2 Corrosion 1

Corrosion
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JPS-E / Corrosion / 1
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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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:
Below a certain limit there is no corrosion Above a certain limit rapid corrosion will develop
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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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Corrosion Speed differ When Exposed to the Same Environment

In a strong alkaline environment Aluminium and Zinc will corrode rapidly, while steel will be passive
Aluminium Zinc Steel
Protective Iron oxide

pH > 10
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Corrosion has a deferent rates
Sea Water
Fresh Water
Start The Video

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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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Electrochemical Corrosion
Start The Video

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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
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 C1 reference electrodes Potential, volt Ag / Ag CL Rapid corrosion
-0.55
Potential, volt Zinc

+ 0.50
General corrosion
Some corrosion
-0.80 +0.25
100% Cathodic protection

-1.05
Increasing polarisation
Overprotection
-1.45
-0.3
Possible coating damage

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How To Measure the Corrosion Potential Of A Structure
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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
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 alkaline solutions prevent corrosion (pH 10 higher)
Zinc and Aluminium Slow corrosion at close to neutral solutions Heavy corrosion in acidic and alkaline solutions
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pH-scale
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Acidic
Neutral
Alkaline
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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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Temperature and Humidity Affects the Corrosion Rate

The corrosion rate for steel will normally increase with
Increasing temperature
Increasing humidity
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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
Cracks Remaining stresses Hydrogen absorption Poor cleaning
Initiation of crevice corrosion Stress corrosion cracking Hydrogen embrittlement Osmotic blistering, crevice
corrosion
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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
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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Sacrificial Anode
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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, Chromate's and Phosphates.
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Cut the Current by Paint
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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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Paint & Cathodic Protection
Start The Video

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Apart from using Paint and CP: How to Protect Against Corrosion ?
Corrosion protection can be achieved in many ways

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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)
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

A. B. Organic inhibitors Inorganic inhibitors I. II. III. Anodic Cathodic Dual: Anodic and cathodic
1. 2. 3.
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Forming thick protective films Reacts with the metal to form a protective film on the surface Adsorption 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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What about Rust Converters ?

Two important properties: Some convert red rust to black rust (magnetite) Some react with iron / rust to form inert reaction products Contaminant containing chromate and / or Phosphate will remain on the surface. Thorough steel brushing is required NB! Water soluble salts will not be removed !
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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
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 Crevice corrosion Pitting corrosion Stress corrosion cracking Titanium Hydrogen embrittlement Fatigue
Aluminium Pitting corrosion Galvanic corrosion

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Copper based alloys Erosion corrosion
Costs involved in Material Selection and Corrosion Protection

1. MATERIAL COSTS Material itself Pre-fabrication Dimensions Components Availability Volume 2. INSTALLATION
3. CORROSION PROTECTION REQUIRED

4. THERMAL INSULATION REQUIRED 5. EXTENT OF MAINTENANCE 6. DESIGN LIFE
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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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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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Welds may Corrode Rapidly If Not The Correct Weld Material is Used
Corrosion attack on weld Filler is less noble than the steel Electrolyte
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 parameters: Anode - Cathode area ratio. Electrolyte resistivity (Conductivity) Difference in galvanic potential of the metals
Fe ++
Cathode Stainless steel

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e-
Anode Steel
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

Anode
Cathode
Unpreferable area ratio Small anode will corrode rapidly
Galvanic Corrosion In A Pipe System
Here the flange will be attacked from both sides
Sacrificial spool: Less noble material than CuNi Will corrode instead of the expensive flange
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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 parameters: Type of metals connected Area ratio
1.00 1.50
Without insulation
With insulating
spool piece, 2m
Surrounding environment
0.50
0.00
0.30
0.80
1.30
1.80
2.30
Distance from coupling, m Paint School

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
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Steel
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
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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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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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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Evaluation of Rust Grades, ISO 8501-1

Rust grade A Rust grade B
Rust grade C
Rust grade D
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Severe Corrosion
Corrosion due to a combination of Sharp edges Rough welds (not grinded) Missing stripe coating
Tank hjrne, notcher
Tykk rust
Kanter 4 - 49
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Severe corrosion in a tank

Corrosion due to a combination of Sharp edges Rough welds (not grinded) Missing stripe coating
Tank hjrne Notcher
Kanter
Tykk rust 4 - 50
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Corrosion due to Back Burning

Hot work on the back
side of the painted surface Premature rust due to: Insufficient pretreatment and paint application
Rd overflate med gamle gjennombrenninger Reparasjonsarbeid drlig utfrt ruster igjennom 4 - 48
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Poor Pre-treatment and Application Technique

Premature rust on
sharp edges, Weld seams and Weld beads These areas should have been grinded Also: Spraying only in one direction: Creates shadows and inferior coating thickness No stripe coating
Rust, sveis, grnn tank

0590 - 06 4226 - 57
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Corrosion of Welds in a Water Ballast Tank

Premature rust on welds Rough weld seams.
Should have been grinded Probably in combination with poor stripe coating (Mud can be seen, particularly on the bottom)
Tank, rust, sveis 0590 - 29 4226 - 54
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Corrosion. Too Thin Paint Film

