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Corrosion

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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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Production and degradation of steel


Reaction between the material and the surrounding environment takes place

Plates, pipes, profiles, etc.

Raw material Iron ore

Rust

The presence of water / humidity and Oxygen is a pre-requisite for corrosion of steel
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Manufacturing / Refining Brings the Material to a Higher Energy Level


Oxidation of metals is a natural process

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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How is rust formed ?

Painted surface exposed to humidity

The water molecules penetrate the paint Due to osmotic forces blisters are formed

The blisters break and corrosion is initiated

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How is rust formed ?


Water Steel

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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Freely corroding steel


Sea water (electrolyte)
O2 + H2O + 2e 2OH

Fe 2+

O2 + H2O + 2e -

2OH

Cathode
2e2e-

Cathode

Anode
2e2e-

Steel plate
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Freely corroding steel

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The corrosion process. A galvanic cell


Materials exposed to seawater
will obtain different electrochemical potentials If two differently charged metals are brought in contact a current will start to flow between them Electrons will transport current between the metals and ions in the electrolyte

CP and corrosion: Corrosion_cell1

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Pre-requisites for corrosion


A galvanic cell consists of:

A Cathode: The noble metal / alloy (or part of metal) An Anode: The less noble metal / alloy An electrical connection between the two metals. Conducting electrical current (by electrons) An electrolyte: Conducting electrical current (by ions)

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A galvanic cell
2e-

Cathode: Steel
O2

Zn = Zn + 2 e

2+

Anode: Zinc

- 2OH O2 + H2 O + 2e - =

In seawater, a calcareous deposit is formed on the steel surface


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Galvanic series in sea water


Energy Metal/alloy
Gold Silver Titanium Stainless steel (316, active) Ni-Al- Bronze Copper Carbon steel Aluminium (pure) Zinc (anode alloy) Aluminium (anode alloy) Magnesium (anode alloy

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 energy required for refining

Least corrosive

High energy required for refining

Very corrosive

*) Potential in seawater measured versus a Copper / Copper Sulphate reference electrode Paint School
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How fast will a metal corrode ?


The speed of a corrosion process depends on:

The properties of the material The surrounding environment

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How fast will a metal corrode ?


A general answer can not be given. In most cases the corrosion speed depend on:

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

Some materials corrode faster than others


The corrosion speed depends on:

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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Some environments are more aggressive than others.


Steel will corrode at different
rates when exposed to dissimilar environments, such as seawater and fresh water Seawater is more aggressive than fresh water and will give a higher corrosion velocity

CP and corrosion: Corrosivity_liquid1

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Corrosion speed differ when exposed to the same environment


In a strong alcaline environment Aluminium and Zinc will corrode rapidly, while steel will be passive
Aluminium Zink Steel

Protective Iron oxide


pH > 10

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Corrosion speed differ when exposed to the same environment


Two metals are exposed to the
same environment One may be almost inert The other metal may corrode very rapidly Important to know the properties of the metal before putting it into service

CP and corrosion: Corrosivity_metals1

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Galvanic potentials in seawater

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What kind of information can be obtained from the galvanic series ?


The difference in Galvanic Potential will tell which of the two materials that will corrode when connected

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

The greater the potential difference, the greater the corrosion.


Rule of thumb: A potential difference less than
50 mV will cause no additional corrosion
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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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How to measure the corrosion potential of a structure


Volt meter Structure

Sea water
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Reference electrode

Elements influencing the corrosion speed of metals


Submerged materials

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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Corrosion speed for carbon steel as function of flow velocity


Corrosion rate (mm/year)
1.2 1.0 0.8 0.6 0.4 0.2

0
0 1 2 3 4

SEAWATER VELOCITY, (m/s)


Source: F.L. La Que, page 134 Paint School
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Temperature and humidity affects the corrosion rate

The corrosion rate for steel will normally increase with

Increasing temperature Increasing humidity

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Corrosion speed for carbon steel exposed to seawater


The corrosion speed will increase with increasing steel temperature, but decrease with increasing seawater temperature
Corrosion rate (mm/year)
0.6 0.5 0.4 0.3 0.2 0.1 0 0 20 40 60

Temperature
b

a) Steel surface
a

b) Sea Water

Temperature, C

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The pH of the solution will affect the corrosion speed


Steel Corrosion increases at lower pH. (Acidic solutions, pH 6 lower) Strong alcaline solutions prevent corrosion (pH 10 higher) Zinc and Aluminium Slow corrosion at close to neutral solutions Heavy corrosion in acidic and alcaline solutions

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pH-scale
Acidic

Neutral

Alcaline

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How to measure the corrosion potential of a structure


+

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Parameters influencing the corrosion speed. Atmospheric corrosion


Humidity Temperature Concentration of salts Amount of air pollution,
including acid rain, soot and dust particles

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Atmospheric corrosion corrosion rate depends on humidity


Corrosion rate

0
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20

40

60

80

100

Relative Humidity, %

Welding is an initiator for corrosion


Metallurgical conditions May give phases with different electrochemical potentials: Galvanic corrosion Initiation of crevice corrosion

Cracks

Remaining stresses
Hydrogen absorbtion

Stress corrosion cracking


Hydrogen embrittlement

Poor cleaning

Osmotic blistering, crevice corrosion

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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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Corrosion protection by paints. Principles


The barrier effect.
Builds a barrier that prevents seawater or other corrosive agents from coming into contact with the substrate. Example: Epoxy paints. The cathodic effect. The paint itself acts as a sacrificial anode (Galvanic effect). Example: Zinc-rich paints. Inhibiting / passivating effect The paint passivates the surface of the steel. Example: Paints incorporating rust preventing pigments. (Red lead, Chromates and Phosphates.
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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

CP and corrosion: Cell_paintprotection1

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Some environments are more aggressive to paints than others.


