Corrosion of tanks caused by Sea Water

Introduction
Corrosion is the deterioration of materials by chemical interaction with their
environment. The consequences of corrosion are many and varied and the effects of these
on the safe, reliable and efficient operation of equipment or structures are often more
serious than the simple loss of a mass of metal. When we are using Sea water for Hydro
Testing of tanks we may encounter Following types of corrosion.

1. CORROSION CAUSED BY CHEMICALS PRESENT IN SEA WATER

2. PITTING CORROSION
3. CONCENTRATION CELL CORROSION (CREVICE)
4. CORROSION CAUSED BY COMBINED ACTION
5. STRESS CORROSION CRACKING

Detailed composition of seawater

at 3.5% salinity
Element At.weight ppm Element At.weight ppm
Hydrogen H2O 1.00797 110,000 Molybdenum Mo 0.09594 0.01
Oxygen H2O 15.9994 883,000 Ruthenium Ru 101.07 0.0000007
Sodium NaCl 22.9898 10,800 Rhodium Rh 102.905 .
Chlorine NaCl 35.453 19,400 Palladium Pd 106.4 .
Magnesium Mg 24.312 1,290 Argentum (silver) Ag 107.870 0.00028
Sulfur S 32.064 904 Cadmium Cd 112.4 0.00011
Potassium K 39.102 392 Indium In 114.82 .
Calcium Ca 10.08 411 Stannum (tin) Sn 118.69 0.00081
Bromine Br 79.909 67.3 Antimony Sb 121.75 0.00033
Helium He 4.0026 0.0000072 Tellurium Te 127.6 .
Lithium Li 6.939 0.170 Iodine I 166.904 0.064
Beryllium Be 9.0133 0.0000006 Xenon Xe 131.30 0.000047
Boron B 10.811 4.450 Cesium Cs 132.905 0.0003
Carbon C 12.011 28.0 Barium Ba 137.34 0.021
Nitrogen ion 14.007 15.5 Lanthanum La 138.91 0.0000029
Fluorine F 18.998 13 Cerium Ce 140.12 0.0000012
Neon Ne 20.183 0.00012 Praesodymium Pr 140.907 0.00000064
Aluminium Al 26.982 0.001 Neodymium Nd 144.24 0.0000028
Silicon Si 28.086 2.9 Samarium Sm 150.35 0.00000045
Phosphorus P 30.974 0.088 Europium Eu 151.96 0.0000013
Argon Ar 39.948 0.450 Gadolinium Gd 157.25 0.0000007
Scandium Sc 44.956 <0.000004 Terbium Tb 158.924 0.00000014
Titanium Ti 47.90 0.001 Dysprosium Dy 162.50 0.00000091
Vanadium V 50.942 0.0019 Holmium Ho 164.930 0.00000022
Chromium Cr 51.996 0.0002 Erbium Er 167.26 0.00000087
Manganese Mn 54.938 0.0004 Thulium Tm 168.934 0.00000017
Ferrum (Iron) Fe 55.847 0.0034 Ytterbium Yb 173.04 0.00000082
Cobalt Co 58.933 0.00039 Lutetium Lu 174.97 0.00000015
Nickel Ni 58.71 0.0066 Hafnium Hf 178.49 <0.000008
Copper Cu 63.54 0.0009 Tantalum Ta 180.948 <0.0000025
Zinc Zn 65.37 0.005 Tungsten W 183.85 <0.000001
Gallium Ga 69.72 0.00003 Rhenium Re 186.2 0.0000084
Germanium Ge 72.59 0.00006 Osmium Os 190.2 .
Arsenic As 74.922 0.0026 Iridium Ir 192.2 .
Selenium Se 78.96 0.0009 Platinum Pt 195.09 .
Krypton Kr 83.80 0.00021 Aurum (gold) Au 196.967 0.000011
Rubidium Rb 85.47 0.120 Mercury Hg 200.59 0.00015
Strontium Sr 87.62 8.1 Thallium Tl 204.37 .
Yttrium Y 88.905 0.000013 Lead Pb 207.19 0.00003
Zirconium Zr 91.22 0.000026 Bismuth Bi 208.980 0.00002
Niobium Nb 92.906 0.000015 Thorium Th 232.04 0.0000004
Uranium U 238.03 0.0033
Plutonimu Pu (244) .
Note! ppm= parts per million = mg/litre = 0.001g/kg.