Corrosion of steel
on a flat area. Paint film is too low. This is verified by film thickness measurements
Mler filmtykkelse
Rep. for tynt pfrt p en flekk

Rust gjennomslag
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Flaking of Paint. Corrosion

The paint has been
applied too thick The film cracks and breaks up. Corrosion has developed on the steel after a short period of time A too thick film is just as dangerous as a too thin
Tykk ls maling, hjrne 4-5
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Corrosion on Sharp Edge and Spot Welds
Early corrosion on
sharp edge and on discontinuous welds Paint has newly been applied Exposed to wind and weather for approximately 2 weeks
Konstruksjon, Alu. maling rust i kant (skarp) Rust i punkt sveis mangelfullt stl og malingsarbeide.
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Corrosion on Weld Seams on Ships Hull

Untreated or poor
treated welds suffering early corrosion Probably wire brushed without washing with fresh water In addition, the paint film is too thin
Skipsside gul/bl Gamle gjennombrenninger Drlig rep. arbeid Rust gjennomslag
4 - 47
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Corrosion on Old Ship Hull

Old vessel, ready for
full maintenance Old paint system Suffering mechanical damages and exposed to wear and tear
Skipsside i dokk Meget rusten T/S - S/B
Stor jobb
Stor ruhet Stort oljeforbruk
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Pitted and Corroded Steel after Blast-cleaning

Corrosion has been going
on too long The steel shows deep pits, sharp edges and is very uneven Difficult for a paint system to give satisfactory protection Overflate med dype rust tringer Nyblst Stor ruhet Vanskelig male, har gtt for lenge
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Spot-blasting and Poor Application Technique.

Spot-blasted steel Loose paint edges Application has been
done in only one direction Corrosion has developed shortly after application Direction of application
Rustkanter T/S
0589 - 75 4226 - 73
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Corrosion on Superstructure
Intersection point
between the steel structure and the rubber packing is a difficult area to paint If not painted well premature rust develop Bad construction Bad stripe coating
Vinduer
4226 - 39 0590 - 43
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Mill Scale on Pipes

Corrosion on the mill
scale Rust and mill scale must be removed prior to paint application. Mill scale can be removed by blastcleaning
Rr, delvis med gldeskall/rust viktig fjerne gl.sk. fr maling. Kan ikke brstes vekk. Bedre med lett rust enn g.l. sk.
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Corrosion Due to Recoil from Blast-cleaning

Blast-cleaning has been
carried out on the opposite side. Recoil of grit has damaged the intact paint This is easily done, but difficult to see during inspection Corrosion develops after a short period of time
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Blseskade 0590 - 09
Thank You !
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2 Corrosion 1

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Corrosion

under formation of corrosion products

Production and Degradation of Steel

Plates, pipes, profiles, etc.

Raw material Iron ore

Manufacturing / Refining Brings the Material to a Higher Energy Level

The resistance to the oxidation (corrosion) varies for

How is Rust Formed ?

Painted surface exposed to humidity

The blisters break and corrosion is initiated

How is Rust Formed ?

Freely Corroding Steel

How Fast Will A Metal Corrode ?

The speed of a corrosion process depends on:

How Fast Will A Metal Corrode ?

Some materials Corrode Faster Than Others

Corrosion Speed differ When Exposed to the Same Environment

Protective Iron oxide

Corrosion has a deferent rates

Start The Video

Pre-requisites For Corrosion

A Cathode: The noble metal / alloy (or part of

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

Start The Video

Galvanic Series in Sea Water

Least energy required for refining

High energy required for refining

What Kind of Information Can Be Obtained From The Galvanic Series ?

The greater the potential difference, the greater the corrosion.

Potential, volt Zinc

100% Cathodic protection

Possible coating damage

How To Measure the Corrosion Potential Of A Structure

Elements Influencing the Corrosion Speed of Metals

Corrosion Speed For Carbon Steel as Function of Flow Velocity

SEAWATER VELOCITY, (m/s)

Corrosion Speed for Carbon Steel Exposed To Seawater

The pH of the Solution Will Affect the Corrosion Speed

Parameters Influencing The Corrosion Speed. Atmospheric Corrosion

Temperature and Humidity Affects the Corrosion Rate

Atmospheric Corrosion Corrosion Rate Depends on Humidity

40 60 80 100 Relative Humidity, %

Welding is an Initiator for Corrosion

Cracks Remaining stresses Hydrogen absorption Poor cleaning

How to Prevent or Reduce Corrosion

Start The Video

Corrosion Protection By Paints Principles

Cut the Current by Paint

Start The Video

Paint Can Be Used To Reduce Galvanic Corrosion

Paint & Cathodic Protection

Start The Video

Systems With Flowing Water Must Be Designed To Avoid Turbulent Flow

Avoid Stagnant Water At Bottoms Of Tanks and Containers

Avoid solutions where Dust / Humidity Collects

Material Selection - Maintenance Philosophy

Resistant material that will last the total design

Corrosion Properties of the Materials

Corrosion inhibitors are chemicals mostly

Various Ways Of Classifying Corrosion Inhibitors

Inhibitors Classified According to Mechanism

II. Cathodic inhibitors:

III. Dual inhibitors: