Corrosion Engineering (Practical)

Name: Farwa Naeem Roll No: 16MME-S2-317

Semester: 6th Session: 2016-20

Date of Submission: 14/01/2020

Experiment No. 9
Calculate the anodic slope, cathodic slope, corrosion potential (Ecorr), corrosion current (Icorr) and
corrosion rate from polarization curves according to ASTM G3.

Lab Instructor Signature: ________________

Grade/Marks: _______________
 Short Circuited
current

Figure 1: Evan's Diagram

Figure 2: Hypothetical Cathodic and Anodic Polarization Diagram

Figure 3: Increased cathodic reaction and decreased anodic reaction caused by introducing
electrons from an external source.
Experiment Title
Calculate the anodic slope, cathodic slope, corrosion potential (Ecorr), corrosion current (Icorr) and
corrosion rate from polarization curves according to ASTM G3.
Objective of Tafel polarization test
The main objective of the Tafel polarization test is to measure the anodic slope, cathodic slope,
corrosion potential (Ecorr), corrosion current (Icorr) and corrosion rate from polarization curves.
Principle
The point where the dissimilar metal curves meets, we can calculate different characteristics of
polarization curve that are anodic slope, cathodic slope, corrosion potential (Ecorr), corrosion
current (Icorr) and corrosion rate.
Background
Polarization
The hindrance in the flow of current is called polarization. It is a non-spontaneous process.
Shifting potential from high to low or from low to high means polarization. Polarization is
independent of pH.
 Deviation in potential of the electrode as a result of the passage of the current.
 When the anodic and cathodic areas of a corroding structure are short circuited current
(Figure 1) flow between them and their open circuit potential are shifted (polarized)
towards each other.
 The polarization behavior of anodic and cathodic areas determines the corrosion current.
 If the polarization increases than corrosion current decreases.
Anodic polarization
Shifting of potential from low potential to high potential, the electrode behaves more anodic.
Cathodic polarization
Shifting of potential from high potential to low potential, the electrode behaves more cathodic.
Figure 2. Figure 3 represents anodic reaction. In anodic area metal dissolute, electron went to
cathodic areas. Providing electrons from external source (cathodic polarization), metal will not
dissolute. i.e. anodic reaction stops. Cathodic reaction increased. Too much electrons may also
result in hydrogen evolution in cathodic reaction. Hydrogen evolution thus damage coatings
(used to protect material from environmental effects).
Nativepotential/
Standard/open
circuit potential

D
P E
O P
L O
A L
R A
T R
S T
A S
T A
T
I I
O O
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Corrosion mitigation

Figure 4: Polarization of structure. (Red anode. Green cathode)

Mechanism of cathodic polarization
Figure 4 shows a steel structure, subjected to cathodic polarization. Red represents anode.
Current flow from anode to cathode. Potential will be more negative.
Step 1
Native potential -0.5V shift to -0.58V. No other value changed. We got 3 cells
Step 2 (shifting to more negative potential)
Potential -0.58V shift to -0.6V and -0.55V shift to -0.65. Number of cells decreased down, we
got 2 cells
Step 3
Potential -0.6V shift to -0.65V. Number of cells decreased down, we got 1 cell.
Step 4
Potential -0.65V shift to -0.7V. Structure have same potential throughout i.e -0.7V. All cells
disappeared.
Hence in cathodic polarization, we remove anodes and made the whole surface cathode.
Cathodic reaction will take place on the surface. Surface potential will be more negative in
cathodic polarization. In figure 4, downward direction shows polarization whereas if we reverse
the direction, anode will start forming. This phenomenon is called depolarization.
Depolarization is more fatal at that stage.
Figure 5: Effect of external current on the metallic structure

Figure 6: Anodic and Cathodic reactions on a metal surface

Figure 7: Represents solution resistance (Non short circuited)

