HARMONIC ANALYSIS FOR CORROSION MONITORING

P. Slepski1, H.Gerengi2, G.Bereket3, A.Samandar2

1
Corrosion and Materials Engineering, Gdansk University of Technology,
11/12, 80-952 Gdansk, Poland
2
Kaynaşlı Vocational college, Düzce University, 81900 Kaynaşlı-Düzce
3
Department of Chemistry, Faculty of Arts and Science, Eskişehir Osmangazi University,
26480 Eskişehir, Turkey

1. Abstract

Corrosion is the destructive attack of a material by reaction with its environment. The
multidisciplinary aspect of corrosion problems combined with the distributed responsibilities
associated with such problems only increase the complexity of the subject. Corrosion control
is achieved by recognizing and understanding corrosion mechanisms, by using corrosion-
resistant materials and designs, and by using protective systems, devices, and treatments. We
know that corrosion is a natural process and also an electrochemical process so
electrochemical techniques and electrochemical instrumentation can be used to study the
corrosion process. A number of electrochemical techniques have been developed specifically
for corrosion measurement. Harmonic analysis is the one of those techniques. We can obtain
all kinetic parameters in a short time from results of this method. No other technique offers
this facility. The aim of this work is to give information about how to use harmonic analysis
method for corrosion monitoring.

Keywords Corrosion; Harmonic Analysis

*
Corresponding author. Tel: +90-5053987953; E-mail address: husnugerengi@duzce.edu.tr

2. Method description

The determination of the rate of corrosion by the measurement of polarization

resistance is most frequently employed. The corrosion current density is evaluated from Rp,
the polarization resistance, using the stern –Geary equation:

βa βc 1
icorr =
2,303(β a + β c ) R p

where βa and βc are the anodic and cathodic Tafel slopes, respectively.

Mansfeld [1] compiled a comprehensive review of that technique in the mid-seventies

while recently Nagy and Wesson [2] published a thorough evaluation of it. In accordance with
other authors they came to the conclusion that while the simplicity is an obvious advantage of
the method, however, its application is hindered by systematic errors caused by arbitrary
assumptions and simplifications. The most important sources of error are the following:
a) Erroneous estimation of the Tafel slopes or their determination by extrapolation
b) Determination of the polarization resistance using finite amplitude

1
 Instantaneous corrosion rate measurements are often obtained through the use of
electrochemical measurements such as LP, ER and EIS. Probes are inserted into flow lines to
conduct electrochemical measurements. Instruments employing techniques such as LP, ER
and EIS can be coupled to automated systems, allowing for continuous monitoring of
corrosion. For LP and ER, problems can arise if the pipeline solution has a low conductivity,
and/or if the probe is coated by oil/hydrocarbon. Consequently, ER and LP probes must be
carefully inserted into pipelines to ensure that they are immersed in water, yielding accurate
readings. For this reason, they are often placed in a bypass loop, out of the main flow, where
it is easier to keep them immersed in an aqueous phase [3].
The disadvantages of the aforementioned electrochemical corrosion monitoring
techniques may be overcome by using a technique based on the measurement of harmonic
currents. The main advantage of harmonic analysis (HA) is that the measurement of corrosion
rate does not employ presumed values for the Tafel slopes [4], and measurements can be
undertaken in a fraction of the time of conventional methods (e.g., LP, ER and EIS).
Rangarajan [5], Devay and Meszaros [6] proposed harmonic analysis method in
corrosion measurements. In this method if the perturbing signal is a sinusoidal voltage then
the corrosion current density can only be calculated from the current response at the
fundamental and the second and third harmonics; without the need for the Tafel constants.
The harmonic responses contain sufficient information to describe the anodic and cathodic
process and the corrosion current; essentially, the fundamental and the two harmonics provide
three equations, or data sets, which are solved to give three unknowns, Icorr, ba and bc [7].

And for sinusoidal input of amplitude U0

1 1
i f = icorr  − U 0 Amplitude of fundamental or first harmonic (1)
 ba bc 
i  1 1 
i2 f = corr  2 − 2 U 02 Amplitude 2nd harmonic (2)
4  ba bc 
icorr  1 1 
i3 f =  3 − 3 U 03 Amplitude of 3rd harmonic (3)
24  ba bc 

Solving eqs 1, 2 and 3 gives

i 2f
icorr = (4)
(48)0.5 (2i f i3 f − i22 f )
0.5

A simple approach is used to calculate the anodic Tafel slop (ba) and the cathodic Tafel slope
(bc) from the amplitude U0 and the current if and i2f

If ba <bc
1 1  if 4i2 f 
=  +  (5)
ba 2U 0 i if 
 corr 

2
1 1  if 4i 2 f 
=  −  (6)
bc 2U 0 i if 
 corr 

or if ba>bc
1 1  if 4i 2 f 
=  −  (7)
ba 2U 0 i if 
 corr 

1 1  if 4i2 f 
=  +  (8)
bc 2U 0 i if 
 corr 

Different corrosion methods results were compared [8] with each other and it was
clear that there was good correlation between Harmonic Analysis and Tafel extrapolation
method. Harmonic Analysis experiments took about 3 minutes but the other techniques such
as LP, ER and EIS took more time than expected [9].

3. Scheme of Harmonic Analysis method

Signal processor

Corrosion cell

Potentiostat
NI6120 PCI
S series Multifaction Card
for to obtain “sine wave”

4. Conclusions

Harmonic analysis was found to be a practical and rapid technique for corrosion rate
determination. A major advantage of this method was also determination of both the Tafel
constants and Stern-Geary B values. No other technique offers this facility. Also this method
can be used in on-line corrosion monitoring systems. But, the voltage of angular frequency
“w” and voltage amplitude “U0” must be correctly choose.

3
References

[1] F.Mansfeld, Advances in Corrosion Science and Technology, vol: 6, Plenum Press, (1976)
[2] Z.Nagy and J.M.Wesson, J.electrochem.soc. vol: 139, pp.1261, (1992)
[3] W.Durnie, R.D.Marco, A. Jefferson, B.Kinsella, “Harmonic analysis of carbon dioxide
corrosion”, Corrosion Science, vol: 44, pp. 1213, (2002)
[4] M.I. Jafar, J.L. Dawson, D.G. John, "Electrochemical Impedance and Harmonic Analysis
Measurements on Steel in Concrete", ASTM STP 1188, 1993, pp. 384-403.
[5] S.K. Rangarajan, “Non-linear relaxation methods: III.Current-controlled perturbations”
J.Electroanal. Chem., vol: 62, pp. 31, (1975)
[6] J. Devay and L. Meszaros, Acta Chimica Academia Hungary, 104 (3), pp. 311-316(1980)
[7] J.Majewska, PhD Thesis, “Wykorzystanie metody analizy harmonicznej oceny zagroŜenia
korozyjnego w warunkach polaryzacji”, Gdańsk Universty of Technology, Poland 2000.
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carbon steel in artificial seawater using Eis, Deis and Harmonic analysis”, Corrosion Science
and Engineering, vol: 14, pp.3, (2006)
[9] A.Pırnat, L.Meszaros, B.Lengyel, “A comparison of electrochemical and analytical
chemical Methods for the determation of the corrosion rate with very efficient inhibitors”,
Corrosion science, vol: 37, No.6, pp. 963, (1995)