This is a general Composition of Sea Water, among these chemicals most

corrosive chemicals are chlorine and sulphur. About 55% of sea water consists of
Chlorine and it causes the major corrosion.

CHEMISTRY OF CORROSION

Common structural metals are obtained from their ores or naturally-occurring compounds
by the expenditure of large amounts of energy. These metals can therefore be regarded as
being in a metastable state and will tend to lose their energy by reverting to compounds
more or less similar to their original states. Virtually all corrosion reactions are
electrochemical in nature, at anodic sites on the surface the iron goes into solution as
ferrous ions, this constituting the anodic reaction. As iron atoms undergo oxidation to
ions they release electrons whose negative charge would quickly build up in the metal
and prevent further anodic reaction, or corrosion. Thus this dissolution will only continue
if the electrons released can pass to a site on the metal surface where a cathodic reaction
is possible. At a cathodic site the electrons react with some reducible component of the
electrolyte and are themselves removed from the metal. The rates of the anodic and
cathodic reactions must be equivalent according to Faraday’s Laws, being determined by
the total flow of electrons from anodes to cathodes, which is called the “corrosion
current”, Icor. Since the corrosion current must also flow through the electrolyte by ionic
conduction the conductivity of the electrolyte will influence the way in which corrosion
cells operate. The corroding piece of metal is described as a “mixed electrode” since
simultaneous anodic and cathodic reactions are proceeding on its surface. The mixed
electrode is a complete electrochemical cell on one metal surface.
 The most common and important electrochemical reactions in the corrosion of
iron are thus
Anodic reaction (corrosion)

FeÆ Fe2+ + 2e

Cathodic reaction (corrosion)

H2O +1/2 O2+2eÆ2OH-

Fe2+ + 2OH-ÆFe(OH)2
Iron (II) hydroxide

Pure iron (II) hydroxide is white but the material initially produced by corrosion
is normally a greenish colour due to partial oxidation in air.

Fe(OH)2+H2O+1/2O2Æ 2Fe(OH)3
Hydrated ironIII oxide

Further hydration and oxidation reactions can occur and the reddish rust that eventually
forms is a complex mixture whose exact constitution will depend on other trace elements
which are present. Because the rust is precipitated as a result of secondary reactions it is
porous and absorbent and tends to act as a sort of harmful poultice which encourages
further corrosion.

Reactions of Chlorine

Cl2 + H2O Æ HOCl + HCl

Cl2 + H2 Æ 2 HCl

NaClÆNa+ +Cl-

Fe+2 + 2ClÆFeCl2
2 FeCl2 + Cl2 Æ 2 FeCl3

Ferrous chloride is a corrosive mineral acid. When exposed to oxygen it oxidises to ferric
chloride.

Prevention Method:
Monitor the pH and keep in the range 10-13.Research indicates best inhibiting
solutions have a high pH. Marine archeologists typically use a 5 percent sodium
carbonate solution (soda ash). This has a high pH and will passivate (stop further
corrosion) the iron

Electrochemical Control:
Since corrosion is an electrochemical process its progress may be studied by
measuring the changes, which occur in metal potential with time or with applied
electrical currents. Conversely, passing anodic or cathodic currents into the metal may
control the rate of corrosion reactions.

Impressed Current Cathodic Protection

Cathodic protection can be also applied if the metal to be protected is
coupled to the negative pole of a direct current (DC) source while the positive
pole is coupled to an auxiliary anode. Since the driving voltage is provided by
the DC source there is no need for the anode to be more active than the
structure to be protected. There are basically three types of anode materials:

• Inert or non consumable anodes

• Semi-consumable anodes
• Consumable anodes

All items to be protected shall be electrically connected and should have a

welded or brazed connection to an anode. For bolted or clamped assemblies
without an all welded brazed electrical grounding, the electric resistance
should be less than 0.10 ohm. Coating on contact surfaces shall be removed
prior to assembly.
Schematic of an Impressed Current CP System

In the impressed current CP, the large electrochemical is formed between an

anode and the structure to be protected by a power supply that is controlled
by reading a reference electrode close to the structure.

Non Consumable Anodes

This type of anode supports other anodic reactions on their surfaces. In

environments where water and chloride ions are present, chlorine evolution
and oxidation of water are possible.
• Platinized substrates: Platinum is the ideal permanent impressed
current anode material. It is one of the most noble metals and in
practically all environments forms a thin invisible film which is
electrically very conductive. In addition, the exchange current densities
of most anodic reactions on the Pt surface are greater than on other
anode materials. Due to its high cost, platinum is applied as a thin
coating (1-5 μm) on metallic substrates such as titanium, niobium and
tantalum.

