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Electrochemical

Techniques for Corrosion


Measurements
Assignment
Present a critical examination of the
proposed mechanisms of CO2 and
H2S corrosion with particular
emphasis on the cathodic (oxidation)
reactions.

Due Date 5 June 2009


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


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even though solution resistance might alter.
The Manual Potentiostat
Variable High
Voltage Source
50-300 V

Ammeter
(current)
High Impedance
Voltmeter 1012

Working Reference Auxiliary


Electrode Electrode Electrode
Electrochemical Impedance
Spectroscopy
Resistance
Ohms Law R E
I
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
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
E as
t E sin
0
t
a function of time

Et potential at time t
E0 the amplitude of the voltage
the radial frequency
Electrochemical Impedance
Spectroscopy
The relationship between radial frequency
(radians s-1) and frequency (f) hertz is:
2f

The response to the AC voltage is given by:


I t I 0 sin t

I t response current
I 0 the amplitude of the current
the phase shift
Electrochemical Impedance
Spectroscopy
Similar to Ohms law

Et E0 sin t sin t
Z Z0
It I 0 sin t sin t

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 90o
There is no phase shift for a pure resistor
Electrochemical Impedance
Spectroscopy
Current phase shift due to impedance. Through a
capacitor this phase shift is 90o

Applied
Voltage

Resulting
Current
Electrochemical Impedance
Spectroscopy
Randles circuit for a simple corroding system

Rs = the solution resistance


Rct = the charger transfer (polarisation resistance)
Cdl = the double layer capacitance
Electrochemical Impedance
Spectroscopy
Nyquist plot for the Randels circuit

Capacitance
Increasing
Frequency

Charge transfer
resistance = Rtotal - Rs

Solution
Resistance
Resistance
EIS Nyquist Plots
A Nyquist plot is made up of a series of vectors
representing the total magnitude of the
resistance and capacitance components

Non Resistive
Component

Phase angle
Electrochemical Impedance
Spectroscopy
Bode impedance plot

Impedance Rct
Solution
resistance

Frequency
Electrochemical Impedance
Spectroscopy
Bode Phase plot

Phase angle

Frequency
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)

Bode
Impedance
(Magnitude

Nyquist

Bode Phase
Angle
Linear Polarization Method
Valid for corrosion under activation control.
Involves applying a small perturbation to the potential around Ecorr
(i.e., E 10 mV).

N.B. i for
summed curve
= ia + |ic|
(ia=x)

Slope of summed curve (measure E vs i


for system) is difference between
slopes of curves for the coupled
reactions: Sa - Sc
The curves are ~linear within ~20mV Sa and Sc are constant. For
E around Ecorr, Sa and Sc are related to icorr (the required quantity):
assuming the high-field approximation for the individual reactions

dE ba dE bc
Sa Sc
di anodic 2.303icorr di redox 2.303icorr

Now: E E
slope S a slope S c
x i x
E S a S c
i Sa Sc
1 ba bc i
or icorr
2.303 ba bc E

Polarization Resistance .. E .. is measured. The Tafel coefficient ba and


bc must be known. i
Remember: during linear polarization measurements
we plot E vs i (not log i) around the corrosion potential:

E
= polarization resistance
i

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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 Ecorr 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
Rp 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 icorr.
Measure potential and current at some distance on
either side of Ecorr extrapolate E - log i curves (in
same quadrant) back to Ecorr Plot of the total current
(iT = io + ic) versus
potential showing the
extrapolation of the
Tafel regions to the
corrosion potential,
Ecorr, to yield the
corrosion current, icorr.
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
The polarization curve for the anodic reaction of a
passivating metal drawn for potentials more noble
than the equilibrium potential (Ee)a

Oxidative dissolution of oxide (e.g.,


Cr2O3 CrO42-)

(Ee)M/MO is the equilibrium potential


Flade
for oxide/hydroxide formation

Tafel region
(icrit is min. reaction rate required to
initiate film growth by precipitation
of Mn+)

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.
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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 Eoc (or
Ecorr)
2) Performing the cathodic curve on one
electrode starting the scan from Eoc. Turning off
the potentiostat and monitoring Eoc until it
returns to its original value. The anodic scan is
then recorded again starting at the Eoc.
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 Ecorr 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 U0, 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
Zero Resistance Ammeter

Working Electrode 1 Working Electrode 2

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