Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

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.

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

Typical cathodic polarization curves with respect to Tafel behaviour are also given. Extrapolation of cathodic and anodic Tafel slopes back to the corrosion potential (Ecorr) are shown. Intersection point corresponds to corrosion current density (icorr) or corrosion rate (Fig. 10.1). ia = ic = icorr (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 Ecorr. Polarization of a metal in deaerated acid solution To determine values of Ecorr and icorr, 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 = H2 Ecorr and icorr values can be directly determined from the cross-over point (Fig. 10.2).

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

Fig 10.1 Polarization behaviour of a metal (M) in deaerated acid solution

At the corrosion potential, Ecorr, 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

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

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

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

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.

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

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 (Ecorr), the rate of hydrogen reduction is equal to rate of metal dissolution. Corrosion rate (icorr) 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

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

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

Linear polarization resistance

Change potential by about 10-20 mV from Ecorr and measure corresponding current (i). Plot a linear graph for (Eapp Ecorr) Vs i. iapp (anodic) is positive while iapp (cathodic) is negative. The slope of the potential current density plot near Ecorr is defined as POLARIZATION RESISTANCE (Rp). Rp = E / i (E O) For reactions under activation, Rp can be related to icorr as: -icorr = B / Rp Log Rp = log B log icorr When B = a c / 2.3(a + c) See Fig. 10.7

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 (icorr) can be estimated within a factor of 2 (even of Tafel constants are not available).
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Course Title: Advances in Corrosion Engineering Course Co-ordinator: Prof. K. A. Natarajan, IISc Bangalore

Lecture 10: Polarization Techniques Corrosion Rate Determination

NPTEL Web Course

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 threeelectrode or two-electrode types. These techniques permit accurate measurement of even very low corrosion rates (< 0.1 mpy).

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