Platinized titanium is often used in marine environments. To

avoid the dissolution of titanium at unplatinized locations on the
surface, the operating voltage of the anode is limited by the
anodic breakdown potential of titanium which is in the range of 9
to 9.5 V in the presence of chlorides. Hence the maximum
recommended operating voltage of platinized titanium anodes is 8
V. The corresponding maximum current density output is
approximately 1 kA m-2. For cathodic protection systems where
operating voltages are relatively high, niobium and tantalum
based anodes are generally selected. This is because these two
substrates have anodic breakdown potentials greater than 100 V
in chloride containing electrolytes. The wastage rate of platinized
anodes is approximately 8 mg A-1 y-1.

The rate of platinum consumption has been found to accelerate in

the presence of AC current ripple. Most wastage was observed to
occur with AC frequencies of less than 50 Hz. The repeated
oxidation/reduction processes result in the formation of a
brownish layer of platinum oxide. To avoid the occurrence of this
phenomenon, a single or a three phase full-wave rectification is
recommended. The consumption rate of platinized anodes is also
adversely affected by the presence of organic impurities such as
sugar and diesel fuel.

• Magnetite: Magnetite is a cheap and naturally occurring material. It is a

non-stoichiometric oxide and has an electrical conductivity of 1.25 Ω-1
m-1. Due to its brittleness, the anode is cast as a hollow cylinder and
closed at one end. The inner surface is then copper plated and the
cylinder is filled with polystyrene. Epoxy resin is used to fill any
remaining space. The anode cable is soldered to the copper plate.
Magnetite anodes have been successfully used in the cathodic protection
of buried structures and those immersed in seawater. The maximum
operating current density is 0.115 kA m-2 and the anode consumption
rate is approximately from 1 to 4 g A-1y-1.
• Lida: This is a recently developed anode. It is claimed that it has
superior mechanical, consumption and electrochemical properties
compared with conventional anodes. The anode is composed of an inert
 metal oxide , ruthenium oxide coated titanium. The operating current
density is 0.8 kA m-2 and the consumption rate is in the range of 0.8 mg

Semi-Consumable Anodes
Semi-consumable anodes such as graphite and high silicon iron have been in
service since the first industrial electrochemical systems were built.

• Graphite: Graphite anodes are widely used. Carbon has been used as an
anode in chlorine production since the end of the nineteenth century.
Graphite, which is less porous and more electrically conductive, is now
preferred for use in impressed anode materials. However, graphite can
still be highly porous, with the porosity being exacerbated by gas
evolution. For this reason, graphite is often impregnated with resins to
reduce solution ingress and improve mechanical strength. Graphite
anodes are inert when chlorine evolution is occurring, chlorine being
produced efficiently at low polarizations. But if oxygen formation
predominates, as in low chlorine media, graphite is oxidized to carbon
dioxide. Graphite deterioration also increases with decreasing pH
and increasing sulfate ions concentration.

To eliminate the possibility of galvanic corrosion caused by

detached pieces, graphite is not recommended for use in closed
systems. In addition, graphite suffers high consumption rates in
water at temperatures above 50oC. Consumption rates measured
for graphite depend on the environment and thus range from
0.045 in seawater to 0.45 kg in freshwater. Similarly the
corresponding operating current densities vary from 2.5 to 10 A m-
2
. The maximum operating voltage for graphite anodes is only
limited by excessive consumption rate and brittleness of the
material. The main disadvantages of graphite compared to other
impressed anodes are low operating current densities and inferior
mechanical strength. Graphite is generally used in conjunction
with carbonaceous back-fills in soil based impressed anode
systems.

• High silicon iron (HSI) alloys: These anodes are widely used. HSI
anodes contain about 14.5% silicon and certain alloys have 4.5%
chromium. Chromium has now replaced molybdenum as an alloying
element in this type of anode. The high silicon content ensures that the
alloy forms a protective film containing silicon dioxide, SiO2. A
prerequisite for the formation of this film is that the anode must initially
corrode during the first few hours of operation. The mechanism of this
passivating film is not well understood. The high electrical conductivity
of the film is believed to be due to the presence of iron oxides. Silicon
 dioxide is highly resistant to acids but it is readily dissolved in alkaline
conditions. High silicon iron anodes are extremely hard and cannot be
machined easily. They are generally cast and then stress relieved by
annealing. Although brittle these anodes have superior abrasion and
erosion characteristics compared to graphite.

