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Definition of Corrosion
Corrosion is a reaction between Material and Surrounding environment under formation of corrosion products
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Rust
The presence of water / humidity and Oxygen is a pre-requisite for corrosion of steel
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The resistance to the oxidation (corrosion) varies for different materials When brought in contact with an electrolyte (aqueous solution that conducts electricity) some metals easily dissolve into ions. These are called Base metals Noble metals have a very strong resistance to corrosion and do not react to form ions unless exposed to very aggressive chemicals
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The water molecules penetrate the paint Due to osmotic forces blisters are formed
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Fe (OH)2 OH Fe 2+ Anode
Cathode e
Cathode: O2 + 2 H2O + e 4 OH
Anode: Fe Fe 2+ + e
Water, Iron ions and Hydroxyl ions combine to give rust : Fe (OH)2 , Fe2O3. n H2O
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Fe 2+
O2 + H2O + 2e -
2OH
Cathode
2e2e-
Cathode
Anode
2e2e-
Steel plate
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A galvanic cell
2e-
Cathode: Steel
O2
Zn = Zn + 2 e
2+
Anode: Zinc
- 2OH O2 + H2 O + 2e - =
Potential (volts) *
+0,500 - 0,205 - 0,225 - 0,235 - 0,380 - 0,435 - 0,600 - 0,800 - 1,080 - 1,140 - 1,550
Corrosion
Least corrosive
Very corrosive
*) Potential in seawater measured versus a Copper / Copper Sulphate reference electrode Paint School
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Type of material Type of electrolyte / surrounding environment Service conditions Contaminants aggravating the conditions Corrosion protection
In some cases there are threshold limits:
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Below a certain limit there is no corrosion Above a certain limit rapid corrosion will develop
Electrochemical potential (Noble / base metal) Formation of protective oxide films on the surface of the base material Conductivity of electrolyte Presence of aggressive ions Service conditions
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The metal with the more negative potential will corrode The metal with the more positive potential will be protected
Corrosion speed depends on the difference in potential between the metals
Steel in Seawater
Potential versus Zinc & Ag/Ag Cl ref. electrodes
Ag / Ag Cl
Potentials in volt
Rapid corrosion
Zinc
Cu / CuSO4
- 0.55
+ 0.50
- 0.60
General corrosion
- 0.80
Some corrosion
100% Cathodic protection
+ 0.25
- 0.85
-1.05
Increasing polarisation
+ 0.0
-1.10
- 1.30
Overprotection
Possible coating damage
- 0.25
- 1.35
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Sea water
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Reference electrode
Temperature Salinity Oxygen content Water velocity Acidity (See below) Type of electrolyte ( e.g. cargo or chemicals) Content of contaminants / pollution that
promotes corrosion Micro-organisms.
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0
0 1 2 3 4
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Temperature
b
a) Steel surface
a
b) Sea Water
Temperature, C
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pH-scale
Acidic
Neutral
Alcaline
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0
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20
40
60
80
100
Relative Humidity, %
Cracks
Remaining stresses
Hydrogen absorbtion
Poor cleaning
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Corrosion protection
There are many ways of preventing corrosion Here: Focus on Paints and Cathodic Protection (CP) For submerged structures our
general recommendation is: Use Paint as the primary corrosion protection system Back up the paint system by a CP system. CP will protect weak points and damaged areas of the paint film and thereby prolong the lifetime of the structure
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Several paints protect the steel by forming a barrier to the surrounding environment
A barrier will increase the
resistance in the galvanic circle A thick barrier will give better protection than a thin
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Two paint systems are exposed to the same environment One system may be almost inert to the surrounding environment The other may deteriorate rapidly and corrosion starts It is important to know the properties of the system before putting it into service
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Apart from using paint and CP: How to protect against corrosion ?
