1st Stern method (Tafel) - Operating procedure Principle The principle of the first Stern method (Tafel) is described

in the Principle topics. Before calling the Tafel command:

. Display the curve within current = f(potential) axes. Select X = potential and Y1 = current in the curve type bar. . Display a part of the curve having a zero-current potential. Use the Curve Traject command or the Zoom function. Note: If you are processing a curve issued from several other curve branches (after an Append operation for example), sort the curve by potential before calling the Tafel processing tool. Operating procedure

Smoothing (1 to 9) Calcul. zone Enter, in mV, a potential interval within which the search for the Tafel parameters should be performed. This interval lies on either side of the corrosion potential E(i=0) with the Calcul. zone as the interval amplitude. The Calcul. zone could not include less than 10 points of the voltammetric curve. Segment Enter, in mV, the interval within which VoltaMaster 4 will try to fit the curve to a line. This segment is moved all around the Calc. zone interval defined above. The Segment cannot include less than 5 points of the voltammetric curve.

Atomic mass Valence - Density The atomic mass of the oxidized species, the number of electrons which are lost during the oxidation reaction (valence) and density of the oxidized species are displayed for information,. They cannot be changed here. These three parameters are entered in the Cell setup dialogue box before starting the sequence. Select the Plot button: VoltaMaster 4 starts performing the operations described hereafter.

Operations performed by VoltaMaster 4 1. VoltaMaster 4 searches for the best tangent for the curve: the Segment is moved around the curve point by point as explained above. At the end of this operation, VoltaMaster 4 displays the best tangent, calculates and displays the slope of the tangent (Ba or Bc depending on whether it is the anodic or the cathodic branch of the curve), and the Coef. linear correlation coefficient found for that tangent.

2. VoltaMaster 4 determines and displays the E(i=0) zero current potential.

3. VoltaMaster 4 determines the slope of the i=f(E) curve at the E(i=0) value: the Rp polarisation resistance found is displayed (a parabolic regression of the curve is performed as for the second Stern method).

4. The second Tafel tangent is plotted from the point of intersection between the first Tafel tangent and the line of equation E=E(i=0). VoltaMaster 4 calculates and displays the slope of that new tangent (Ba or Bc depending on whether it is the anodic or cathodic branch of the curve).

5. VoltaMaster 4 determines and displays the corrosion current as the ordinate of the intercept between the 2 Tafel lines extrapolated at the E = E(i=0) corrosion potential.

6. VoltaMaster 4 calculates and displays the corrosion rate Corr. in mm/year: this rate is calculated from the i cor. corrosion current density found, the D density and the M atomic mass and V valence entered in the Tafel dialogue box. The calculation is performed as follows:

With: 3270 = 0.01 x [1 year (in seconds) / 96497.8] and 96497.8 = 1 Faraday in Coulombs. The Print button is used to print out the contents of the Tafel dialogue box (curve and results) with curve information data and method parameters if selected in the Page Setup dialogue box. Saving the results The results are saved in the Result folder under a NAME.TXT file by clicking the Save command button in the Tafel box (if NAME.CRV is the name of the curve file). Clicking the Save button will add the current results to the existing ones (consequently, the old results are not erased). To view the post run processing results of one curve, load the curve (File - Open curve(s) command) then select the Results thumbnail. In the results window, all the post run processing results saved for the curve are listed (i.e. the contents of the TXT file).

Note (polarisation resistance): The Rp polarisation resistance can also be determined by using the 2nd Stern method (select the Processing 2nd Stern method command). The 2nd Stern method also displays the linear regression results used for the Rp determination. The polarisation resistance is calculated by the same way in the two Stern methods.

The Tafel equation gives access to the corrosion current regularly present at the surface of a metal which is in contact with a corroding solution. The corrosion is expressed in loss of metal thickness per year. The Thermodynamical Ba and Bc parameters of the Butler Volmer equation are also determined. To start processing a curve by the 1st Stern (Tafel) method, select the Processing - 1st Stern method: Tafel command (or click the icon in the General bar) from an i = f(E) voltammetric curve having a zero-current potential.

The first Stern method is based on the search for the Tafel lines on a log(i) = f(E) voltammetric curve. This curve must have a potential for which the measured current is equal to zero. The intercept of the 2 Tafel lines (anodic and cathodic lines) extrapolated at the zero current potential gives a point the co-ordinates of which are the E(i = 0) corrosion potential and i cor. corrosion current:

The existence of the Tafel lines depends on the following conditions for the anodic and cathodic processes: . The anodic and cathodic reactions are situated far from their equilibrium. . The anodic and cathodic reactions are entirely controlled by the charge transfer. In practice and in almost all cases, the complexity of the reaction (the reaction rates of other Red/Ox couples are relatively high and should be taken into consideration), the ohmic drop, the formation of superficial films, etc. reduce or eliminate the linear potential range of the log(i) = f(E) curve, and the extrapolation can lead to inaccurate or wrong results.

Note (polarisation resistance): The Rp polarisation resistance can also be determined by using the 2nd Stern method: select the Processing 2nd Stern method command. The polarisation resistance is calculated by the same way in the two Stern methods. See also 1st Stern method (Tafel) - Operating procedure.