High silicon iron anodes are widely used usually in conjunction

with carbonaceous backfills in soils. They have also found limited
use in marine and freshwater environments. The maximum
operating current density is determined by the type of alloy and
the environment. For instance, in groundbeds with backfills the
current density is limited to between 10 and 20 A m-2 because of
problems caused by gas entrapment. In marine environments, a
high iron chromium anode can be operated up to 50 A m-2. As for
graphite, the maximum operating voltage is limited by excessive
consumption and brittleness of the material. The consumption
rate of these anodes is influenced by the operating current
density and the nature of the environment. Generally, a lower
current density reduces the consumption rate. Wastage rates
range from 0.10 to 0.50 kg A-1 y-1. Sulfate ions in particular have
been noted to enhance the dissolution rate of these materials.

• Lead alloys: The function of lead as an impressed current anode

depends on the formation of a protective and electrically conductivity
film (101-102 Sm-1) of lead dioxide, PbO2. This film is non-stoichiometric
oxide and exists in two forms:
o alpha - PbO2 (orthorhombic)
o beta - PbO2 (tetragonal).

Lead dioxide is surprisingly stable in the presence of chloride ions.

The insoluble lead chloride, PbCl2, is believed to be responsible
for healing the defects in the film. This ensures that Pb/PbO2
behaves as an inert electrode and hence allowing at high
polarization the evolution of chlorine and oxygen. To form an
adherent and stable film of PbO2, lead is generally alloyed with
Ag and Sb. A typical alloy composition is Pb 6 Sb 1 Ag.

Owing to the low overvoltage of chlorine evolution on the surface

of these anodes, lead alloys are mostly used in seawater
applications. Maximum operating voltage and current density of
these anodes are 24 V and 1 kA m-2 respectively. The consumption
rate is in the range 1-10 g A-1 y-1. It should be added that lead
alloy anodes are sometimes used with platinum pins. It has been
found that a platinum microelectrode inserted into the surface of
 the lead enhanced the formation of PbO2. It is also worthwhile
noting that the performance of lead alloy anodes (with and
without Pt pins) is adversely affected at operation depths greater
than 30 m in seawater.

Consumable Anodes
Examples of this type of anode include scrap iron or steel and cast iron. The
anode is deliberately dissolved to provide the electrons required to polarize the
structure. Consumable anodes can be used in buried or under immersed
conditions. They have consumption rates of approximately 9 kg A-1 y-1. and
maximum current densities are in the order of 5 A m-2. Due mainly to their high
consumption rate the use of such anodes is rather rare unless a redundant
source of iron or steel is readily available such as an old ship beached below
low tide, a disused pipeline, well string etc. However, since such structures are
frequently massive, they represent a very low resistance to earth and therefore
can make the cathodic protection engineer's life much simpler.

Zinc Sacrificial Anodes

Schematic description of the cathodic protection of copper with a zinc anode:

In the large galvanic cell so formed, the zinc cylinder corroded away in a
manner that can be explained using the following electrical diagram:

where:
1. Represents the electrical resistance of the wire connecting the two
metal
 2. .. the electrical resistance through the copper plate
3. .. the electrical resistance through the zinc cylinder
4. .. the complex equivalent circuit for the metallic interfaces

Electrochemical Cell
The optimization of cell design in order to save energy while guaranteeing a
high product quality is a continuous task. Some of the general requirements of
cell design are:

• Simple modular design applicable to high current densities

• Large specific electrode area
• Low ohmic losses
• Applicable to multiphase systems
• Reliable operation with low maintenance
• Easy to scale-up

Basic components in an electrochemical cell

 • Planar electrodes (X and Y) made of electrically conductive materials:
metals, carbon, composites ...
• Reference electrodes (A, B, C) in electrolytic contact with an electrolyte
trough Luggin capillaries
• The cell itself or container made of an inert material: glass, Plexiglass,
...
• An electrolyte (solution containing ions)

Luggin Capillary

The Luggin capillary in a laboratory cell is made from glass or plastic. It is

generally filled with the test solution. The Luggin holds the reference
electrode. The tip of the Luggin capillary near the working electrode is open to
the test solution. The reference electrode senses the solution potential at this
open tip. Note that the Luggin tip is significantly smaller than the reference
electrode itself. The Luggin capillary allows sensing of the solution potential
close to the working electrode without the adverse effects that occur when the
large reference electrode is placed near the working electrode.

