Corrosion Protection

Ahmad Ivan Karayan, ST, MEng

Department of Metallurgy and Materias Engineering

University of Indonesia

ivan@metal.ui.ac.id

 CATHODIC PROTECTION
ANODIC PROTECTION
MATERIAL SELECTION
ALTERATION OF ENVIRONMENT
(INHIBITOR)
PROPER DESIGN
COATINGS & WRAPPING

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Cathodic Protection Theory

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Cathodic Protection
Sacrificial Anode
(Galvanic Cathodic
Protection)
Impressent Current

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Cathodic Protection Criteria in

Accordance with NACE RP0169

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Cathodic Protection Criteria in

Accordance with NACE SP0169
Replacing NACE RP0169

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Voltage (IR) Drops

The difference between the the real potential and the displayed potential
Methods suggested for determining IR drop involve one or more of the
following:

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ON and OFF Potential

ON Potential is the potential adjusted from the T/R when

T/R is on regardless IR Drop, so CP criteria -850 mv
shall be measured by OFF Potential
OFF Potential Potential measured when T/R is off
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How to Measure Structure Potential

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Reference Electrode

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Components of Galvanic Cathodic

Protection

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Galvanic Cathodic Protection

Alloys of magnesium, zinc, and

aluminum have been
developed to enable the anode
to remain active and extend
the life of the anode. The pure
forms of the metals are often
not suitable as anodes
because they undergo too
much self corrosion in the
environment and do not stay
active. Galvanic anode alloys
include: magnesium, zinc,
aluminium

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Types Anodes for Galvanic

Cathodic Protection

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Types Anodes for Galvanic

Cathodic Protection

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Galvanic Anode Efficiency

The efficiency of a galvanic anode depends on the alloy
of the anode and the environment in which it is installed.
The consumption of any metal is directly proportional to
the amount of current discharged from its surface.
For galvanic anodes, part of this current discharge is
due to the cathodic protection current provided to the
structure and part is caused by local corrosion cells on
its surface.
Anode efficiency is the ratio of metal consumed
producing useful cathodic protection current to the total
metal consumed.
For magnesium, the anode efficiency is generally less
than 50%, while zinc has an efficiency of 90%.
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Applications of Galvanic Anode

System

The following are among the conditions where galvanic anodes are
used:
When a relatively small amount of current is required.
Usually lower resistivity electrolytes.
For local cathodic protection to provide current to a specific area on
a structure. Some pipeline operators install galvanic anodes at each
location where a leak is repaired rather than installing a complete
cathodic protection system. Such practices may be encountered on
bare metal or very poorly coated systems where complete cathodic
protection may not be feasible because of cost.
When additional current is needed at problem areas. Some
structures with overall impressed current cathodic protection
systems may have isolated points where additional current in
relatively small amounts is needed. These requirements can be met
with galvanic anodes.

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Poorly coated buried valves

Interiors of water storage tanks
Shorted casings that cannot be cleared (to improve potentials in the
surrounding area)
Underground storage tanks
Isolated sections where the coating has been badly damaged
Areas where electrical shielding impairs effective current distribution from
remotely located impressed current systems
In cases of cathodic interference, if the conditions are suitable, galvanic
anodes can be used at the discharge point to return interfering current.
To provide protection to structures located near many other underground
metallic structures where conditions make it difficult to install impressed
current systems without creating stray current interference problems.
Galvanic anodes can be an economical choice for a cathodic protection
current source under such conditions.
Galvanic anodes find extensive use in protecting the interior surface of heat
exchanger water boxes and other vessels. They are also used within oil
heater-treater vessels, depending on the quality of the interior lining and the
fluid chemistry and temperature.
On offshore structures, large galvanic anodes may be used to protect the
underwater components.