2nd Stern method - Operating procedure Principle The principle of the second Stern method is described in the Principle topics. Before calling the Stern command:

. Display the curve within current = f(potential) axes. Select X = potential and Y1 = current in the curve type bar. . Display a part of the curve having a zero-current potential. Use the Curve Traject command or the Zoom function. Operating procedure

Smoothing (1 to 9) Segment Sets the interval within which VoltaMaster 4 will try to find the best parabola to the curve (parabolic regression). This regression is performed within the interval:

[E(i=0) - Segment / E(i=0) + Segment] The Segment cannot include less than 5 points of the voltammetric curve. Select the Plot button: VoltaMaster 4 starts performing the operations described below. Operations performed by VoltaMaster 4 1. VoltaMaster 4 searches for the best parabola to the curve within the interval [E(i=0) - Segment / E(i=0) + Segment]. At the end of this operation, the parabola is plotted in red and the parabolic regression coefficient Coef. is displayed.

2. VoltaMaster 4 determines and displays the E(i=0) zero current potential. This potential is the point where the parabola crosses the abscissa axis.

3. VoltaMaster 4 plots in yellow the tangent to the parabola at the E(i=0) determined beforehand.

4. VoltaMaster 4 determines the slope of this tangent and displays the Rp polarisation resistance. The Print button is used to print out the contents of the 2nd Stern dialogue box (curve and results) with curve information data and method parameters if selected in the Page Setup dialogue box. Important: On noisy signal curves, VoltaMaster 4 may find a parabola which not fits this curve. If this happens, we recommend you to smooth this curve (Smoothing parameter set to 5) before processing the curve again by clicking on the Plot button. Saving the results The results are saved in the Result folder under a NAME.TXT file by clicking the Save command button in the Stern box (if NAME.CRV is the name of the curve file). Clicking the Save button will add the current results to the existing ones (consequently, the old results are not erased). To view the post run processing results of one curve, load the curve (File - Open curve(s) command) then select the Results thumbnail. In the results window, all the post run processing results saved for the curve are listed (i.e. the contents of the TXT file).

2nd Stern method Principle he second Stern method, based on a second degree regression around the zero current potential value, gives the polarisation resistance value and another linear regression facility. To start processing a curve by the 2nd Stern method, select the Processing - 2nd Stern method command (or click the from an i = f(E) voltammetric curve having a zero-current potential. icon in the General bar)

This method consists of determining the Rp polarisation resistance as the slope of the E = f(i) voltammetric curve at the zero-current potential. VoltaMaster 4 performs a parabolic regression of the E=f(i) curve and determines the tangent slope of the parabola at the zero-current potential (polarisation resistance Rp). Then, the software plots the parabola and the tangent and displays the zero-current potential (E(i=0) corrosion potential), the Rp polarisation resistance, and the parabolic correlation coefficient found for the tangent.

Note (polarisation resistance): The Rp polarisation resistance can also be determined by using the 1st Stern (Tafel lines) method: select the Processing 1st Stern method: Tafel command. The polarisation resistance is calculated by the same way in the two Stern methods.

See also 2nd Stern method - Operating procedure.

General corrosion (Rp) Principle General corrosion tests are useful to investigate the efficiency of inhibitors used to prevent general (uniform) corrosion. Automatic calculation of the polarisation resistance (Rp) is determined from cyclic or linear voltammetries performed around the rest potential. The polarisation resistance measures the instantaneous corrosion rate occurring at the electrochemical interface. This Rp can be used to evaluate the anti-corroding strength of an inhibitor. Signal Imposed Depending on the Initial scan option selected, 4 potential scans are possible: Initial scan = Anodic

Initial scan = Cathodic

Initial scan = None A

Initial scan = None C

Default settings Individual voltammetries are recorded at 10 mV/s. The WORK versus REF potential is scanned (in cathodic direction) from instantaneous OCP to {OCP 40 mV} and then back (in anodic direction) to {OCP +40 mV}. The potential steps are 0.5 mV and 0.05 seconds. 7 Rp determinations in all are recorded. Between two successive measurements, the circuit is opened and the cell is at rest (OCP) for 1 minute. The real-time display plots each individual voltammetry (Current versus potential) during its acquisition and the Rp versus time when the cell is at rest. The experiment will last 7.4 minutes (7 minutes and 24 seconds) plus the time involved in each individual voltammetry. The circuit is opened at the end. The voltammetries are not saved (Save raw data = No) as the rest potential versus time. Calculation results (Rp and corrosion rates) are saved versus time (Save calculation data = Yes).