A luggin capillary can be used to bring the potential measuring point in close
proximity to a working electrode under investigation. Such a device can be
made of any material provided it is inert to the electrolytic environment. It
basically consists of a bent tube with a large enough opening to accommodate
a reference electrode and a usually much smaller opening only large enough to
insure diffusional movement of the electrolyte. The device minimizes any iR
drop in the electrolyte associated with the passage of current in an
electrochemical cell.
Silver/Silver Chloride Electrode

This is by far the most common reference type used today because it is simple,
inexpensive, very stable and non-toxic. It is mainly used with saturated
potassium chloride electrolyte, but can be used with lower concentrations such
as 1 M potassium chloride. Note that changing the electrolyte concentration
changes the potential. Silver chloride is slightly soluble in strong potassium
chloride solutions, so it is sometimes recommended the potassium chloride be
saturated with silver chloride to avoid stripping the silver chloride off the silver
wire.

The silver-silver chloride electrode is the most common due to its ease of
manufacture and its superior temperature range, actually usable even above
130oC. The electrode is a silver wire that is coated with a thin layer of silver
chloride either by electroplating or by dipping the wire in molten silver
chloride. When the electrode is placed in a saturated potassium chloride
solution it develops a potential of 199 mV vs the standard hydrogen electrode.
The potential developed is determined by the chloride concentration of the
solution, as defined by the Nernst equation. The potential of the electrode
remains constant as long as the chloride concentration remains constant. The
silver-silver chloride reference electrode develops a potential proportional to
the chloride concentration, whether it is sodium chloride, potassium chloride,
ammonium chloride or some other chloride salt.

The concentration of chloride in the reference electrolyte determines the

potential of the reference element. Potassium chloride is the most widely used
electrolyte because it does not generally interfere with pH measurements
and the mobility of the potassium and chloride ions are nearly equal. This
equal transference minimizes junction potentials since the (+) potassium and (-
) chloride ions move at the same rate. These ions provide the conductive path
between the reference element and the sample, commonly referred to as a
salt bridge.

Most of reference electrodes use a saturated KCl solution with an excess of KCl
crystals. The extra KCl dissolves into the electrolyte as the potassium and
chloride ions diffuse out through the liquid junction in normal use. This extra
buffer of KCl extends the time before the reference cell starts to drift due to
the depletion of chloride ions in the electrolyte.

The silver-silver chloride electrode simplicity of fabrication and fundamental

ruggedness makes it a good candidate for many industrial applications where
the electrochemical potential has to been measured or controlled. The
following commercial electrode is specifically to be embedded in reinforced
concrete.
Pitting corrosion

Pitting corrosion occurs in materials that have a protective film such as a

corrosion product or when a coating breaks down. The exposed metal gives up electrons
easily and the reaction initiates tiny pits with localised chemistry supporting rapid attack.
Control can be ensured by:

1.Selecting a resistant material

2.Control of the chemistry of fluids and use of inhibitors
3.Use of a protective coating
4.Maintaining the material’s own protective film.

CONCENTRATION CELL CORROSION (CREVICE)

If two areas of a component in close proximity differ in the amount of reactive
constituent available the reaction in one of the areas is speeded up. An example of this is
crevice corrosion which occurs when oxygen cannot penetrate a crevice and a differential
aeration cell is set up. Corrosion occurs rapidly in the area with less oxygen. The
potential for crevice corrosion can be reduced by:

1.Avoiding sharp corners and designing out stagnant areas

2.Use welds instead of bolts or rivets
CORROSION CAUSED BY COMBINED ACTION
This is corrosion accelerated by the action of fluid flow sometimes with the added
pressure of abrasive particles in the stream. The protective layers and corrosion products
of the metal are continually removed exposing fresh metal to corrosion. Prevention can
be achieved by:
1.Reducing the flow rate and turbulence
2.Use of replaceable or robust linings in susceptible areas
3.Avoiding sudden changes of direction
4.Streamlining or avoiding obstructions to the flow

STRESS CORROSION CRACKING

The combined action of a static tensile stress and corrosion which forms cracks and
eventually catastrophic failure of the component. This is specific to a metal material
paired with a specific environment. Prevention can be achieved by:
1.Reducing the overall stress level and designing out stress concentrations
2.Selection of a suitable material not susceptible to the environment
3.Design to minimise thermal and residual stresses
4.Developing compressive stresses in the surface the material
5.Use of a suitable protective coating