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Anode Backfill

Zinc and magnesium anodes used in cathodic protection pplications

in soil are sometimes supplied prepackaged with a prepared backfill
material in a cloth or cardboard container.
The special backfill prevents direct soil contact to reduce localized
corrosion of the anode, prevents passivation of the anode caused
by reactions with soil salts, provides a low-resistivity environment
around the anode, and expands when wet to fill the hole and
eliminate air voids.
The most common backfill material contains 75% hydrated gypsum,
20% bentonite clay, and 5% sodium sulfate.
Zinc anodes can also be packaged in a backfill consisting of 50%
hydrated gypsum and 50% bentonite clay.
Since zinc anodes are normally installed in low-resistivity soil, it is
not necessary to add sodium sulfate to lower resistivity.

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Wiring and Connections

Galvanic anodes can be attached to the structure either directly by

welding or bolting integral straps to the structure, e.g., hull mounted
anodes and bracelet anodes, or by connecting a wire between the
anode and structure.

If a wire is used, the manufacturer attaches it to the anode. The wire

is attached to the structure using a mechanical connection, thermite
weld, or other suitable method. The thermite weld is the preferred
method since it provides the most reliable connection. The wire
should be coated with a dielectric insulation and the connections
should be coated.

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Component of Impressed Current

Cathodic Protection
The components of an impressed
current cathodic protection system
are anodes, anode backfill, a
power supply (rectifier), structure,
wiring, and connections.
The anodes used in impressed
current CP systems are different
from those used in galvanic
systems.
Impressed current anodes are
manufactured from materials that
are consumed at low rates.
Impressed current CP systems
generally operate at higher current
and driving voltage levels than
galvanic anode CP systems.
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Applications of Impressed Current

Typical uses of impressed current are:
For large current requirements, particularly for bare or poorly coated
structures
In all electrolyte resistivities
As an economical way of protecting structures having dissipated galvanic
anodes
To overcome stray current or cathodic interference problems
For protection of large heat exchanger water boxes, oil heater-treaters, and
other vessels
For interiors of water storage tanks
For exterior bottoms (both primary and secondary) of aboveground storage
tanks
For underground storage tanks
For underwater components of offshore structures
For foundation piles and sheet piling, both underground and in the water.
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Anodes for Impressed Current

Graphite
Graphite anodes are used in soils, flowing seawater, and
mud. They are practically immune to chlorine attack.
Graphite anodes are usually impregnated with a sealer
to prevent mechanical failure from gas evolution in
pores. Graphite is also brittle. Consumption rates are
0.45 kg/A-y (1 lb/A-y) in seawater, 0.9 kg/A-y (2 lb/A-y) in
carbon backfill, and 1.36 kg/A-y (3 lb/A-y) in mud.
Graphite anodes are usually available as cylindrical
anodes.

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Anodes for Impressed Current

Conductive Polymer
Carbon is used as filler in polymer materials having a
copper core for use as an impressed current anode. This
type of anode looks like an insulated wire but the
covering is conductive. (Note: this type of anode wire
must not be used where dielectrically insulated wire is
needed.) This material has a maximum rating of 51
mA/m (16 mA/ft) of material.
Carbon has also been used as conductive filler in wateror solvent- based coatings for application as an anode to
protect reinforced concrete structures.
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Anodes for Impressed Current

High-Silicon Chromium-Bearing Cast Iron
High-silicon cast iron (HSCI) is a chemically resistant
alloy containing silicon, chromium, and iron. HSCI
anodes are commonly used in fresh water, seawater, or
underground applications. HSCI is very brittle and forms
a SiO2 film on the surface in underground applications
that can increase the resistance of the anode in dry
environments. The consumption rate of HSCI ranges
from 0.25 to 1 kg/A-y (0.55 to 2.20 lb/A-y).

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Anodes for Impressed Current

Lead
Lead-silver alloys have been used in seawater
applications. The lead under anodic current develops a
PbO2 film that is conductive and prevents deterioration
of the lead. The consumption rate of lead-silver alloys is
on the order of 0.09 kg/A-y (0.2 lb/A-y).
Extruded lead with platinum pins has also been used in
seawater applications. The purpose of the platinum pins
is to promote the ormation of the PbO2 film.

