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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)
Ammeter (current)
Working Electrode
= 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
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
Resulting Current
Rs = the solution resistance Rct = the charger transfer (polarisation resistance) Cdl = the double layer capacitance
Capacitance
Increasing Frequency
Charge transfer resistance = Rtotal - Rs
Solution Resistance
Resistance
Phase angle
Impedance
Rct
Solution resistance
Frequency
Phase angle
Frequency
EIS (Summary)
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
Bode Phase
EIS Equivalent Circuit for a Mixed Kinetic and Charge Transfer Controlled Process
Impedance
Phase
EIS Equivalent Circuit for a Filmed Corroding Surface (E.g. Failed Coating)
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
Remember: during linear polarization measurements we plot E vs i (not log i) around the corrosion potential:
E = polarization resistance i
26
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
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
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
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
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