Potential difference vs corrosion rate.
By reducing potential difference, rate of flow of current decreases. Less the current, less will be
the corrosion rate. In polarization we reduce potential difference to avoid corrosion. Effect of
external current is also shown in figure 5.
Evans diagram/kinetic diagram/ E log I diagram/ Tefel diagram/ polarization diagram
Anodic polarization slope represents anodic slope. Cathodic polarization slope represents
cathodic slope. Slope is resistance. Anodic reaction fast/ slow or cathodic reaction fast/ slow will
be decided by its slope. Reaction kinetics is also described by the slop values as shown in figure
2. ASTM standard G3 provide full guidance in it. In Evans diagram, x-axis is current, and graph
is straight line. Changing x-axis from current to log current, graph will become exponential, and
is called polarization curves. For anodic polarization, potential is moved from low to high,
oxidation/anodic reaction takes place and vice versa for cathodic polarization.
Reduction/cathodic reaction takes place. There are three cathodic reactions depends upon pH.
(Depends on aerated or deareated)
2H+ + 2e- = H2
Steeper the slope, more resistance will be, best polarization takes place.
Solution resistance
Practically, anodic and cathodic polarization do not short circuit. Because between anode and
cathode, their always exist some resistance in the form of solution (electrolyte) known as
solution resistance. Figure 7 represents solution resistance
Rate of reaction (Reaction kinetics) relation with polarization slope
 Anodic slope low, reaction will be fast.
 Anodic slope increases, rate of dissolution reaction decreases.
 Cathodic slope increases, rate of deposition reaction decreases.
Why we are discussing anodic/cathodic polarization?
Cathodic/anodic polarization is linked with cathodic/anodic protection. Therefore
cathodic/anodic polarization is important. Potential is getting higher (Positive potential); means
we are doing anodic protection. More negative potential means cathodic polarization.
Figure 8: Represents types of polarization

Figure 9: Represents active, concentration polarization.

Figure 10: Comparison of Pourbaix vs E log I diagram
Types of polarization
1. Activation polarization
2. Concentration polarization
3. Resistance polarization
Activation polarization
It is associated with the electrode-metal property. From figure 8, horizontal straight line
represents activation polarization. Kinetics of electrode
Concentration polarization
It is associated with the electrolyte property. From figure 8, bend region represents concentration
polarization. Always give exponential graphs.
Resistance polarization
It is associated with the film formed on metal. From figure 8, vertical straight-line region
represents resistance polarization. If barrier film does not exist, there will be no resistance
polarization region as shown in figure 9.
Pourbaix vs E log I diagram
Pourbaix diagram is made between pH and potential where as polarization diagram was made
between log I and potential E, when we compare both diagrams we can concluded that cathodic
polarization is actually lowering the potential to bring metal into immune region and in case of
anodic polarization we actually highering the potential to bring metal into passive region and in
passive region oxide layer is formed on the metal. Figure 10.
And also we can conculed both the diagrams, anodic polarization is occur above the red line and
cathodic polarization is occur below the red line and line show the limit of cathodic polarization.
Figure 11: Represents Potentiostat schmetically

Figure 12: Represents three electrode system

Figure 13: Represents Anodic and cathodic polarization

Electrochemical testing
 Corrosion potential test or open circuit potential (OCP), will tell the potential up to which
polarization is done in order to protect a structure from corrosion.
 Tafel scan is the E log I diagram, that will help find anodic slop, cathodic slop, E corr, Icorr
and corrosion rate.
Potentiostat
Potentiostat like power source, is an equipment that provide potential. But its potential is more
controlled as compared to power source. Figure 11.
Three electrode system
1. Working electrode
2. Reference electrode
3. Counter electrode
Working electrode
The electrode on which work is done i.e. the subjected electrode.
Reference electrode
It will tell the potential of working electrode.
Counter electrode/ Auxiliary electrode
Counter electrode help the working electrode. When working electrode is anode, counter
electrode will become cathode and vice versa. Counter electrode and working electrode both
completes the cell. Counter electrode should be an inert material. E.g. Graphite, Platinum wire,
Gold wire.
Principles of OCP
1. Standard potential of the metal in the given solution.
2. Predict the formation of oxide or barrier film on the metal due to the electrolyte
3. Active or noble behavior of the material in the selected solution for specific time. Emf
series or galvanic series formation. i.e. more negative potential a material has, more
prone it will be to form anode.
Figure 14: Experimental setup of Tefel Scan

Figure 15: Polarization curve for 316 L-HAZ stainless steel in Ringer’s solution

Figure 16: The kinetic parameter of 316 L-HAZ stainless steel in Ringer’s solution
Tefel scan
We will calculate following, using tefel scan
1. Corrosion current
2. Corrosion potential
3. Corrosion rate
4. Kinetic information for anodic and cathodic reaction (through slop)
5. Galvanic coupling of two dissimilar metals
6. Rate of dissolution and deposition reaction.

Scan rate is fast for active metal and is slow for Noble metal. For more accurate graph, sample
period should be less. Sample area should be 1cm 2 (Current density = current). Density and
equivalent weight should be calculated accurately before input.
For mere anodic polarization, initial value we put is zero with respect to E oc , upper curve form
only and for cathodic polarization, final value will be zero.

