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Cathodic Protection Methods

CP
Most widely used method
Can prevent corrosion of any metal/alloy exposed to any
aqueous electrolyte
Properly maintained system can provide corrosion
protection indefinitely
First: 1820s British used CP on copper fittings of wooden
sailing vessels
Suppression of toxic corrosion products allowed growth of marine
organisms => sailing speed
1920s, for buried steel pipelines of the USA in Gulf coast
oilfields
1950s, for steel hulled ships
Greatest use for coated C-steels
Extends service life of thousands of miles of buried steel
pipelines, oil & gas well casings, offshore oil drilling
structures, ships, water tanks, chem. equipt
CP criterion
CP: process whereby the corrosion rate of a metal
is decreased or stopped by decreasing the
potential of the metal from Ecorr to some lower
value (cathodic polarization) and in the limit to
EM, the thermodynamic equilibrium half-cell
potential
At E = EM,
iox,M = ired,M = io,M,
=> net transfer of metal ions to the solution no longer
occurs.
This is the criterion for complete cathodic
protection.
Fundamentals
CP reduces the corrosion rate by cathodic polarization of
the corroding metal surface
Eg. Iron corroding in dilute aerated neutral electrolyte
Fe Fe 2 2e (1)
O2 2 H 2O 4e 4OH ( 2)
Cathodic polarization reduces rate of (1)
This also the rate of (2)
Application
Any metal can be protected by cathodic polarization
Widest use: C-steel in mildly corrosive neutral aqueous
environ.
Stainless steel & Cu: intrinsically corrosion resistant-
dont need CP
Al & Zn: undergo cathodic corrosion due to alkalinity
generated by cathodic rxn
CP -not economical when corrosion rate is high
eg. Steel in strong acids
Require high currents and large rectifiers
Copious evolution of flammable H from
cathodic rxn- hazardous
Coatings to minimise the current requirements
fail in acid solutions
Max CR of uncoated steel in aerated quiescent
water ~ 0.47 mm/y
Tolerated in many applications
Not tolerated for permanent steel structures requiring
long life eg. buried pipelines, drilling platforms CP
Choice of methods
Cost-effectiveness
Cathodic protection is generally accomplished by
one of the following two methods
Cathodic Protection by Impressed Current
Factors
capital costs for power sources
Cost of semi-permanent anodes
running costs to supply the electric power
Generally large and particularly inaccessible systems eg long
pipelines, & food and chemical plants where contamination from the
corrosion of sacrificial anodes cannot be tolerated
Cathodic Protection by Sacrificial Anodes
Factors
initial and replacement costs of the anodes
labor and facilities needed to replace them
the costs of regular inspection
Cathodic Protection by Impressed Current
Rectifier- supplies impressed Single or multiple anodes
current after converting AC to distribute cathodic
to DC currents
Remote locations- diesel
gensets/solar power cells Buried structures,
seawater, freshwater-
graphite anode
(economical, an additional
1.7 V needs to be applied
to make it anode)
High Si cast iron, Pt
coated Ti*
Anodes are backfilled with
conductive material (eg
granulated coke)
-Spreads current over
greater area
oxide on bare titanium protects it from corrosion but it resist the passage of the
protecting current into an aqueous medium
Pt coating produces an efficient anode with a substrate that is protected in the
event of local failure of the platinum film.
Steel in acid
CR decreases by 103 to 1 A/cm2.
a decides the extent of reduction
Each 40 mV decreases by a factor of 10

Unpolarized CR
CR from polarization of 120 mV
Impressed current density, iapp = 1.5 x 10-2 A/cm2 = 15,000 A/cm2
to protect 1 m2, we need 150 A
Can we use coatings to reduce current requirements? NO
Coatings fail rapidly in strong acidic solution
CP is impractical in aggressive acidic solutions with high corrosion rates
More usual case of CP of steel in neutral aerated water/ seawater
Dissolved oxygen diffusion control
CR = 100 A/cm2
In neutral pH range & quiescent conditions,
accumulation of Fe(OH)2 decreases this to 20
A/cm2
Cathodic polarization CR = 0.1 A/cm2
Iapp = 100 A/cm2
This is also very high!
use coatings along with CP !
Coatings are resistant in neutral solutions

In seawater containing Mg & Ca


salts, local alkaline conditions at
CP surfaces precipitate insoluble
coatings in situ!