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Anodes for Impressed Current

Mixed-Metal Oxide
Mixed-metal oxide (MMO)anodes, also called
dimensionally stable anodes, consist of rare earth oxides
baked onto a titanium substrate. These anodes were
developed for the electrolytic production of chlorine and
hypochlorites, but are now used for cathodic protection
applications. The consumption rate is on the order of 1
mg/A-y. This anode material is typically available in rod,
wire, tubular, or mesh form.

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Anodes for Impressed Current

Platinum
Platinum is used as an anode material when either metallurgically clad or
plated onto either a titanium or niobium substrate. Titanium and niobium
form stable oxide layers when made anodic. These layers are stable up to
12 V in the case of titanium and 90 V in the case of niobium. The
consumption rate of platinized anodes is on the order of 6 to10 mg/A-y.
Platinized anodes are available in wire or mesh form. Platinized anodes are
subject to rapid deterioration if the breakdown voltage is exceeded or if the
environmental conditions surrounding the anode become acidic. Other
deleterious factors include the presence of low-frequency AC ripple, current
reversal, biofouling, scales, and the presence of certain organic materials.
Platinized anodes are most suitable in fresh-or salt-water applications rather
than in underground applications.

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Anodes for Impressed Current

Scrap Metal
Scrap iron or steel can be used as an anode material. In
situations where the current requirements are low, scrap
iron is readily available, and the anode can be readily
replaced, scrap iron might be an economical choice.
The consumption rate of iron is 6.8 to 9.1 kg/A-y (15 to
20 lb/A-y). The relatively rapid dissolution rate and
difficulty in maintaining the integrity of the connection
between the power supply and anode are disadvantages
of this material.

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Anodes for Impressed Current

Metallized Titanium
Thermal Sprayed Zinc and Aluminum
Alloys
Magnetite
Aluminum

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Anode Backfill
Carbon is used as a backfill material around impressed
current anodes for underground CP applications. The
purpose of the backfill material is to:
Reduce the resistivity of the environment surrounding
the anode to increase the amount of current the anode
can discharge
Extend the anode surface area, thus increasing the
amount of current the anode can discharge; and
Reduce consumption of the anode since the carbon
becomes the part of the anode consumed before the
anode itself.

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Anode Backfill
Carbon backfill for
cathodic protection
purposes is available as
calcined petroleum or
metallurgical coke, each
being the product of its
respective industry. Noncalcined carbon is also
available, but is not
suitable for CP use since
it can have too high an
electrical resistance.

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Power Supply (T/R)

Unlike galvanic anode systems where the
natural potential difference between the
anode and cathode provides the driving
force for current, an impressed current CP
system must be supplied with power from
an external source.

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Wiring and Connections

In impressed current CP systems, all wiring and connections must
be made to totally isolate the metal from the electrolyte. Unlike a
galvanic anode system where exposed wire and connections are
protected by the anode, any exposed metal in an impressed current
CP system is part of the anode. Thus, exposed metal will corrode
rapidly. Only cable having approved cathodic protection dielectric
insulation can be used. Types of insulation found on CP cables
include:
High-Molecular-Weight Polyethylene (HMWPE) commonly used
for direct burial cathodic protection installations for both anode and
structure wiring.
Halar/Polyethylene Layered Insulation.
Kynar/Modified Polyolefin.

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Anode Configurations
Distributed anode

Remote anode

Configurations is chosen based on calculation

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Stray Current
Stray currents are currents flowing in
the electrolyte from external sources.
Any metallic structure, for example a
pipe line, buried in soil represents a
low resistance current path and is
therefore fundamentally vulnerable to
the effects of stray currents

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Stray Current
Stray current tends to enter a buried structure in a
certain location and leave it in another. It is where the
current leaves the structure that severe corrosion
expected.
Overprotection might also occur at a location where the
high current density of stray current enter a structure.
There are a number of source of undesirable stray
currents, including foreign cathodic protection
installations, dc transit systems such as electrified
railways, subway systems, and streetcars, welding
operations, and electrical power transmission systems.

