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Trethewey & Chamberlain; Ch-16

Fontana; Ch-6
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The theoretical basis
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Free corrosion potential E
corr
of iron in
aerated water is in the range of -600 to -
700 mV SSC at pH 7.
Different ways of affecting the condition of
the system at point O are:
Decreasing the pH
Increasing the pH
Apply a more negative potential
Cathodic Protection (CP)
Make the potential more positive
Anodic Protection (AP)
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CPDesign Considerations
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The corrosion rate, i
p
, at a given polarization
cathodic to E
corr
(at which the corrosion rate is i
corr
)
is expressed by
K T
Z
T R
F Z
i i
corr p
283
2
5 . 0
) exp(
=
=
=
=
o
q o
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For a given polarization of -200 mV, we get
corr p
corr p
i i
x
x x x
i i
00027 . 0
283 314 . 8
494 , 96 2 ) 2 . 0 ( 5 . 0
exp
=
|
|
.
|

\
|

=
Therefore, the corrosion rate at -850 mV SSC will be reduced to 0.03%
of the rate of unprotected steel.
At -750 mV SSC, corrosion rate is reduced to 2% of the rate at E
corr
.
Cathodic Protection
The most important of all approaches to corrosion control.
Using an externally applied electric current, corrosion is reduced
(approaching zero).
The mechanism of cathodic protection depends on external current that
polarizes the entire surface to the thermodynamic potential of the
anode.
The surface becomes equipotential (cathode and anode potentials
become equal), and corrosion currents no longer flow.
Or, looked at another way, at a high enough value of external current
density, a net positive current enters the metal at all regions of the
metal surface (including anodic areas); hence, there is no tendency for
metal ions to enter into solution.
Cathodic protection can be applied in practice to protect metals, such
as steel, copper, lead, and brass, against corrosion in all soils and in
almost all aqueous media.
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Pitting corrosion can be prevented in passive metals, such as the
stainless steels or aluminum.
Cathodic protection can be used effectively to eliminate
stress - corrosion cracking (e.g., of brass, mild steel, stainless steels,
magnesium, aluminum),
corrosion fatigue of most metals (but not fatigue),
intergranular corrosion (e.g., of Duralumin, 188 stainless steel), or
dezincification of brass.
It can be used to avoid SCC of high-strength steels, but not
hydrogen cracking of such steels.
Corrosion above the water line (e.g., of water tanks) is not affected,
because the impressed current cannot reach metal areas that are
out of contact with the electrolyte.
Nor does the protective current extend into electrically screened
areas, such as the interior of water condenser tubes (unless the
auxiliary anode enters the tubes), even though the water box may
be adequately protected.
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Types of CP
Two types:
1) Sacrificial anode CP (SACP)
2) Impressed current CP (ICCP)
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Example of Sacrificial Anode CPover ground
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Example of Sacrificial Anode CPover ground
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Sacrificial anodes
The sacrificial anodes are usually composed of magnesium or magnesium-
based alloys.
Occasionally, zinc or aluminum has been used.
Approximately 10 million pounds of magnesium is annually used for this
purpose.
The open-circuit potential difference between magnesium and steel is about
1 V.
This means that one anode can protect only a limited length of pipeline.
However, this low voltage can have an advantage over higher
impressed voltages in that the danger of overprotection to some portions of
the structure is less; and because the total current per anode is limited, the
danger of stray-current damage to adjoining metal structures is reduced.
Magnesium anode rods have also been placed in steel hot-water tanks to
increase the life of these tanks. The greatest degree of protection is
afforded in hard waters where the conductivity of the water is greater
than in soft waters.
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Anode Requirements
To provide cathodic protection, a current density
of a few milliamps (mA) is required.
To determine the anodic requirements, it is
necessary to know the energy content of the
anode and its efficiency.
From this data the necessary calculations can
be made to size the anode, determine its
expected life, and determine the number of
anodes required.
The three most common metals used are
magnesium,
zinc, and
Aluminum.
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Principle of impressed current CP
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Potentials more negative than -850 mV SSC show even
less metal loss. Why not use -1000 mV SSC, or lower?
There are two reasons:
1) More hydrogen evolution at more negative
potentials. It may cause damage like
hydrogen embrittlement etc.
2) More negative potentials produce high local
concentrations of hydroxyl ions which ,may
cause chalking or damage any barrier
coatings such as paint.
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Current should be controlled or potential?
Fixing current may cause decrease in current
density if the area is increased by damage in
coating. This may change potential towards
E
corr
.
Area may increase or decrease
Regulating potential can provide required
current density.
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Sacrificial Anode Design
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Protection PotentialE
p
It is the least negative potential necessary
to achieve a satisfactory level of
protection.
For steel in aerated seawater, this is
considered to be 800 mV SSC
The anodes connected for protection are
termed as Sacrificial Anodes.
The anodes are usually welded or
mechanically coupled with the structure at
predetermined points.
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Anodes Material
Usually Zinc, Magnesium & Aluminum
Traditionallyfor steel in seawater; Zinc &
Cast Iron
Using sacrificial anodes on Copper reduced
the consumption, however, fouling was
increased.
C-Sentry __ Zn-alloy with
0.10.5% Al,
0.0250.15% Cd.
Extensively used by marine industry.
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Sacrificial anodes are supposed to be
