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Corrosion Measurements
Assignment
Present a critical examination of the proposed
mechanisms of CO
2
and H
2
S corrosion with
particular emphasis on the cathodic
(oxidation) reactions.
Due Date 5 June 2009
3
Corrosion Measurements
Involve the use of a potentiostat for applying a potential (relative to a
reference electrode) and measuring the current (flowing from the working
electrode to the counter or auxiliary electrode)
The Manual Potentiostat
Variable High
Voltage Source
50-300 V
High Impedance
Voltmeter 10
12
Auxiliary
Electrode
Working
Electrode
Reference
Electrode
Ammeter
(current)
Electrochemical Impedance Spectroscopy
Resistance
Ohms Law
For a resistor, R, it follows Ohms Law at all current and
voltage levels
The resistance value is independent of frequency
AC current and voltage signals through a resistor are in phase
with each other
I
E
R =
Electrochemical Impedance Spectroscopy
Impedance
Impedance applies to AC voltage and current
Like resistance impedance is a measure of the ability of a
circuit to resist the flow of electrical current
The excitation potential or AC voltage can be expressed as a
function of time
( )
frequency radi al the
vol tage the of ampl i tude the
t ti me at potenti al
0
0
=
=
=
=
e
e
E
E
t E E
t
t
sin
Electrochemical Impedance Spectroscopy
The relationship between radial frequency (radians s
-1
) and
frequency (f) hertz is:
The response to the AC voltage is given by:
( )
shi ft phase the
current the of ampl i tude the
current response
0
0
=
=
=
+ =
|
| e
I
I
t I I
t
t
sin
f t e 2 =
Electrochemical Impedance Spectroscopy
Similar to Ohms law
The important point to remember is that when an AC voltage
is applied to a pure capacitor the resulting AC current is
shifted in phase by 90
o
There is no phase shift for a pure resistor
( )
( )
( )
( ) | e
e
| e
e
+
=
+
= =
t
t
Z
t I
t E
I
E
Z
t
t
sin
sin
sin
sin
0
0
0
Electrochemical Impedance Spectroscopy
Current phase shift due to impedance. Through a
capacitor this phase shift is 90
o
Applied
Voltage
Resulting
Current
Electrochemical Impedance Spectroscopy
Randles circuit for a simple corroding system
R
s
= the solution resistance
R
ct
= the charger transfer (polarisation resistance)
C
dl
= the double layer capacitance
Electrochemical Impedance Spectroscopy
Nyquist plot for the Randels circuit
Resistance
Capacitance
Increasing Frequency
Solution
Resistance
Charge transfer
resistance = R
total
- R
s
EIS Nyquist Plots
A Nyquist plot is made up of a series of vectors representing
the total magnitude of the resistance and capacitance
components
Phase angle
Non Resistive
Component
Electrochemical Impedance Spectroscopy
Bode impedance plot
Impedance
Frequency
Solution
resistance
R
ct
Electrochemical Impedance Spectroscopy
Bode Phase plot
Frequency
Phase angle
EIS (Summary)
We start here at the
high frequency
EIS
Diffusion or Mass Transfer controlled process
Nyquist plot - Warburg Impedance
Frequency
EIS
Diffusion or Mass Transfer controlled process
Bode Impedance plot
Impedance
Frequency
EIS
Diffusion or Mass Transfer controlled process
Bode Phase plot
Phase Angle
Frequency
EIS Mass Transfer Controlled Process (Summary)
Nyquist
Bode
Impedance
Bode
Phase
EIS Equivalent Circuit for a Mixed Kinetic and Charge
Transfer Controlled Process
EIS Bode Plots for the Mixed Controlled Reaction
Impedance
Phase
EIS Equivalent Circuit for a Filmed Corroding
Surface (E.g. Failed Coating)
EIS for a Filmed Corroding Surface (E.g. Failed Coating)
Nyquist
Bode
Impedance
(Magnitude
Bode Phase
Angle
Linear Polarization Method
Valid for corrosion under activation control.
Involves applying a small perturbation to the potential around E
corr
(i.e., E 10
mV).
Slope of summed curve (measure E vs i
for system) is difference between slopes
of curves for the coupled reactions: S
a
-
S
c
N.B. i for
summed curve
= i
a
+ |i
c
|
(i
a
=x)
The curves are ~linear within ~20mV S
a
and S
c
are constant. For
E around E
corr
, S
a
and S
c
are related to i
corr
(the required quantity):
assuming the high-field approximation for the individual reactions
Now:
Polarization Resistance .. .. is measured. The Tafel coefficient b
a
and
b
c
must be known.
corr
a
a
anodic
i
b
S
di
dE
303 . 2
= =
corr
c
c
redox
i
b
S
di
dE
303 . 2
= =
i
E
A
A
E
i
b b
b b
i
c a
c a
corr
A
A
+
=
303 . 2
1
or
x
E
S
a
A
= slope slope
x i
E
S
c
A
A
=
c a
c a
S S
S S
i
E
=
A
A
26
Remember: during linear polarization measurements we
plot E vs i (not log i) around the corrosion potential:
i
E
A
A
= polarization resistance
Linear Polarization
This involves the application of low over-potentials and
therefore the currents are relatively very small. This
means that the charging current (capacitance current)
can make a significant contribution to the noise or
background current.
Use slow scan rates and perform a cyclic scan to check
whether you are measuring capacitance.
The reverse scan should produce an iE curve that
retraces over the forward recorded iE curve.
The iE curve can be curved due to a difference in the
anodic and cathodic Tafel slopes.
Linear Polarization
It is important to view the iE curve. If the iE curve is
curved, the polarization resistance can be obtained by
drawing a line that is tangential to the curve at E
corr
and
at zero current.
Some portable instruments use a potential-step method.
In this case the current, at, for example, -10 mV and +10
mV is measured and R
p
is computed from these
measurements.
The advantage of this technique is that the current
measurements are made at a constant voltage and
therefore the charging current is zero.
The disadvantage is that no iE curve is recorded and
therefore an error can be introduced if there is curvature
in the iE graph
Linear Polarization
The portable instruments that use the potential-step
technique, usually apply a high frequency AC signal
before the measurement to determine the solution
resistance and subtract this value from the measured
polarization resistance.
Tafel Extrapolation
Tafel Method We can only measure the net current across
the specimen electrode at the corrosion potential there is no
net current (only local anode cathode currents which constitute
the corrosion current). We cannot measure corrosion rate
directly, though we need i
corr
.
Measure potential and current at some distance on either side of
E
corr
extrapolate E - log i curves (in same quadrant) back to E
corr