Unpolarized CR
CR from polarization of 120 mV
More usual case of CP of steel in neutral aerated water/ seawater

Excessive cathodic polarization


2H 2O 2e H 2 2OH
Direct reduction of water is
thermodynamically feasible.
H evolution destroys the coating
Waste of cathodic current

Unpolarized CR
CR from polarization of 120 mV
Cathodic Protection by Sacrificial Anodes

Connection to a
second active metal-
sacrificial anode
Nobler structure is
cathodically polarized
Active metal is
anodically dissolved
Anodes: Mg, Zn, Al
Few kgs to hundreds
of kgs

Fe Fe 2 2e
This rxn is suppressed by surplus of electrons provided by sacrificial anode
Reduction reaction is accelerated
Sacrificial Anode Cathodic Protection

io,H io,H
+ 2(M) 2(N)

EH2/H+ icorr(M)
icorr(M-N)
E
Ecouple
io,M

- icorr(M-N)

io,N
icorr(N)
EM/M+

log i
Sacrificial anodes

Anode alloy characteristics


Potential must be sufficiently active to drive the
protective current through the electrolyte. Higher the
electrolyte resistance OR greater the separation of
anode & cathode, more negative must be the
potential
Polarization at anode should be low enough to permit
current flow.
Electrochemical equivalent (charge theoretically
available to provide galvanic current per unit mass of
alloy) should be high
Efficiency (actual output) of the alloy should be high
Properties of Anode Materials in neutral water &
seawater
Alloys of Mg, Zn, Al have necessary physical, chemical and
economic properties
Property Mg (alloy) Zn Al alloys Steel
(protected
structure)
Corrosion potential, 1.68 1.1 1.05 0.4
V vs SCE
Output A-h/kg 2200 810 2000
Efficiency, % 50-60 >90 >90
Density 1.7 7.1 2.7
Use High resistivity Sea- Pure Al: passive,
media water polarizes
-Soil, add <1% Zn, Hg,
-pure water, hot In, Sn maintain
water tanks activity in Cl
*overprotection in Seawater use
seawater (also rapid -low cost
consumption)
Potential criterion for CP
Ep is decided empirically based on experience
For steel in seawater, Ep= -0.78 V vs SCE
maintain Ec < Ep
Relationship between Potential and Corrosion Risk
for Buried Steel
CP- risks
Cathodic disbonding of paint coatings due to hydroxide
ions (OH) and possibly H2 produced in the cathodic
reactions.
Common paint systems for marine applications usually
tolerate E down to 1.1 V vs. SCE
For lower potentials, a special documentation of the
systems resistance to cathodic disbonding is required.
Hydrogen embrittlement - absorbed H atoms produced
in the cathodic rxn.
particularly at high tensile stresses and for materials with
high TS and hardness.
y > 550 MPa, qualification testing should be carried out at
1.1 V vs SCE
Types of sacrificial anodes for offshore oil installations
Design data for Al- and Zn-based sacrificial anodes
Advantages sacrificial anode CP systems
No external power sources required
Ease of installation (and relatively low installation
costs)
Unlikely cathodic interference in other structures
Low-maintenance systems (assuming low current
demand)
Relatively low risk of overprotection
Relatively uniform potential distributions
Some limitations
Limited current and power output.
High-resistivity environments or large structures may
require excessive number of electrodes. Maximum
resistivity of 6000 to 10,000 .cm is generally
regarded as the limit, depending on coating quality.
Anodes may have to be replaced frequently under
high current demand.
Anodes can increase structural weight if directly
attached to a structure.
Stray Current
DC flowing in the earth from a source other
than that associated with the affected
structure
Stray DC must flow from an outside source
onto the pipeline (structure) in one area and
then flow along the line to some other area or
areas where they leave the pipe to re-enter
the earth (with resulting corrosion) and
complete the circuit by returning to the
original DC power source
Stray current sources
Impressed current CP systems on other pipelines
DC transit systems
DC mining operations
DC welding operations
high voltage DC transmission systems
disturbances of the earths magnetic field
Power supply
Ground level

Steel Anode
Tank current

Localized
Corrosion

Steel pipe
Current from a CP system will pass through a nearby low resistance current
path in the earth (pipeline) before it returns to the protected structure (tank)
Protection current is attenuated- incomplete protection
Cathodic protection of pipeline where the current enters the pipeline
Increased anodic corrosion where the current leaves the pipeline
Power supply
Ground level

Steel Anode
Anode Tank current
connection
Insulated

Steel pipe

Prevention by proper design