cathode beneath the coating
O & H2O must migrate through the coating for (1) to occur
Alkalinity reacts with organic polymer to disbond the coating
Oxide lifting
Anodic corrosion products (oxides) accumulate under the
coating
Lifting action and resultant undercutting
Occurs only during alternate wetting & drying (not continuous
immersion)
Possible Mechanism
-flocculent oxide corrosion
products in water are
compacted by drying
-rust/scale forms an inner layer
of Fe2+ & Fe(OH)2 ppt
-these oxidize to Fe3O4
-Lamellar compact oxide
corrosion product layers are
formed from alternate
wetting/drying cycles.

Cathodic rxns occur at the exposed metal surface/ or on magnetite (conducting)


Electrochemical corrosion during wet exposure
Deposition of colloidal corrosion products during dry periods- buildup of compact products
- Conversion coatings inhibit disbondment
Electrochemical testing
EIS (Electrochemical impedance spectroscopy)
Advanced research tool for coating development &
evaluation
Development of an electrical equivalent circuit to
simulate the electrochemical behavior of the metal-
electrolyte interface
Generally suitable circuit for modeling the coated metal
systems

Rp= polarization resistance


R = solution resistance
Rcp = Coating pore resistance
Cd = double-layer capacitance
Cc= coating capacitance
Areas for using EIS

fast evaluation of coatings


inhibitor performance
extremely low CR (<104 mm/year)
rapid estimation of CR ( 30 min to 24 h)
Low conductivity media
Ideal Resistor

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

apply a sinusoidal voltage purturbation


(AC potential) to a cell and measure
the current through the cell => get
impedance
Electrochemical Impedance is normally
measured using a small excitation
signal.
This is done so that the cell's response is
pseudo-linear.
In a linear (or pseudolinear) system, the
current response to a sinusoidal potential
will also be sinusoidal at the same
frequency but shifted in phase.
Pseudo-linear response
Impedance analysis of linear circuits is much easier than analysis of non-linear
ones
Electrochemical cells are non-linear (doubling the voltage does not necessarily
double the current response)
But it can be pseudo-linear if very small perturbation pulse is applied
1-10mV AC

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

v(t ) Vm sin( t ) sin( t )


Z Zm
i (t ) I m sin( t ) sin( t )
Impedance is expressed in terms of magnitude Zm, and a phase shift
Impedance as a complex function
complex number representation of impedance is more powerful for circuit
analysis purposes
vt Vm exp( jt )
it I m exp( jt )
vt
Z ( ) Z m exp( j )
it
using Eulers relationship: Imaginary Part
Real Part

Z ( ) Z m (cos j sin )

If we plot real Z on the abscissa and imaginary Z on the ordinate =>


Nyquist Plot
The Nyquist Plot with impedance vector

eqvt ckt with


one time
constant

each point on the plot is impedance at a given frequency,


low frequency data are on the right (no magnitude is depicted, only range)
impedance is a vector of length IzI and phase angle is (=arg Z)
The Bode Plot
It shows the frequency information
log IZI vs log (), and
Phase angle () vs log()
Log

Log
Fitting of EIS data

EIS data is analyzed by fitting it to an eqvt ckt model


Common circuit elements:

Circuit V-I Impedance


Component relationship
Resistor V=IR Z=R
Capacitor V=C dV/dt Z=1/jC
resistor: impedance is independent of frequency, has no imaginary component
Inductor V=L di/dt Z=jL
With only a real impedance component, the current through a resistor stays in
phase with the voltage across the resistor.
Capacitor: its impedance decreases as the frequency is raised.
Capacitors also have only an imaginary impedance component.
The current through an capacitor is phase shifted 90 degrees with respect to
the voltage.
Inductor: opposite to that of a capacitor i.e. impedance increases as frequency
increases, have only an imaginary impedance component.
Hence, the current through an inductor is phase-shifted -90 degrees with
respect to the voltage.
Combinations of ckt elements

series and/or parallel


series: Z = Z1+Z2+Z3+

1 1 1
parallel: ....
Z Z1 Z 2
Application of perturbation- centered on
free corrosion potential
cathodic protection potential
Modeling of Impedance Spectra

assuming a circuit made of different elements


Find/ fit values of elements
Relate these values to a physical phenomena
so that it reasonably represents a corrosion
process
Physical Significance of Circuit Elements

elements in the model should have physical significance in the


electrochemistry
Solution Resistance, R ~ Resistor,
it is calculated when EIS data is fitted to a model
Double Layer : Cdl
on a bare metal in an electrolyte ~ 20-60 f/cm2
Rp ~ resistor
Coating Capacitance : Cc
Virtual Inductor- a curve fitting ckt element
formation of a surface layer like passive layer or fouling
(accumulation of unwanted material on surface)
may result from errors in measurement, non-ideal potentiostat
Types of Models

In a physical model, each of the model's components is


postulated to come from a physical process in the
electrochemical cell
The choice of which physical model applies to a given cell is made
from knowledge of the cell's physical characteristics
EIS analysts can use the shape of a cell's EIS spectrum to help choose a
model for that cell
Models can also be partially or completely empirical.
The circuit components in this type of model are not assigned to
physical processes in the cell.
The model is chosen to give the best possible match between the
model's impedance and the measured impedance
Which is the best eqvt. ckt?

EIS spectrum
software packages to fit the spectra to
analogous circuits

possible equivalent circuits (a circuit model is not unique!)

physical model should be verified!


alter a single cell component (for example increase a paint
layer thickness) and see if you get the expected changes in
the impedance spectrum
Schematic Nyquist plot
showing effects of partial
diffusion control (either
concentration polarization
or diffusion through a
coating) with Warburg
impedance W
Degreased, alkaline derusted, coated with 8 m
polybutadiene
v. high z

Degreased, coated with 8 m polybutadiene


decrease in low frequency z, which measures Rcp
rust at coating/metal interface induced coating
defects => Rcp
Cc (measured by linear portion of curves is same for
(a) & (b) => coating shows little/no water uptake that
would affect Cc.

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