Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

1
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore


Lecture 10
Polarization Techniques Corrosion Rate Determination
Keywords: Corrosion Rates, Polarization Diagrams, Linear Polarization Resistance.
A weighed sample coupon of metal introduced into the corrosion process and
after desired exposure period removed, cleaned of all corrosion products and
reweighed. Weight loss can be converted to average corrosion rate (mpy) using
Faradays law. There are ASTM standards G1, G4 and G31 for preparing,
cleaning and evaluating corrosion test specimens, conducting corrosion coupon
tests in plant equipment and laboratory immersion corrosion testing.
Using corrosion coupons for weight loss (corrosion rate) measurements has
advantages such as cheap and simple, permits analysis of corrosion products and
can easily be done in a laboratory or on a service equipment. However, it
requires long term exposures to be more accurate as short-term tests can yield
misleading information. Different shapes of corrosion coupons, such as flat, ring
type or cylindrical can be used. Coupons can be placed in industrial equipment
using holders (electrically isolated) .
Polarization techniques to determine corrosion rate
Tafel extrapolation and polarization resistance are two methods to measure
corrosion rates. Polarization methods are faster experimental techniques
compared to classical weight loss estimation. Tafel relationship with respect to
activation controlled anodic and cathodic processes has been discussed earlier.
For an electrochemical reaction under activation control, polarization curves
exhibit linear behavior in the E Vs log ( i ) plots called Tafel behavior. Typical
polarization behavior of metals in acid solution in the presence and absence of
oxygen are illustrated below.
Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

2
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore


Typical cathodic polarization curves with respect to Tafel behaviour are also
given. Extrapolation of cathodic and anodic Tafel slopes back to the corrosion
potential (E
corr
) are shown. Intersection point corresponds to corrosion current
density (i
corr
) or corrosion rate (Fig. 10.1).
i
a
= i
c
= i
corr
(mixed potential theory)
At least one decade of linearity in Tafel extrapolation is desirable to ensure good
accuracy. When concentration polarization and ohmic resistance come into the
picture, accuracy in Tafel extrapolation becomes more and more difficult. Steady
state polarization curves need be obtained to be more representative of corrosion
reactions. Potentiostatic and galvanostatic methods need be compared to
ascertain the choice of a better technique to determine corrosion rates.
There are some demerits in Tafel extrapolation. Since polarization curves are not
reversible and are influenced by experimental and environmental conditions,
Tafel constants can vary from system to system. Often anodic curves may not
exhibit linear behavior near E
corr.
Polarization of a metal in deaerated acid solution
To determine values of E
corr
and i
corr
, extrapolated linear sections from the
anodic and cathodic curves are used as shown in Fig. 10.1.
Anodic reaction M = M
++
+ 2e
Cathodic reaction 2H
+
+ 2e = H
2

E
corr
and i
corr
values can be directly determined from the cross-over point (Fig.
10.2).


Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

3
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore



Fig 10.1 Polarization behaviour of a metal (M) in deaerated acid solution
At the corrosion potential, E
corr,
rate of cathodic reduction is equal to rate of
anodic reaction (metal corrosion).
Tafel constants (
a
and
c
) are calculated from the anodic and cathodic slopes

Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

4
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore



Fig 10.2 Tafel plot to estimate Tafel constants
A plot of overpotential against log i showing exchange current density is
illustrated in Fig 10.3.

Fig 10.3 Overpotential vs log i Tafel plot
Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

5
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore


Current against overpotential for a reversible reaction such as the ferric ferrous
couple on a noble electrode surface is shown in Fig. 10.4.
Anodic and cathodic curves along with the resultant current behavior for
reversible reaction is illustrated.
Fe
+++
+ e = Fe
++


Fig 10.4 Polarization plot for a reversible reaction
Polarization behaviour of a metal (M) in a stagnated aerated electrolyte at near
neutral pH is illustrated in Fig 10.5. Total cathodic current corresponds to the
sum of the currents for both hydrogen and oxygen reduction reactions and has to
be balanced by the single anodic reaction current. Depending on the level of
electrolyte agitation the magnitude of the limiting current for the oxygen
reduction will vary.
Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

6
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore



Fig 10.5 Polarization behaviour of metal M in unstirred aerated near neutral solution
Another graphical example of electrochemical measurement of corrosion rate
through Tafel extrapolation is illustrated in Fig. 10.6. At the corrosion potential
(E
corr
), the rate of hydrogen reduction is equal to rate of metal dissolution.
Corrosion rate (i
corr
) in terms of current density can be estimated. Tafel constants
(
a
and
c
) can be calculated from anodic and cathodic portions of the Tafel plots.

Fig 10.6 Tafel extrapolation method
Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

7
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore


Linear polarization resistance
Change potential by about 10-20 mV from E
corr
and measure corresponding
current (i).
Plot a linear graph for (E
app
E
corr
) Vs i.
i
app
(anodic) is positive while i
app
(cathodic) is negative.
The slope of the potential current density plot near E
corr
is defined as
POLARIZATION RESISTANCE (R
p
).
R
p
= E / i (E O)
For reactions under activation, R
p
can be related to i
corr
as:

Fig 10.7 Linear polarization curve

The extent of linearity of the potential current plot depends on
a and

c
values.
Tafel slopes are necessary to calculate B.
Since B varies within a factor of 2 around a value of 0.065 V for long range Tafel
constants, corrosion rate (i
corr
) can be estimated within a factor of 2 (even of Tafel
constants are not available).
-i
corr
= B / R
p
Log R
p
= log B log i
corr

When B =
a

c
/ 2.3(
a +

c)

See Fig. 10.7

Lecture 10: Polarization Techniques Corrosion Rate Determination NPTEL Web Course

8
Course Title: Advances in Corrosion Engineering
Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore


A Three-electrode cell is used for measurement of polarization resistance in a
laboratory. Linear polarization corrosion probes are used in chemical process
and water treatment industries for online monitoring, The probes are either three-
electrode or two-electrode types. These techniques permit accurate measurement
of even very low corrosion rates (< 0.1 mpy).