dissolving at uniform rate.
Commercially pure zinc corrodes in seawater
forming an impermeable skin which severely
limits its current output.
Fethe most detrimental impurity
Its solubility in Zn is so low (<0.0014%) that any
excess is present as discrete particles.
This forms local galvanic cellsproducing a
coating of insoluble non-conducting Zn-hydroxide
or Zn-carbonate.
Addition of Al is beneficiala less noble Al-Fe
intermetallic is formed which reduces the effect of
local corrosion cells.
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Addition of Cdreduces the adverse effect of Pb
impurity
Aluminum
undergoes pitting corrosion in seawater because of
cathodic oxide film
Therefore, pure Almost unreliable for use as sacrificial
anodes
Al-alloys containing Zn & Hg or Zn & In
Have much higher electrical power/weight ratios than Zn-
alloys
Magnesium
Too vigorous corrosion rate in seawater
Used in soil or estuarine waters where resistivity is
relatively high to limit effectiveness of Alor Znalloys
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Efficiency of anodes
Magnesium in seawater
E
corr
~ -2.12 V SCE (theoretical)
E
corr
~ -1.7 V SCE (practical)
Theoretically, 1 kg should yield ~ 2200 A h
Practically, 1200 A h
Therefore, efficiency = 5060%
Efficiency for Zn and Al alloys is >90%.
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Factors that affect current requirements are:
1. The nature of the electrolyte
2. The soil resistivity
3. The degree of aeration
The required current to provide cathodic
protection can vary from 0.5 to 20 mA/ft
2
of bare
surface.
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Benefit of coating
Less anode material is required for a coated
structure
A surface with a fresh coal tar paintwill be well
protected with a current density of 2030 mA/m
2
to accommodate holidays in the coating
A bare steel structure requires >100 mA/m
2
.
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Few important terminologies
Capacity of an anode
The no. of Ampere-hours supplied by each kg of
the material
Wastage rate
Current output per unit of exposed surface
areaexpresses the rate of loss of metal by
volume or mass
Throwing power
The effective distance between the metal and
the anode
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Total weight of anode material required to protect a
structure for its projected life is:
C
L A i
W
av
8760 * * *
=
W= total mass of anode material (kg)
A = area of structure (m
2
)
i
av
= mean current density demand of the structure (A m
-2
)
C = anode capacity (A h kg
-1
)
L = Design life (years)
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Total weight of anode material must equal or
exceed W
Each individual anode must be able to supply
current for the design lifetime and be able to
meet varying demands.
Current output from an anode will vary
according to its shape.
The anode output I therefore, is dependant
on
The anode shape
The resistivity of environment
The protection potential E
p
(usually ~ -0.8 V SSC)
The anode operating potential E
a
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I = (E
p
E
a
)/R
a
Where R
a
is the anode resistance (depends on
shape)
Anode life L is then given by
L = (M
a
U)/(I W
w
)
M
a
is the mass of single anode
I is the anode current
W
w
is the waste rate by weight (kg (Ay)
-1
U is the utilization factor which depends on
anode geometry and is the fraction of
material consumed when the remaining
material is no longer able to provide the
required current.
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Anodes distribution
A good protection is achieved with more
anodes, but
It increases cost and weight
Correct protection potential should be
maintained at points of structure most
vulnerable to stress
E.g. welded joints of offshore platform, called
nodes
Danger may be associated with overprotection
and hydrogen embrittlement
Anode-cathode distance is also important
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Testing for Completeness of Protection
The preferred method is to take potential
measurements.
Position of reference electrode
as close as possible to the protected structure
avoids and minimizes internal resistance (IR)
drop through the soil.
For buried pipelines, a compromise location is directly over
the buried pipe at the soil surface because cathodic
protection currents flow mostly to the lower surface and are
minimum at the upper surface of the pipe buried a few feet
below the surface.
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Overpotential of steel structures,
If to a moderate degree, does not cause any problems.
The primary disadvantages are
waste of power and
increased consumption of auxiliary anodes.
hydrogen can be generated at the protected structure,
causes
blistering of organic coatings,
hydrogen embrittlement of the steel, or
hydrogen cracking.
Overprotection of systems with amphoteric
metals (e.g., tin, lead, aluminum, zinc)
will damage the metal by causing increased attack
instead of reduced corrosion.
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Several ways to check effectiveness of protection.
1. Coupon test. A metal coupon is shaped to conform to the contour of the pipe,
weighed, and attached by a braze-connected cable to the pipe. Both the cable
and the surface between the coupon and the pipe are coated with coal tar. The
coupon is allowed to remain buried for weeks or months, uncovered, cleaned,
and weighed. The weight loss, if any, is an indication as to whether or not the
cathodic protection is complete.
2. Colorimetric test. A piece of absorbent paper soaked in potassium ferricyanide
solution is placed in contact with a cleaned section of the buried pipeline and
the soil replaced. After a relatively short time, the paper is retrieved. A blue
ferrous/ferricyanide reaction indicates incomplete cathodic protection, whereas
an absence of blue on the paper indicates that cathodic protection is complete.
3. Potential measurements. By measuring the potential of the protected
structure, the degree of protection, including overprotection, can be quantitavely
determined. This measurement is the generally accepted criterion and is used
by corrosion engineers. The basis for this determination is the fundamental
concept that cathodic protection is complete when the protected structure is
polarized to the open-circuit anodic potential of the local action cells.
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