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What is corrosion ?
When steel is immersed in sea water for example, an electrical potential is set
up at the metal/electrolyte (seawater) interface. The predisposition for this to
happen will be dependent on the characteristics of the particular grade of steel
and the electrolyte involved.
The corrosion process (anodic reaction) of the metal dissolving as ions generates
electrons. These electrons are utilised by a further process (cathodic reaction).
It is important to realize that these two processes have to balance their charges.
The sites hosting these two processes can be located close to each other on the
metal's surface, or far apart depending on the circumstances.
For corrosion to occur, all four of the following conditions need to be present;
It should also be noted that changes in any of the four conditions can have a
significant effect on the rate that the corrosion process will occur.
In the corrosion cell illustrated below, iron atoms give two electrons to become
positively charged ions. Oxygen and water combine to form negatively charged
ions as illustrated below:
Corrosion site
Steel
Anodic
Area
Fe=> Fe 2+ +2e-
electrons
Oxygen + Water
O2 + 2H20+4e =>4OH-
In acidic environments
Cathodic
Area O2 + 4H + 4e => 2H20
Hydroxide
Water
Non exotic steels submerged in the electrolyte (seawater) will suffer from
corrosion damage due to the formation of anodic and cathodic areas over its
surface. Various standards have been issued which state that the corrosion
rate for steel in seawater is in the region of 0.1mm/year. Frequently however,
non-uniformity of electrolyte, inhomogeneity of the metal, the variability of
oxygen access or the presence of corrosion products and bacteria can combine
at specific locations leading to localised corrosion, often referred to as pitting
corrosion. The corrosion rates when pitting occurs can be substantially higher
than general corrosion rates and is typically one of the main causes of corrosion
failure.
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The first application of CP dates back to 1824 when the British scientist Sir
Humphrey Davy used iron to cathodically protect the copper bottoms on Royal
Navy vessels.
Cathodic protection is one of the most widely used methods for preventing the
corrosive deterioration of metallic structures in contact with any form of
electrolytically conducting environments, i.e. environments containing enough
ions to conduct electricity such as soils, seawater. Cathodic protection reduces
or halts the corrosion rate of a metallic structure by reducing its corrosion
potential, bringing the metal closer to an immune state. The two main methods
of achieving this goal are by using either:
A schematic indicating the mechanisms for both sacrificial anodes systems and
an impressed current system is shown below.
Electrical Seawater
bond (cable)
Electron
flow Electron
flow
Pipeline
Seawater
m =>m+
Pipeline Electrical
bond (cable)
The distribution of potential field lines caused by the CP system and the effect
of local variations is illustrated below.
-920mV-
-922mV-
General
-925mV-
Potential
Level
-930mV-
-995mV
Activity; -925mV
Pipe Surface to -1005mV
approx 3m -915mV
Zn –Zn 2+
-1050mV -905mV
2e-
Anode Damage
If the potential reading is more positive than -800 mV, the point of
measurement is considered to be under-protected creating a possible
environment for corrosion action on the steel surface. It should be stated that
the rate with which corrosion actually takes place varies significantly between
that of freely corroding steel with a potential of –650mV wrt Ag/AgCl and the
protection potential of –800mv.
On areas of potentials more negative than -1050 mV/-1100 mV, the production
of hydrogen ions instead of hydroxyl ions may lead to the possibility of
hydrogen being produced at the cathode of the steel surface. Atomic hydrogen
being very small can enter through the metal atomic lattice structure and there
recombine to form atomic hydrogen, as this continues the atomic hydrogen can
exert large forces if unable to disperse. If this occurs at the site of a defect,
grain boundary or at the tip of a micro crack rapid failure can occur especially
if combined with fatigue or in high tensile conditions.
It has been found that certain high strength steels and exotic steel alloys which
have been cathodically protected have actually failed with potentials levels as
positive as –800mV. In these cases specialised anodes with inbuilt voltage
limiting devices have to be used to avoid this problem.
