Linear Polarization Resistance (LPR) and the Stern-Geary Equation

With this widely used technique in corrosion monitoring, the polarization resistance of
a material is defined as the slope of the potential-current density (DE/Di) curve at the
free corrosion potential, yielding the polarization resistance Rp that can be related (for
reactions under activation control) to the corrosion current by the Stern-Geary
equation:

where:
Rp is the polarization resistance
icorr the corrosion current
The proportionality constant , B, for a particular system can he determined empirically
(calibrated from separate weight loss measurements) or, as shown by
Stern and Geary, can be calculated from ba and bc, the slopes of the anodic and
cathodic Tafel slopes, i.e.

Corrosion Monitoring
Linear Polarization Resistance (LPR)
Polarization resistance is particularly useful as a method to rapidly identify corrosion
upsets and initiate remedial action, thereby prolonging plant life and minimizing
unscheduled downtime. The technique is utilized to maximum effect, when installed
as a continuous monitoring system. This technique has been used successfully for
over thirty years, in almost all types of water-based, corrosive environments. Some of
the more common applications are:
Cooling water systems
Secondary recovery system
Potable water treatment and distribution systems
Amine sweetening
Waste water treatment systems
Pickling and mineral extraction processes
Pulp and paper manufacturing
Hydrocarbon production with free water
The measurement of polarization resistance has very similar requirements to the
measurement of full polarization curves. There are essentially four different methods
of making the measurement according to whether the current or the potential is
controlled and whether the current (or potential) is swept smoothly from one value to
another, or simply switched between two values. In addition the measurement may be
made between two nominally identical electrodes (a two-electrode system), or a
conventional three-electrode system (working, reference and counter) may be used

Electrochemical impedance spectroscopy (EIS)

EIS has been successfully applied to the study of corrosion systems for thirty years and been
proven to be a powerful and accurate method for measuring corrosion rates. But in order to
access the charge transfer resistance or polarization resistance that is proportional to the
corrosion rate at the monitored interface, EIS results have to be interpreted with the help of a
model of the interface.
An important advantage of EIS over other laboratory techniques is the possibility of using very
small amplitude signals without significantly disturbing the properties being measured. To make
an EIS measurement, a small amplitude signal, usually a voltage between 5 to 50 mV, is applied
to a specimen over a range of frequencies of 0.001 Hz to 100,000 Hz.
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The EIS instrument records the real (resistance) and imaginary (capacitance) components of the
impedance response of the system. Depending upon the shape of the EIS spectrum, a circuit
model or circuit description code and initial circuit parameters are assumed and input by the
operator.
The program then fits the best frequency response of the given EIS spectrum, to obtain in fitting
parameters. The quality of the fitting is judged by how well the fitting curve overlaps the original
spectrum. By fitting the EIS data it is possible obtain a set of parameters which can be correlated
with the coating condition and the corrosion of the steel substrate.
Amongst the numerous equivalent circuits that have been proposed to describe electrochemical
interfaces only the following apply in the context of a freely corroding interface at or close to
kinetic equilibrium:
Simplest RC representation of an electrochemical interface
One relaxation time constant with extended diffusion
Two relaxation time constants
Impedance of pitting processes of Al based materials.

Model for a corroding paint on steel substrate

Electrochemical Noise
Electrochemical Noise, commonly abbreviated ECN, is an
electrochemical technique in which the potential and/or current
signals that arise directly from the electrochemical reactions taking
place on an electrode surface are measured and interpreted. ECN is
of intense ongoing interest because of the totally non-invasive
nature of the measurement when performed with a Zero Resistance
Ammeter (ZRA). The electrochemical instrument is not applying any
signal to the sample that might improperly influence the result. This
perturbation may be of concern in every electrochemical experiment
other than noise.

ECN can also be measured with the electrochemical instrument

configured as a potentiostat or galvanostat. The number of actual
applications of this sort is quite small. Most ECN experiments are
carried out with ZRA's, so that no signal at all is applied to the
sample by the instrument.ECN has been used to monitor localized
corrosion (pitting), uniform corrosion through measurement of the
Noise Resistance, and the deterioration of paints on metal
substrates. ECN does not yet enjoy the level of acceptance of DC
techniques and Electrochemical Impedance Spectroscopy.