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Direct Stray Current

Direct stray currents come from foreign
cathodic protection systems, transit
systems, and dc high voltage transmission
line.
Direct stray current can cause :
1. Anodic interference
2. Cathodic interference
3. Combined interference

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Anodic interference

It is found in relatively close proximity to a buried anode.

At location close to anode the pipeline will pick up current. This
current will be discharged at a distance farther away from the
anode.

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Anodic interference
In the current pickup region, the potential of
the pipeline will shift in the negative region. It
receives a boost of cathodic protection
current locally. This local current boost will
not necessarily be beneficial, because a state
of overprotection could be created. Excess
of alkaline species generated can be harmful
to aluminum and lead alloys

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Cathodic Interference
Cathodic interference is produced in relatively
close proximity to a polarized cathode.
Current will flow away from the structure in
region in close proximity to the cathode. The
potential will shift in the positive direction where
the current leaves this structure, and this area
presents the highest corrosion damage risk.
Current will flow onto the structurew over a large
area at farther distance from the cathode.

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Cathodic Interference

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Combined Anodic and Cathodic

Interference
Current pickup occurs close to an anode, and
current discharge occurs close to a cathodically
polarized structure.
The degree of damage of the combined stray
current effects is greater than in the case of
anodic or cathodic interference acting alone.
The damage in both the current pickup
(overprotection effects) and discharge regions
(corrosion) will be greater.

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ivan@metal.ui.ac.id

Controlling Stray Current Corrosion

In implementing countermeasures against stray current

effects, the nature of stray currents has to be
considered. For mitigating dc interference, the following
fundamental steps can be taken:
Removal of the stray current source or reduction in its
output current.
Use of electrical bonding
Cathodic shielding
Use of sacrificial anodes
Application of coatings to current pickup areas

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Use of A Drainage Bond

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Cathodic Shielding

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Use of Sacrificial
Anode

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Stray Current Associated with DC

Transit System

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Anodic Protection

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Corrosion control of metal structure by

impressed anodic current.
Interface potential of the structure is
increased into passive corrosion domain.
Protective film is formed on the surface of
metal structure which decrease the
corrosion rate down to its passive
current.
Can
be
applied
metals/alloys only.
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for

active-passive

Anodic protection can decrease

corrosion rate substantially.
Anodic protection of 304SS exposed to an
aerated H2SO4 at 300C at 0.500 vs. SCE
Acid
concentration, M

NaCl, M

Cor. Rate m/y

(Unprotected)

Cor. Rate m/y

(Protected)

0.5
0.5
0.5
5
5
5

10-5
10-3
10-1
10-5
10-3
10-1

360
74
81
49000
29000
2000

0.64
1.1
5.1
0.41
1.0
5.3

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Metals which can be passivated

and de-activated
The metals which can be passivated by
oxidation and activated by reduction are those
which have a higher oxide less soluble than a
lower oxide and will thus each corrosion
domain forms an angle.
The lower the apex of this angle in the diagram
(such as titanium, chromium and tin etc.), the
easier it will be to passivate the metal by
oxidation and it will be difficult to reactivate
the passivated metals by reduction.
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Experimental potential - pH diagram for chromium

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Anodic polarization curve of

AISI 304 SS in 0.5 M H2SO4

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Anodic protection parameters :

(can be obtained from anodic
polarization measurement)
Range of potential in which metal is in
passivation state (protection range)
Critical current density
Flade potential
Optimum potential for anodic protection
is midway in the passive region
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Flade potential (EF)

E F E n 0,059pH
O
F

In which EFO : Flade potential at pH = 0

n : a constant (between 1 and 2) depends of
metal composition and environment
conditions
Metals having EF < equilibrium potential of
hydrogen evolution reaction (HER) can be
passivated by non oxidizing acid (i.e.
titanium)
Increasing temperature will reduce the
protection potential range and increase the
critical current density and therefore anodic
protection will be more difficult to be applied.
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Parameters that should be

considered for anodic protection
design (Flade potential is not
included in the figure)

57

Influences of temperature and chloride concentration on

anodic polarization curve of stainless steels
(schematic figure)

