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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)

The Manual Potentiostat


Variable High Voltage Source 50-300 V

High Impedance Voltmeter 1012

Ammeter (current)

Working Electrode

Reference Auxiliary 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 as sinfunction of time E = E a ( t )
t 0

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

Nyquist plot for the Randels circuit

Electrochemical Impedance Spectroscopy

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

Bode impedance plot

Electrochemical Impedance Spectroscopy

Impedance

Rct

Solution resistance

Frequency

Bode Phase plot

Electrochemical Impedance Spectroscopy

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 di
Now:

= Sa =
anodic

ba 2.303icorr

dE di

= Sc =
redox

bc 2.303icorr

slope S a =

E x

slope S c =

E i x

E = S a S c
i Sa Sc
or icorr

ba bc 1 i = 2.303 ba + bc E

Polarization Resistance .. E .. is measured. The Tafel coefficient ba and i bc must be known.

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 overpotentials 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

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 potentialstep 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

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 Plot of the total current same quadrant) back to Ecorr (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-)

Flade

(Ee)M/MO is the equilibrium potential 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. 33

Tafel Extrapolation Technique


Involves measurements at high overpotential 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 E .

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 overpotential 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

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 A V

Working Electrode 1

Working Electrode 2

Reference Electrode

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

Rotating dual cylinder electrode (RDCE)

Potential Noise and Current Noise

Voltage Noise PSD


1.E-03

Voltage PSD / V2/Hz

1.E-06

1.E-09

1.E-12

3.5 days

1.E-15 1.E-04

1.E-03

1.E-02 Frequency/Hz

1.E-01

1.E+00