These devices ensure that the potential difference between anodes and
structure cannot be less than -300mV, leading to protection potentials in the
range ~-800 to -75OmV. This does, of course, means that the generally
accepted criterion for protection of any carbon steel in the structure (-800mV)
may not be fully achieved, but in practice, corrosion rates even at -75OmV will
be acceptably low. Potential limiting devices have been applied offshore,
particularly on mobile jack-ups.
*Polarisation
Typically this type of probe can be either used by a diver or through the ROV
umbilical, with the data read on a voltmeter.
Voltmeter
Surface umbilical
Sub sea
Exploded view
Single Cell showing
Stabber Ag/AgCl half cell
Stab tip
Anode Pipeline
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These readings are obtained from measuring the IR drop between two half cells
in seawater (see below and can be used in conjunction with data analysis to
V2 Cell 2
-
Vfg Vcp
d2
V1 Cell 1
Vd d1
VT
As can be seen potential values (CP) can only be obtained at the time of making
contact on the pipeline or structure.
Survey
Vessel
Remote
half cell
Pipeline
ROV with
Anode
Probe &
Digitser
In the example above a remote Ag/AgCl half cell is deployed over the side of the
survey vessel. The reason the cell is called a “remote” half cell is that this half
cell is sufficiently far away from the pipeline to ensure that the pipeline CP
system does not affect the potential, thereby providing a baseline with which to
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measure the differences between the half cell on the probe which are caused by
the local variations in the CP system close to the pipeline or structure as the
ROV surveys along the pipeline.
-950mV
-1000mV 3 metres
-1010mV
2 metres
-1040mV
-1070mV
Schematic Data Input Lines from Twin Half Cell contact & remote probe
During the survey, cell drift and global potential changes can affect the
accuracy of the measured potential. To compensate for these variations, regular
calibration contact measurements are required to remove these offsets. Shown
below is a schematic of how the stab and calibration adjustment is undertaken.
ContinuousCP
Continuous CPprof
prof ile
ile
whichcomprises
which comprisesofoflalast
st Stabvalue
Stab valuemeasured
measuredduring
during
stabvalue
stab value ++C1
C1vvRe
R emote
mote contactperiod
contact periodprior
priorto
to
measuringC1C1vvStab
Stab
Vm1 measuring
VM
Vo VT =VM
VT
VM1 Correctedcontinuous
continuous
Vo Corrected
potential
potential
VCal
VV
M
= Measured Potential (ref. Remote cell)
M = Measured Potential (ref. Remote cell)
VVT ==True
T
TruePotential
Potential
STAB VV
o
= Offset
o = Offset
VVm1 ==Potential
m1
Potentialof
ofstabb
stabbed
edanode
anode
(Vcal
(V =VVm1
cal= m1++VVoo))
The potential profiles and field gradient readings obtained along the pipeline
give valuable information of the corrosion protection level and CP system
performance. The potential gives general protection level information while the
field gradient may give more detail on anode activity and areas requiring higher
current distribution such as at damaged areas, field joints, and spool pieces,
etc. Also, from field gradient readings, anode current output can be calculated
and the remaining anode life can be estimated.
Therefore, from the close relation between potential and field gradient
measurements, along the pipeline it is possible to compute the level and
distribution of potential and current density along the pipeline giving a general
representation of the efficiency and effectiveness of the CP system and the
quality of the pipeline coating integrity.
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The remaining life of the anode is calculated as a function of the anode current
output value (calculated from the measured electric field strength).
Calculation of current density
2
R 2
1
R1
= 2R, Diameter
R
Pipe or Anode
1. ∆E2-1 =ρ * R * i * ln (R2/R1)
2. FG = dE/dr = ρ * R/r * i
Where;
In the case of anodes, after calculating the current density it is now possible to
calculate the surface area of the anode and thus obtain the anode current
output. i.e. Current output = current density x surface area. The estimated
remaining anode life can then be calculated.
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The following formula is used to calculate the remaining life for anodes stabbed:
I x m(Y-Yo)
W = __________
u
and
(Wo x u)-W
R.L.= __________
Ixm
Where;
It should be stated that the remaining life is only an estimation because the
anode current may change considerably with different conditions of the pipeline
i.e. coating damage or breakdown.
If accurate anode wastage values are known these can also be brought into the
equation and used to recalculate the surface area and remaining anode mass.