Corrosion Protection Methods

Coatings

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: eg galvanizing sheet
Batch process: galvanising fabricated parts,
nuts, bolts, fastners

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 scratchperformance

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 (216)

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 atmospeheres,

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

food should not be retained in tinplated cans after
opening
Sn has high hydrogen overpotential H+ reduction is
insignificant

Al coatings
Steel is aluminized by hot-dipping/spraying/cementation
Molten bath Al+ Si to retard formation of brittle iron
aluminide layer
Oxidation resistance up to 680C
Use: automotive mufflers, oven construction, hot-dip Al coated
409 SS- auto exhaust systems: 760C
Al-44Zn-1.5Si: cathodic protection, excellent resistance to
marine and industrial atmospheres, and oxidation resistance at
high T

Sprayed Al coatings: sealed with laquers/paints

0.08-2mm thick, longer life than Zn in industrial atm.

Cemented Al coatings (Calorizing)

Al powder+ Alumina + NH4Cl as flux in Hydrogen atm at 1000C
Al-Fe surface alloy forms- resists oxidation in air/oil-refining
sulphurous atm up to 950C
Protect gas turbine blades (Ni based alloys) from oxidation

Cr coatings
Cr highly resistant to atmospheric corrosion
thin bight overlay over other coatings
Retains decorative appeal for long time
Extreme hardness
Low
Non-galling ( galling: wear caused by adhesion between
sliding surfaces)
Corrosion resistance

used where wear & abrasion resistance is required

Protects underlying Ni layer from fogging

Cladding

Cladding dissimilar metals

High-T roll bonding/ co-extrusion
Pressure welded diffusion bond
Composite sheet/plate/tubing has favorable
properties of both the alloys
eg. SS clad on to Cu- for corrosion resistance, retaining
thermal & electrical conductivity of Cu
Roll bonding thin Al alloy layer (active) on high
strength Al alloy plate
Sacrificial, pitting, exfoliation & SCC of high strength alloy is
inhibited

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

Troweling, 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,
protect 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 imp layer is ~3 m
phosphate coating thinnest yet it anchors
subsequent layers

 Oxide coatings on steel

Controlled high T oxidation in air
Or Immersion in hot conc. alkali solutions containing nitrate,
chlorates
Blue/brown/black in color (mostly Fe3O4)
Corrosion protection is obtained after rubbing in inhibiting
oils/waxes eg. Oxidized gun barrels

Oxide coatings on Al
Room T anodic oxidation (anodizing) in suitable electrolyte (eg. 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
hydrated aluminum oxide (boehmite) has a greater volume
than the aluminum oxide
Steam/hot water exposure for several minutes

Hot dilute chromate solution

seal provides better protection
Oxide coating may be dyed for
colors

 Anodized coats provide good base for paints on Al

MgF2 on Mg by anodizing in (10-30% NH4HF2) at 90120V - base for finishing treatments
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 futher 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
(suggested)

Conditions

Unpainted

Structural steel embedded in concrete, or protected by fireproofing membrane in dry interiors

Latex or 1 coat

Interior- dry, very mild

Oil base

Exterior: normally dry, life >6 years

Vinyl, coal-tar epoxy,

epoxy, chlorinated
rubber

Frequent wetting by fresh water: condensation, splash, spray,

frequent immersion

Vinyl, coal-tar epoxy,

epoxy, Zn rich

Frequent wetting by salt water

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

 Primer coats:
resins that have good adhesion to the metal
substrate and readility amenable to further
coating
Improve durability of top coats

Top coats
Have maximum resistance to weather & chemical
envorns.

 Oil based coatings (enamels)

Alkyd resins
2/3 rd of the coatings used for corrosion protection
Polymerize and cross-link by oxidation (air) during
drying/evaporation of the oil solvent
Ease of application & low cost
Suitable for steel surfaces exposed to atmosphere

Modified alkyds
Additional organic groups (modifiers)
Silicon modified alkyds- durability, gloss retention, moisture &
heat resistance
Marine maintenance, petroleum processing equipment
Amino-resin-modified aldehydes
High humidity applications (fridge, washing machines)
Phenolic modifications
For water immersion