Corrosion protection can be achieved in many ways
Good design Avoid corrosion traps Improved accessibility - maintenance Proper materials selection Insulate between dissimilar materials Change the surrounding environment Remove water / humidity Apply metallic coatings Use corrosion inhibitors (closed systems)
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Humidity is trapped
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Resistant material that will last the total design life. (No maintenance) Non-resistant material. (Will be replaced when corroded) Material with fairly good resistance. Corrosion protection system must be applied
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Knowledge is required for selecting the correct material for a given application
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Corrosion inhibitors
Corrosion inhibitors are chemicals, mostly added to closed systems Inhibitors will, even at low concentrations, reduce the dissolution (corrosion) of the metal They are divided into groups, often in accordance with their protection mechanism
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Mechanism
Anodic Cathodic Dual: Anodic and cathodic
Film forming
1. 2.
3.
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Forming thick protective films Reacts with the metal to form a protective film on the surface Adsorbsion on the metal surface
II.
Cathodic inhibitors:
Reduces the cathodic reaction
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Types of corrosion
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.
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Uniform corrosion Galvanic corrosion Selective (preferential) corrosion Pitting corrosion Crevice corrosion Micro biological corrosion (bacteria) Corrosion fatigue Stress corrosion cracking Erosion corrosion Cavitation Stray current corrosion
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2. Make the optimal selection of materials 4. Change the environment Inhibitors Remove Oxygen Reduce water flow velocity Change pH Change temperature Reduce relative humidity, % RH
Uniform corrosion Uneven corrosion (deep pits) Galvanic corrosion Stress corrosion cracking
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Aluminium
Erosion corrosion
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Uniform corrosion
A steel surface consists of noble and less noble areas This can be looked upon as small galvanic cells The anodic parts will corrode
Rust
-
+ + -
+ -
+
+
+ + +
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General corrosion
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Uniform corrosion
A corrosion attack that is uniformly distributed over the entire surface
Corroded area
Steel
Thickness after corrosion Original thickness
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General corrosion
General corrosion is uniform by nature Still, deep pits or uneven areas are found
CD 0026-001
CD 4911-0004
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Steel
Steel
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Seawater
Ingress of seawater
Plate Paint
Stainless Steel
Corroded areas
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Welds may corrode rapidly if not the correct weld material is used
Corrosion attack on weld Filler is less noble than the steel Electrolyte
Steel
Cathode Anode Cathode
NOTE The weld material (filler) must always be more noble than the base material
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Galvanic corrosion
Pre-requisites: Water (Electrolyte) Two metals with different potentials Electrical contacts between the metals
Important parametres: Anode - Cathode area ratio. Electrolyte resistivity (Conductivity) Difference in galvanic potential
of the metals
Fe ++
e-
Anode Steel
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Corroded area
Electrolyte (Seawater)
Anode
Cathode
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Galvanic corrosion
(or Bimetallic corrosion)
The severity of the attack depends on: Conductivity of the electrolyte Anode - Cathode area ratio
Electrolyte with good conductivity Wide corrosion attack
Anode
Cathode
Anode
Anode
Cathode
Anode
Anode
Cathode
Correct solution
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Sacrificial spool: Less noble material than CuNi Will corrode instead of the expensive flange
RV
RI
EE
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Without insulation
With insulating
spool piece, 2m
0.50
0.00
0.30 0.80 1.30 1.80 2.30
Water
Pitting corrosion
Oxide film
Stainless steel
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Pitting corrosion
Pitting corrosion is a localised attack on a material normally protected by a passive film The passive film may be destroyed mechanically or by aggressive ions in an electrolyte Severe corrosion may take place beneath the passive layer
Pitting corrosion
Passive layer
Stainless steel
Seen from above
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Cross section
CD 0026-004
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Erosion corrosion
Erosion corrosion on a plane surface
Cross section From above
Flow direction
Erosion corrosion
Erosion corrosion caused by the uneven joint
Direction of flow
Corrosion fatigue
Corrosion Fatigue is a combined effect of an
aggressive environment and dynamic loads on a structure
Load
Fatigue only
Corrosion fatigue
- +
Quay To earth
Pontoon
Corrosion
Seawater
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