CORROSION MECHANISM

Yves GUNALTUN

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 INTRODUCTION
INTRODUCTION TO
TO CATHODIC
CATHODIC PROTECTION
PROTECTION

• CORROSION MECHANISMS

• CAUSES OF EXTERNAL CORROSION

• MAIN PARAMETERS

• CORROSON CONTROL BY CATHODIC PROTECTION

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 CORROSION MECHANISM

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BEHAVIOUR
BEHAVIOUR OF
OF METALS
METALS IN
IN THE
THE NATURE
NATURE

• In nature, elements are present in their most stable form(s)

• Some elements are in metallic form, for example gold.

• Most of elements are in "combined" form (chemical compounds like

mineral salts)

• Iron, which is the main construction material, is present mainly as iron

oxide(s) and iron sulphur.

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STABILITY
STABILITY OF
OF ENGINEERING
ENGINEERING MATERIALS
MATERIALS

EXTRACTIVE
METALLURGY ( G > 0)
IRON OXIDE
IRON (METAL)
IRON SULPHIDE
CORROSION ( G < 0)

IT IS IMPOSSIBLE TO STOP CORROSION.

BUT

IT CAN BE DELAYED OR ITS RATE CAN BE REDUCED.

• Different metals and environments have different energy levels

associated with them.
• Any reaction can occur only if it is thermodynamically possible.
• The change in energy must always be from the higher energy
state to the lower one.

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DEFINITION
DEFINITION

CORROSION:

• DAMAGE OF ENGINEERING MATERIALS BY A CORROSIVE AGENT.

• But not every process necessarily leads to damage.

• Damage is said to occur when the function is impaired.

• CORROSION IS AN ELECTROCHEMICAL PHENOMENON

• However, in addition, pure chemical reactions or entirely

physical process can also be occurring.

• DAMAGE CAN BE CLASSIFIED AS UNIFORM, LOCALISED

(SHALLOW PIT, PITTING, CREVICE CORROSION, SELECTIVE
DISSOLUTION) AND CORROSION CRACKING.

• But metal loss is not necessarily the unique cause of failure.

Hydrogen embrittlement is the penetration of hydrogen into
metal matrix under a cathodic process.

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CAUSES
CAUSES OF
OF CORROSION
CORROSION IN
IN OIL
OIL AND
AND GAS
GAS PRODUCTION
PRODUCTION

Liquid water Wetting of the metal

Corrosive agent CO2 H2 S O2 Cl2 Organic acids

Heterogeneities In the electrolyte On the metal surface In the metal matrix

Water
Steel

Favourable / accelerating parameters

Time 1 day 1 month 1 year 10 years...

Production parameters Temperature Salts Flow effects Constraints Sand

Human impact Bacteria Conditions of use Bad design /construction

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CORROSION
CORROSION -- CONDITIONS
CONDITIONS

Corrosion takes place if

• free water is in contact with metal

• corrosive agent is dissolved in the water phase. Corrosive agent
can be O2, CO2, H2S, acids (H+), Cl2.
• there is heterogeneity in the corrosive medium or on the metal
surface resulting in potential difference between two locations
on the metal surface.
• Some other parameters can modify the corrosivity of the effluent

• Corrosion resistance of the material

• Time
• Environmental / operating conditions
• External causes

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CONSTRUCTION
CONSTRUCTION

Bad construction practices can be more dangerous than any corrosive agent.

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 CAUSES
CAUSES OF
OF CORROSION
CORROSION IN
IN OIL
OIL AND
AND GAS
GAS PRODUCTION
PRODUCTION

INTERNAL CORROSION EXTERNAL CORROSION

• By the produced effluents: By external environment:

CO2, H2S, organic acids,
Solids • atmosphere,
• By the injected effluents Oxygen
Oxygen, bacteria
bacteria, chlorine • sea water
• By the fluids used for Oxygen, bacteria
« utilities » • soils,
Geological cells
Oxygen, bacteria

IN OIL AND GAS PRODUCTION THE TEMPERATURE OF THE PRODUCED

FLUID IS GENERALLY BELOW 250°C.

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HETEROGENEITY
HETEROGENEITY IN
IN THE
THE CORROSIVE
CORROSIVE MEDIUM
MEDIUM

Heterogeneity in the corrosive medium is generally initiated by the corrosion

reaction. Example: depletion of oxygen in the cavities.

WATER
TEFLON

STEEL

IRON I Bubbling of air in water allows

AIR ARGON saturation of water in oxygen
(increase of oxygen concentration
in water).
Na+ Na+
Cl - The bubbling of a gas like Nitrogen
Cl -
or Argon in water allows the
removal of the dissolved oxygen.