Steel will corrode at different
rates when exposed to dissimilar environments, such as seawater and fresh water Seawater is more aggressive than fresh water and will give a higher corrosion velocity

CP and corrosion: Corrosivity_liquid2

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Paint systems show different properties when exposed to one environment


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

CP and corrosion: Corrosivity_liquid2

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Paint systems show different properties when exposed to one environment


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

CP and corrosion: Corrosivity_environment1

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Paint can be used to reduce galvanic corrosion


Two different materials are in electrical contact They are both exposed to the same, corrosive
environment
Protective measure Perform proper pre-treatment and paint the cathode Never paint the anode only

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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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Systems with flowing water must be designed to avoid turbulent flow


Erosion corrosion will develop at sharp bends and intrusions

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Avoid stagnant water at bottoms of tanks and containers


Unfortunate Better Best solution

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Avoid solutions where dust / humidity collects


Unfortunate Better Best solution

Humidity is trapped
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Material selection - maintenance Philosophy


When selecting materials there are basically three options:

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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Corrosion Properties of the materials



All materials have their strong sides But, they also have their weak points

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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Various ways of classifying corrosion inhibitors


Organic / inorganic
A. B. Organic inhibitors Inorganic inhibitors I. II. III.

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

Inhibitors Classified according to mechanism


I. Anodic inhibitors:
Reduces the anodic dissolution of the metal

II.

Cathodic inhibitors:
Reduces the cathodic reaction

III. Dual inhibitors:


Reduces both the anodic and 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

Costs involved in material selection and corrosion protection


1. Material costs Material itself Pre-fabrication Dimensions Components Availability Volume 2. 3. 4. 5. 6. Installation Corrosion protection required Thermal insulation required Extent of maintenance Design life

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How to prevent or reduce corrosion


1. Improve the construction Design Position 3. Use corrosion protection Paint Cathodic protection Metallic coatings Erosion resistant coatings Rubber or plastic Anodic protection
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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

Most frequently occurring types of corrosion


On carbon steel

Uniform corrosion Uneven corrosion (deep pits) Galvanic corrosion Stress corrosion cracking

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Most frequently occurring types of corrosion


Stainless steels Titanium

Crevice corrosion Pitting corrosion Stress corrosion cracking

Hydrogen embrittlement Fatigue

Aluminium

Pitting corrosion Galvanic corrosion

Copper based alloys

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 with mill scale


Outdoor exposure The mill scale cracks Corrosion will develop on the steel Mill scale is more noble than steel Mill scale Corrosion

Steel

Steel

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Crevice corrosion occurs under paint spillage or plates


Crevice corrosion occurs in narrow gaps where the oxygen concentration is lower than on the freely exposed part of the material

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 ++

Cathode Stainless steel

e-

Anode Steel

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Galvanic corrosion is to a large extent determined by the conductivity of the electrolyte


The corrosion attack decreases with increasing distance from the cathode due to an increased ohmic resistance

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

Electrolyte with low conductivity Attack close to cathode

Cathode Paint School


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Anode

Cathode

Unfavourable area ratio Small anode will corrode rapidly

Galvanic corrosion in a pipe system


Wrong solution

Here the flange will be attacked from both sides

Correct solution
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Sacrificial spool: Less noble material than CuNi Will corrode instead of the expensive flange

Galvanic Corrosion Corresponding Electrical Circuit


I EU RM

Basic formula, Ohms law: U = RI


I = Current, mA EU = Potential unnoble metal EE = Potential noble metal RI = Resistance in spacer Rv = Electrolyte resistance Rm = Resistance of metal

RV
RI

EE

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Galvanic corrosion can be reduced by using an insulating material.


Corrosion rate of steel when connected to Stainless steel, mm / year. Important parametres:
1.50

Type of metals connected Area ratio Surrounding environment


1.00

Without insulation

With insulating
spool piece, 2m

0.50

0.00
0.30 0.80 1.30 1.80 2.30

Distance from coupling, m Paint School


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Pitting corrosion on stainless steel

Salts with aggressive ions

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

Pitting corrosion on an Aluminium pipe


Corrosion started from the inside Aggressive ions has caused an attack penetrating the pipe wall Photo taken from the outside

CD 0026-004

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Erosion corrosion
Erosion corrosion on a plane surface
Cross section From above

Flow direction

Sharp corners creates turbulence, leading to erosion corrosion


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Erosion corrosion
Erosion corrosion caused by the uneven joint
Direction of flow

Uneven joint Severe corrosion attack on pipe wall


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Corrosion fatigue
Corrosion Fatigue is a combined effect of an
aggressive environment and dynamic loads on a structure

Load

Fatigue only

No failure above line

Corrosion fatigue

No. of dynamic cycles


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Stray current corrosion


Welding transformer

- +

Welding on board Stray current

Quay To earth

Pontoon

Corrosion

Seawater

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