Anodic polarization curves of a mild steel in 10%

sulfuric acid at 22 and 600C
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 For metals exposed in aggressive

ions containing - environment
Interface potential of metal should
be :
Eprot>Elogam>Eflade
Basically : Eflade is equal or slightly
lower than Epp.
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Schematic figure of potential range for anodic

protection of a stainless steel which is
susceptible to pitting corrosion in an
environment containing aggressive ions
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 Increasing of chloride ions

concentration results in a significant
decrease of protection potential
range.
Consequently, in aggressive ions
containing-environment anodic
protection is applied only for metals
which have relatively high protection
potential and high pitting potential.
Increasing temperature leading to a
decrease of Eprot
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Schematic figure of anodic protection

system for protecting inner surface of
storage tank
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CATHODES FOR ANODIC

PROTECTION
Should be permanent and can be used as
current collector without any significant
degradation.
Having large surface area in order to suppress
cathodic overpotential.
Low cost.
Platinum clad brass can be used for anodic
protection cathodes because this cathode has
low overpotential and its degradation rate is
very low, however it is very expensive.
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Cathodes used in recent anodic

protection systems

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Comparison of anodic and cathodic

protection :
Anodic
Cathodic
protection
protection
Applicability

Active-passive
metals only

All metals

Corrosives

Weak to
aggressive

Weak to
moderate

Relative
High
investment cost

Low

Relative
operation cost

Very low

Mediums to
high

Equipment

Potentiostat +
cathode/s

Sacrificial anodes or
DC power supply +
ICCP anode/s

Throwing
power

Very high

Low to high

Significant of
applied current

Often a direct
measure of
protected
corrosion rate

Complex
Does not
indicate
corrosion rate

Operating
conditions

Can be
accurately and
rapidly
determined by
electrochemical
measurement

Must usually be
determined by
empirical
testing

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Typical applications of anodic protection

 Anodic protection has been applied to protect

storage tanks, reactors, heat exchangers and
transportation vessels for corrosive solutions.
Heat exchangers (tubes, spirals and plates
types) including their anodic protection systems
can be easily to purchase in the market.
i.e. AISI 316 SS HE is used to handle 96-98%
sulfuric acid solution at 110 0C.
Anodic
protection decreases corrosion rate of the
stainless steel, initially from 5mm/year down to
0.025mm/year and therefore less contaminated
sulfuric acid can be obtained.
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DATA
Effect of chromium content on critical
current density and Flade potential of iron
exposed in 10% sulfuric acid.

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Effects of nickel and chromium contents on critical current

density passivation potential in 1N and 10 N H2SO4 containing
0.5 N K2SO4

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Requirement of critical protection current densities

for several austenitic stainless steels (18-20 Cr , 8-12
Ni) exposed in different electrolytes
Protection current density : current density required
to maintain passivity

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Effect of sulfuric acid concentration at 240C on the corrosion

rate and critical current density of stainless steel

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Effect of stirring of electrolyte on the corrosion rate and

requirement of current density to maintain passivity on a
stainless steel at 270C

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Current density requirements for

anodic protection

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Anodic Protection Using a Galvanic Cathode

A cylindrical tank of 304 stainless steel for
storing deaerated sulfuric acid (pH=0) is
found to corrode rapidly. To provide anodic
protection, a galvanic cathode of platinum
will be installed. The tank has a diameter
of 5 m and the depth of acid is 5 m.
a. Draw a labeled sketch of the polarization
diagram for the tank and calculate the
passivation potential versus SHE.
b. What is the area of platinum required to
ensure stable passivity?
c. What will the corrosion potential be when
the tank achieves passivity?
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Data:

304 stainless steel:

Ecor = -0.44 V vs SCE

icor = 10-3 A/cm2

Tafel slope anodic = 0.07 V/decade

icrit = 1.4 x 10-2 A/cm2

ipas = 4 x 10-7 A/cm2

H+ reduction on platinum

i0 = 10-3 A/cm2
Tafel slope cathodic = 0.03 V/decade
SCE = +0.2416 V vs.SHE
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