Standard for experiment

 ASTM G 3; Standard Practice for Conventions Applicable to Electrochemical
Measurements in Corrosion Testing.
 ASTM G 82; Standard Guide for Development and Use of a Galvanic Series for
Predicting Galvanic Corrosion Performance.
 ASTM G 102; Standard Practice for Calculation of Corrosion Rates and Related
Information from Electrochemical Measurements.
Procedure to measure the Tafel polarization
Three electrode system was used to conduct experiment. The working electrodes (subjected
electrode) was made up of stainless steel (Grade AISI 316 L) and an exposed area of 1.44 cm 2,
density 7.87 gm/cm2, Equivalent weight 26.58 vs OCP, as shown in figure 12. A graphite rod as
a counter electrode and saturated calomel electrode (SCE) in saturated KCl as a reference
electrode. The Ringer’s solution was used as an electrolyte. The system was connected to the
Gamry instrument potentiosatat (interface 1000 E) as shown in figure 14. A Tafel plot was
performed on a stainless-steel specimen by polarizing the sample with initial voltage 0.25V vs.
Eref cathodically and the final voltage -0.25 V vs. E ref anodically with scan rate of 1 mV/s. The
kinetic parameters of stainless steel were calculated by Tafel extrapolation method using Echem
Analyst software. Basic steps to run software are as follows.
Figure 17: Experimental setup for HAZ

Figure 18: Experimental notes for HAZ

Figure 19: Polarization curve for 316 L-BM stainless steel in Ringer’s solution
 1. Firstly, open the heat affected zone data file in Gamry Echem Analyst software.
2. Select the region over which to perform the Tafel fit.
3. Select Tafel Fit from the Potentiodyamic menu than Tafel fit. Window appears, click on
the liner option than click on the calculate option and close the window.
4. Save the data.
5. Do similar operations for the base metal and save data.
6. Open both the data file in Gamry Echem Analyst software so that overlay graph was
made and save data.

Discussion
Tafel scan results are shown in figure 16 & 20. Corrosion rate of BM is 115.0e-3 mpy and that of
HAZ is 822.0e-3 mpy. Corrosion rate of heat affected zone is greater than that of base metal.
Which means heat affected zone will corrode faster and in future fracture takes place in this
zone.
For BM, anodic slope (βa) is 334.7e-3V/decade and cathodic slope (β c) is 103.3e-3 V/decade and
that for HAZ, anodic slope (β a) is 672.8e-3 V/decade and cathodic slope (β c) is 133.0e-3
V/decade. On comparing we find that slopes of HAZ are higher than BM. As value of slope
indicate polarization, we can say HAZ is best polarized and reaction rate is slow over there. E corr
and Icorr among BM (264.0e-9 A/cm², -228.0 mV) and HAZ (1.890e-6 A/cm², -306.0 mV) are
also changing. On comparison HAZ will act as anode (oxidation) as it shows higher corrosion
rate and tends to undergo corrosion and performed dissolution and BM as cathode which
performed reduction.
Overlaying both graphs as shown in figure 23, it can be seen that they are coupled galvanically.
The galvanic couple between dissimilar metals can be treated by the application of the mixed
potential theory. Under the influence of galvanic coupling, appreciable polarization of the
metals may occur, which may produce a protective film on the metal surface, or which may
cause breakdown of an already existing protective film. This effect is commonly observed with
stainless steel and we need to eliminate it.
The value of galvanic potential at the point of intersection was 283.8 mV between the HAZ and
BM. The value of galvanic current was 751.6e-9 A/cm².
Overall reaction
2Fe + O2 + H2O = 2Fe+2 + 4OH
Figure 20: The kinetic parameter of 316 L-BM stainless steel in Ringer’s solution

Figure 21: Experimental setup for BM

Figure 22: Experimental notes for BM

Results
Dissimilar βa βc Icorr Ecorr Corrosion
Metals (V/decade) (V/decade) (A/cm²) (mV) rate
(mpy)
316L-BM 334.7e-3 103.3e-3 264.0e-9 -228.0 115.0e-3
316L-HAZ 672.8e-3 133.0e-3 1.890e-6 -306.0 822.0e-3
Conclusion
By comparing all kinetic parameters, it is concluded that HAZ will act as anode (oxidation) as it
shows higher corrosion rate and tends to undergo corrosion and performed dissolution and BM
as cathode which performed reduction.

References
1. Corrosion Technology Vol. 1, by Prof. Dr. Ijaz Hussain Khan.
2. Principles of Corrosion Engineering and Corrosion Control, by Zaki Ahmad.
3. Corrosion Engineering principles and practice, Pierre R. Roberge.
Figure 23: Overlay graph showing galvanic coupling between 316 L-BM and 316 L-HAZ
stainless steel.