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HETEROGENEITY
HETEROGENEITY IN
IN THE
THE CORROSIVE
CORROSIVE MEDIUM
MEDIUM

WATER
TEFLON

STEEL

Oxygen concentration 1 ppm 0.1 ppm

Potential - 650 mV - 680 mV Ea - Ec = 30 mV

Oxygen concentration 10 0.1 ppm

Potential - 610 mV - 680 mV Ea - Ec = 70 mV

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 REFERENCE
REFERENCE ELECTRODE
ELECTRODE

• When an electrical current flows through the metal /electrolyte phase

boundary, a potential difference arises at the interface.
• The potential difference between metal and electrolyte can not be directly
measured.
• This potential difference is measured against a reference electrode.

E=Eo + (RT/nF) * Ln (Me++)

Cu

Cu ++
SO4 -
-
CuSO4
POROUS PLUG

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 POTENTIAL
POTENTIAL MEASUREMENT
MEASUREMENT

V
IRON REFERENCE
ELECTRODE

Fe / Fe ++
Cu / Cu ++ Cu ++

SO4 --

ELECTROLYTE

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 HETEROGENEITY
HETEROGENEITY IN
IN THE
THE CORROSIVE
CORROSIVE MEDIUM
MEDIUM

A chemical reaction may change locally the corrosivity around

the corroding surface.

1/2 O2 + H2O + 2e 2OH- pH

CATHODIC SURFACE

WATER
TEFLON

STEEL

ANODIC SURFACE

Fe + 3H2O Fe (OH) 3 + 3 H+ + 3e pH

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 THERMODYNAMIC
THERMODYNAMIC

The corrosion reaction can take place if it is thermodynamically possible

At pH = 0 in de-aerated water,
• potential of H+/H couple is 0 (nil)
• potential of Fe++/Fe couple is about - 0.4 to - 0.44
At pH zero, Iron will corrode.
At pH = 9 in de-aerated water,
• potential of H+/H couple is - 0.53
• potential of Fe++/Fe couple is about - 0.44
At pH 9, in de-aerated water Iron/steel will not corrode.
At pH = 9, in the aerated water:
• potential of O/O-- couple is 0.63
• potential of Fe++/Fe couple is about - 0.44
At pH 9, in aerated water Iron/steel will corrode.
O2 + 4 H+ 2 H2O E O/O-- = 1.23 + (RT/4F) Log (a4 H+ + aO2)

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 HETEROGENEITY
HETEROGENEITY IN
IN THE
THE CORROSIVE
CORROSIVE MEDIUM
MEDIUM

Corrosion under scale or biofilm is well known in oxygenated

water lines.

SCALE OR
BIOFILM

WATER

STEEL

Typical corrosion under corrosion products in

water injection lines with insufficient oxygen
control, low velocity and no cleaning.

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 GEOLOGICAL
GEOLOGICAL CELL
CELL

The oxygen content in clay is lower than in sand due

to low oxygen refurbishment possibility in clay.

Anodic
Clay zone

Clay Sand

Casing
Pipe
Sand Cathodic
zone
Anodic Cathodic
zone zone

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 CORROSION
CORROSION CELLS
CELLS ON
ON MARINE
MARINE STRUCTURES
STRUCTURES

Oxygen content

Riser or jacket
Depth

Air

Cathodic zone Sea

Anodic zone

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 WELDING
WELDING DEFECTS
DEFECTS

Anodic zone Anodic zone

Anodic zone
Support

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 CORROSION
CORROSION OF
OF STAINLESS
STAINLESS STEELS
STEELS

Iron Iron oxide

Stainless steel

Iron
Cracks if oxide
stress is
present

Stainless steels need oxygenated environment to remain passivated

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 CORROSION
CORROSION -- ELECTROCHEMICAL
ELECTROCHEMICAL ASPECT
ASPECT

AT METAL - SOLUTION INTERFACE

Oxidation at anode
Fe Fe++ + 2 e-

IA = « Anodic » current
Without the contribution of
an external current,
Reduction at cathode IA = - IK
2 H2O + O2 + 4 e- 4 OH-
H+ + e- 1/2 H2
H2O + e- 1/2 H2 + OH-

IK = « Cathodic » current

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 HETEROGENEITY
HETEROGENEITY ON
ON THE
THE METAL
METAL SURFACE
SURFACE

STEEL STEEL

Breakdown of the protective film

Non-metallic inclusion
Mesa corrosion by CO2

EXAMPLES OF OTHER HETEROGENEITIES:

Precipitated metallic compounds and impurities at the grain

boundaries

Junction of two or more different metals (galvanic corrosion)

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 ANODIC
ANODIC AND
AND CATHODIC
CATHODIC ZONE
ZONE ON
ON A
A CORRODED
CORRODED WELD
WELD

At the beginning of experience After a few hours of exposure

Anodic zones : yellow to corrosive
Cathodic zones : blue environment

Samples are immersed in water containing 0.1 % NaCl under 1 bar of CO2

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 SUMMARY
SUMMARY -- INHIBITION
INHIBITION

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 SUMMARY
SUMMARY -- INHIBITION
INHIBITION

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 SUMMARY
SUMMARY -- INHIBITION
INHIBITION

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GALVANIC
GALVANIC CORROSION
CORROSION &
& INTERGRANULAR
INTERGRANULAR CORROSION
CORROSION OF
OF S.
S. S.
S.