 Vinyls
Do not cross-link during curing, soften with T
14% PVA (polyvinyl acetate- a copolymer) disrupts the 86%
PVC (polyvinyl chloride) chains to allow dissolution in
ketones
Curing: solvent evaporation deposits uncross-linked long
chain polymer- consolidates into a film (such coating are
called laquers)
Pigment: rutile TiO2
Multiple coats make the lacquers durable
Can act as primers for other more resistant top coats,
vinyl coatings partially dissolve in many organic solvents =>
good adherence

 Chlorinated rubber coatings

Thermoplastic
Cure by solvent evaporation (like vinyls)
Prepared by reacting Cl with natural/synthetic
rubber + add stabilizers/plasticizers
Resist water vapour penetration

 Epoxies
Thermosetting coatings
Highly cross-linked & unreactive ( difficult to top coat)

Mix dissolved resin (glycidyl ether + pigment) with curing

agent (polyamine/polyamide) before application
Curing agent co-polymerizes with resin
Polyamine is a smaller molecule => tight, more chemical resistant
coating
Polyamide => flexible coatings, slightly reduced resistance to
chemicals

Modified epoxies
Application-wise tailored properties
Coal-tar epoxies- coal tar as filler improves moisture resistance
Phenolic cross-linked epoxies: resistant to alkalies, acids, solvents
Coatings for tanks, cans, drums process equipment

 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

Surface preparation
Must for adherence & subsequent
performance
Poor coating applied to well-prepared surface
is better than vice versa
Time & expenses are justified
Contaminants
Oxides, scales, loose dirt, organic matter- grease,
oil

Specification

Description

Solvent cleaning

Oil, grease, soil, salt by cleaning with solvent, alkali, steam etc.
Does not remove rust/mill scale

Hand-tool
cleaning/ power
tool cleaning

Loose rust & mill scale, loose paint- hand/power toolchipping,

scraping, sanding, wire brushing, grinding

Blast cleaning

Removal of all visible rust, mill scale, paint, foreign matter by

blast (dry/wet using sand/grit/shot)

Pickling

Removal of all mill scale, rust by chemical reaction or electrolysis

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
scribe 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 nereby cathod 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
-flocculant 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 (<10-4 mm/year)
rapid estimation of CR ( 30 min to 24 h)
Low conductivity media

Ideal Resistor
R

E
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

v (t ) V m sin( t )

Purturbation (excitation)
signal

2f

v is potential at time t
Vm is the amplitude
is the radial frequency, rad/s
f is in Hz

In (pseudo) linear system,

response signal i(t) is shifted
in phase by

v (t )
i (t )

i (t ) I m sin( t )

Vm sin( t )
I m sin( t )

Zm

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

v t V m exp( j t )

it I m exp( j t )
Z ( )

vt
it

using Eulers relationship:

Z m exp( j )
Real Part

Imaginary 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()

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+

parallel:

1
Z

1
Z1

1
Z2

....

 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
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
coatingwith Warburg
impedance W

Validity of Spectra

Before attempting to model impedance spectra, be assured

that the spectra are valid.
When a sine wave is used as the perturbation, the
relationship between the current and applied voltage can
be characterized by
the ratio between the amplitudes of the voltage and the current
=> I Z I
and the phase shift between the vectors which represent the
instantaneous voltage and current.=> phase shift of the vector (a
complex number)

In mathematical terms, the impedance is a transfer

function relating (the Laplace transform of) a response
(e.g., current) to (the Laplace transform of) a perturbation
(e.g., voltage).

Conditions for validity

The transfer function can only become an impedance when

the following four conditions are fulfilled:
1. Causality: The response of the system must be a result only of the
applied perturbation.
difficult to verify (ASTM => equipment & cell)

2. Linearity: The relationship between the perturbation and response is

independent of the magnitude of the perturbation.
easy, generate spectra using higher and lower magnitude and verify the
modulus and phase angle values

3. Stability: The system returns to its starting state after the perturbation
is removed.
generate spectra from high to low freq and then from low to high freq.
(low freq. can upset the system as it takes longest)

4. Finite valued: The transfer function (impedance) must be finite as the

frequency approaches both 0 and and is continuous and finite
valued at all intermediate frequencies.

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.

Bode plots for AISI 1010 steel exposed

for 2 h to aerated 0.5 N NaCl

Uncoated
v. low z (Rcp & Cc are absent, only Rp is
present)
Rp is low => C. Rate

Drawbacks
Complex & expensive instrumentation
Difficulty in quantitative measurements at low
Occasional problems with data interpretation