The "General corrosion (Rp)" parameters Ramp/OCP Scan rate (1 V/s to 300 mV/s or 1 V/s to 10 mV/s for a VoltaLab 21) Sets the rate of the potential scan. The Scan rate and the Overvoltage (see below) parameters set the dt step duration between two successive measurements, the dVg potential step of the scan applied and the number of points of each individual voltammetry. The dt step duration and dVg potential step are displayed for information. Note: the Total duration displayed is the duration of the following scan: 0 mV / -Overvoltage / +Overvoltage. The number of points is limited to 64 000 per individual voltammetry. Overvoltage (1 mV to 99 mV) The Overvoltage and the Initial scan option set the potential to be scanned as follows (see also the 4 figures at the top of this topics): . Initial scan = Cathodic: starts at the open circuit potential (OCP) and scans in cathodic direction to (OCP Overvoltage) then scans back in anodic direction to (OCP + Overvoltage). A 40 mV overvoltage means a potential cycle of: Start (OCP) ----> (OCP 40 mV) ----> End (OCP + 40 mV) . Initial scan = Anodic: starts at the open circuit potential (OCP) and scans in anodic direction to (OCP + Overvoltage) then scans back in cathodic direction to (OCP - Overvoltage). A 40 mV overvoltage means a potential cycle of: Start (OCP) ----> (OCP + 40 mV) ----> End (OCP 40 mV) . Initial scan = None C: starts at (OCP + Overvoltage) and scans in cathodic direction to (OCP - Overvoltage). A 40 mV overvoltage means a potential cycle of: Start (OCP + 40 mV) ----> End (OCP 40 mV) . Initial scan = None A: starts at (OCP - Overvoltage) and scans in anodic direction to (OCP + Overvoltage). A 40 mV overvoltage means a potential cycle of: Start (OCP - 40 mV) ----> End (OCP + 40 mV) OCP Duration (1 s to 999 h) Sets the time during which the system will be left at the OCP between 2 successive Rp determinations. Determine x Rp (x: 1 to 999) Sets the number of Rp determination or the number of points of the calculation data curve. This is also the number of individual voltammetries to be performed. Initial scan (Cathodic, Anodic, None C, None A) Sets the type of potential scan to be applied as shown above.

Calculations Path (Initial, Forward, All) In the Path box, select the path (part) of the voltammetric curve you want to process for Rp determinations. The availability of the Path options depends on Initial scan defined in the Ramp/OCP. In the figures below, the path selected is in red.

Equation (Linear, Stern, GFC) In the Equation box, select the type of algorithm used for Rp determinations: Linear (available if Path = Forward or Initial) Stern (available if Path = Forward) GFC (available if Path = All)

Sample The Cell setup parameters are displayed for information. They are entered in the Cell setup dialogue box and cannot be changed here. These parameters are used to calculate corrosion rates. Others Smoothing (0 to 9) Enter in this box a smoothing criterion between 0 and 9. Rp and corrosion rate determinations are performed on the smoothed i = f(E) voltammetries. Minimum/maximum range (1 A, 10 A, 100 A, 1 mA, 10 mA, 100 mA, 1 A, Auto) D/A OUT initial (0 to 5 000 mV) Not available if a VoltaLab 06 (PST006) or VoltaLab 21 (PGP201) is used and declared in the Instrument setup. D/A OUT final (0 to 5 000 mV) Not available if a VoltaLab 06 (PST006) or VoltaLab 21 (PGP201) is used and declared in the Instrument setup. A/D IN If you want to measure an A/D IN signal at the A/D IN socket of the PGZ or PST050 potentiostat, click in the A/D IN box (a check mark is displayed). The external potential signal will be measured in the same time as the current measurements of the current f(potential) voltammetries. Note: If the A/D IN option is selected, the A/D IN measurements are saved in the raw data curve file if Save raw data = Yes is selected (see below). The A/D IN option is not available if a VoltaLab 06 (PST006) or VoltaLab 21 (PGP201) is used and declared in the Instrument setup. Open circuit at end Select this option (a check mark is displayed when selected) if you want to open the circuit at the end of the General corrosion (Rp) method. Save raw data The raw data comprises the Current/potential measurements versus time of all voltammetries as well as the OCP measured versus time between 2 successive voltammetries. If the A/D IN option is selected, the A/D IN measurements versus time are also saved. If Yes is selected, the raw data curve is saved in a NAMExR.CRV file if "NAME" is the name of the sequence and x the ordering number of the method in the sequence of methods (x is an hexadecimal number from 00 to FF).

Save calculated data The calculated data are the polarisation resistances and corrosion rates calculated for each voltammetric curve. This file also comprises the corrosion potentials or E (i=0) zero-current potentials (see how they are determined below). If Yes is selected, the (Corrosion rate, Rp, E(i=0), time) points are saved in a NAMEx2.CRV file if "NAME" is the name of the sequence and x the ordering number of the method in the sequence of methods (x is an hexadecimal number from 00 to FF). The number of points of a calculated data curve is set by the Determine x Rp parameter (see above). Determination of corrosion potentials Zero-current potentials are determined as follows:

. The raw data curve is smoothed (smoothing criterion selected in the General corrosion (Rp)). . A straight line is plotted between the point having the least positive current (represented as point 1) and the preceding one (represented as point 2). . The intercept between this line and the abscissa axis gives the zero-current potential saved. A zero-current potential is determined each time the smoothed raw data crosses the current axis. This corresponds to the number of voltammetries (or Rp determinations) performed for the method. Related topic: Running a General corrosion (Rp) method