Electrochemical Techniques for

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)









*ensure specimen potential (w.r.t. counter) constant
even though solution resistance might alter.
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 radial the
voltage the of amplitude the
t time at potential
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:
( )
shift phase the
current the of amplitude 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


Plot of the total current
(i
T
= i
o
+ i
c
) versus
potential showing the
extrapolation of the
Tafel regions to the
corrosion potential,
E
corr
, to yield the
corrosion current, i
corr
.
Passivation
Under certain conditions of potential and pH, some
metals form protective films, i.e., they passivate
Pourbaix diagram for the
iron/water/dissolved
oxygen system showing
the effect of potential in
moving the system from a
corrosive (active) region
(point 1) to a passive
region (point 2)
We can exam the kinetics
using a potentiodynamic
scan and Evans diagram
33

The polarization curve for the anodic reaction of a passivating
metal drawn for potentials more noble than the equilibrium
potential (E
e
)
a





Oxidative dissolution of oxide (e.g.,
Cr
2
O
3
CrO
4
2-
)
(E
e
)
M/MO
is the equilibrium potential
for oxide/hydroxide formation
Tafel region
(i
crit
is min. reaction rate required to
initiate film growth by precipitation
of M
n+
)
The region attained by the metal in a given environment depends upon the
cathodic reaction i.e., where the cathodic curve cuts the above anodic curve.
Flade
Tafel Extrapolation Technique
Involves measurements at high over-potential in
which logi is recorded.
The best method of performing these measurements
is by :
1) Using two identical electrodes and recording the
anodic curve on one electrode and the cathodic
curve on the other electrode. In each case starting at
the open circuit potential E
oc
(or E
corr
)

2) Performing the cathodic curve on one electrode
starting the scan from E
oc
. Turning off the
potentiostat and monitoring E
oc
until it returns to its
original value. The anodic scan is then recorded again
starting at the E
oc
.
Tafel Extrapolation Technique
Before commencing a Tafel measurement, it is
generally best to allow your metal electrode to reach
a steady state potential. This can be observed by
performing a potential time measurement in which
E
corr
is monitored with time.
Scan Rates are normally in the range of 0.1 mV to 5.0
mV per second. The cathodic plot is scanned to an
over-potential of about 400 mV.
Anodic potentials can be scanned much higher
depending on what information needs to be
obtained.
Cyclic Pitting Scans
The technique is used to evaluate the susceptibility
of metals to pitting corrosion in a particular
environment. It is applicable to metals such as
stainless steels, high nickel alloys and aluminium,
which form a passive protective film.
With this technique, the potential is scanned to
voltages in the transpassive region.
Exceeding the passive region is indicated by a sudden
increase in current. At this stage the voltage scan is
reversed, usually when the current reaches a certain
current density (0.5 mA cm
-2
)
Cyclic Pitting Scans
The extent of the hysteresis in the reverse scan is an
indication of the susceptibility to pitting corrosion.
Pitting corrosion is considered to stop at the potential where
the iE curve from the reverse scan crosses the iE curve of the
forward scan.
The sudden increase in current can be due to three processes:
1) Onset of pitting corrosion
2) Trans-passive uniform corrosion
3) The oxygen evolution reaction
In the case of trans-passive corrosion, the slope of the iE
curve is not as steep compared to pitting corrosion and
oxygen evolution.
In the case of oxygen corrosion, the reverse iE curve normally
will retrace over the forward iE curve.

Harmonic Analysis
Butler Volmer Equation



When an electrode is polarized near the corrosion potential
by a sinusoidal voltage of frequency and amplitude U
0
, then
the current density of the Faradaic process is given by:

Harmonic Analysis
The current densities of the Faradaic process will
have a distorted sinusoidal form due to the non-
linear nature of the cathodic and anodic partial
processes in a polarization curve.
The amplitudes of the harmonic components can be
obtained by Fourier series expansion of the exponential
terms


Harmonic Analysis
The simplified magnitude of the first three harmonic
components are given by:
Harmonic Analysis
The technique has been verified by the work of Will Durnie,
Curtin University.
He compared corrosion rates from HA with those obtained
using linear polarization measurements and Stern Geary
equation.



When the Tafel slopes obtained from HA were placed in the
Stern Geary equation an excellent correlation was obtained.

Harmonic Analysis
Durnie, W. H.,Curtin University
Electrochemical Noise (ECN)
ECN measures the current/voltage response between two
(largely) identical electrodes.
The two electrodes are coupled together (short circuited
together) through a zero resistance ammeter (ZRA).
The random fluctuations of current is measure by the ZRA.
At the same time the random fluctuations in voltage noise at
the coupled electrodes is measured with respect to a
reference electrode.
Electrochemical Noise Measurement
A
Working Electrode 2
Working Electrode 1
Zero Resistance Ammeter
V
Reference Electrode
Rotating dual cylinder
electrode (RDCE)
Standard electrochemical cell
with reference, auxiliary and
RDCE
The RDCE is useful for
performing ECN Measurements
ECN uses identical electrodes. In
the example shown the
electrode areas are not the
same since this RDCE was used
to investigate preferential weld
corrosion
Potential Noise and Current Noise
Voltage Noise PSD
1.E-15
1.E-12
1.E-09
1.E-06
1.E-03
1.E-04 1.E-03 1.E-02 1.E-01 1.E+00
Frequency/Hz
V
o
l
t
a
g
e

P
S
D

/

V
2
/
H
z
3.5 days