Galvanic corrosion Precipitation of metallic compounds

Precipitation of Cr23C6 if
C>0.03% and T=600-900°C

Water
Chromium content Cr23C6
Stainless
Carbon steel
steel 18 %

GALVANIC CORROSION

13 %

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HETEREOGENEITY
HETEREOGENEITY ON
ON THE
THE METAL
METAL SURFACE
SURFACE -- MESA
MESA CORROSION
CORROSION BY
BY CO
CO22

METAL LOSS : UNIFORM AND/OR LOCALISED CORROSION

LOCALISED CORROSION UNIFORM CORROSION

CATHODIC ZONE ANODIC ZONE

H + + e- H Fe Fe ++ + 2 e-
H+ H2 Na + Cl - WATER
Fe ++

e-
FeCO3 STEEL

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 GALVANIC
GALVANIC CORROSION
CORROSION

Anodic zones Steel Zinc

A
O2 + 2e- + H2O 2OH- Zn Zn++ + 2e-
e-

Steel Water

Zinc
Na+
Zn++
Cl -

Water
Electrical connection

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 STANDARD
STANDARD POTENTIAL
POTENTIAL OF
OF METALS
METALS

Eo (V) Standard E practical EMF : ELECTROMOTIVE FORCE

(TENDENCY TO LOOSE AN ELECTRON)
1.5 Au / Au +++

0.34 Cu / Cu ++
V
0.0 H2 / H+
- 0.25 Ni / Ni ++ Al passivated
Cr. passivated
- 0.44 Fe / Fe ++
Ni / Ni ++ ECr Passivation
- 0.74 Cr / Cr +++
- 0.763 Zn / Zn ++
EFe Fe / Fe ++
-1.66 Al / Al +++
- 2.37 Mg / Mg ++

- 2.71 Na / Na+ Eo Cr
Cr / Cr+++ I

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THE
THE SCALE
SCALE OF
OF GALVANIC
GALVANIC POTENTIALS
POTENTIALS

POTENTIAL (V) / CALOMEL REFERENCE ELECTRODE

0.3 Graphite 0.05

0.2 Platinum
0.0 Nickel - Chromium - Molybdenum alloys, Titanium 0.0
Stainless steels 304, 316, 321, 347, Monel K500
-0.2 Nickel Aluminium bronze
-0.4 Copper , Copper alloys 90/10 and 70/30 - 0.05
Aluminium bronze
-0.6
Carbon steel, low alloy steel
-0.8 - 0.1
-1.0 Aluminium, Zinc
-1.2
-1.4
-1.6 Magnesium CO2 service

In sea water

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 CORROSION
CORROSION POTENTIAL
POTENTIAL

THE POTENTIAL OF A METAL IS DEPENDING ON :

* the electrochemical reaction taking place on the metal.

* the current passing through the electrode surface

For a given anode/cathode ratio higher the potential between two

metals, higher the galvanic current .

Steel potential V1 Steel potential V2

I1 # I2

Steel
I1 I2
V1 # V2

Electrical connection Electrical connection

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POURBAIX
POURBAIX DIAGRAM
DIAGRAM –– THERMODYNAMIC
THERMODYNAMIC DEFINITION
DEFINITION

Ag/ AgCl H+ /H2 ENERGY – pH relationship

electrode electrode

0.95 1.2
V
.75 1.0 Fe+++
0.55 0.8 O2
0..35 0.6 H2 O
0.15 0.4 Fe++
- 0.05 0.2 Fe2O3
Corrosion
- 0.25 0.0
- 0.45 - 0.2 H2 O Passivation
- 0.65 - 0.4 H2
Fe3O4
- 0.85 - 0.6
- 1.05 - 0.8
- 1.25 - 1.0 Fe
- 1.45 - 1.2
Area of Immunity

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH

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 GALVANIC
GALVANIC CORROSION
CORROSION

Anodic zones Steel Zinc

A
O2 + 2e- + H2O 2OH Zn Zn++ + 2e-
-
e-

Steel
Zinc
Na+
Zn++
Cl -

Electrical connection

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CATHODIC PROTECTION PRINCIPAL

- 730 mV

- 720 mV
- 650 mV

- 725 mV

Water
Steel Zinc

- 725 mV

- 720 mV

Electrical connection

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 SUMMARY
SUMMARY

Corrosion control:
Corrosion takes place if:

• Free water is present Dehydration

• A corrosive (oxidising) agent is present Removal of oxygen
or acids
• A heterogeneity is present either :

WATER
• in the electrolyte Cleaning of the pipes
STEEL

Avoiding precipitation at the

• in the metal structure grain boundaries

• on the metal surface Cathodic protection

Coating/painting
Inhibition

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