Application Area: Corrosion

Evaluation of organic coatings on metals using Autolab PGSTAT

based on ISO 17463 – Paints and Varnishes

Keywords A Metrohm Autolab flat cell was used as electrochemical cell,

suitable for measuring flat samples up to 17 cm² in size
Corrosion, Coatings, ISO, Standard, accelerated cyclic
(Figure 2).
electrochemical technique

Introduction
The International Standard ISO 17463 describes the
determination of the anticorrosive properties of high
impedance organic protective coatings on metals. This is
done by exploiting the accelerated cyclic electrochemical
(ACE) technique. In order to learn about the details of ISO
17463 standard, please refer to International Organization for
Standardization (ISO).
This technique uses cycles composed of electrochemical
impedance spectroscopy (EIS) measurements, cathodic
polarizations and potential relaxation. The cathodic
polarization is applied for the degradation of the coating,
while EIS and potential relaxation monitor the change of the Figure 2 – The Metrohm Autolab flat cell.
coating and its properties. The ACE technique is used to
evaluate the permeability of the coating. The working electrode was a metal substrate, covered by the
coating under study. As reference electrode, a Metrohm
Ag/AgCl 3 mol/L KCl was chosen. Finally, the stainless steel
Experimental Setup
counter electrode of the Metrohm Autolab flat cell was
A Multi Autolab M204 with three PGSTAT channels and three employed.
FRA32M modules was used. The Multi Autolab M204 can
As electrolyte, an aqueous solution of NaCl 3.5% was used.
accommodate up to 12 channels, and one optional module
per channel, with a maximum of 6 channels and 6 modules. After an initial EIS measurement, to determine the initial
A typical example of Multi Autolab M204 is shown in Figure status of the coating, a cycle of electrochemical
1, with 6 channels and 6 different modules. Nevertheless, this measurements is applied n times. Each cycle consists of a
experiment can be executed using the Autolab single channel cathodic polarization, followed by a relaxation process. The
potentiostat as well. last step of each cycle is an EIS measurement, to determine
the state of the coating after the polarization and the
relaxation.
More details of the three parts of the ACE cycle are presented
below:

1. Cathodic polarization
During the cathodic polarization, a constant potential is
applied. If the potential is negative enough, the electrolysis of
Figure 1 – The Multi Autolab M204 pgstat.
water can occur. The resulting hydroxide ions and/or
hydrogen molecules can cause delamination between the
substrate and the coating.
 Application Area: Corrosion
Evaluation of organic coatings on metals using Autolab PGSTAT
based on ISO 17463 – Paints and Varnishes

In this experiment, the potential for the cathodic polarization

was set to −4 V for 20 minutes.

2. Potential relaxation
The relaxation process allows the formation of a new stable
equilibrium. By recording the potential during the relaxation
process, additional information about the coating and the
substrate–coating interface can be obtained.
The relaxation time was set to 180 minutes. Figure 4 – Bode plot taken before and during the six cycles. The
arrow indicates the cycle number, from before the cycles, (tail of the
3. EIS arrow) to the sixth (tip of the arrow).

The EIS measurements are used to retrieve information on

the coating properties. The fitting of the EIS data can give the Here, it can be noticed that the modulus of the impedance
values of the pore resistance and the coating capacitance. decreases with increasing the cycle number, while the phase
is increasing (the negative phase values are plotted). This
A frequency range from 100 kHz to 10 mHz was applied, with
can be due to the water absorbed by the coating (water
5 points per decade, and a signal amplitude of 20 mV RMS.
intake), during the experiment.
The EIS data were fitted with the equivalent circuit shown in
Results and Discussion Figure 5.
In Figure 3, the plot of the potential during the relaxation time
at different cycles are shown. The arrow indicates the cycle
number, from the first (tail of the arrow) to the sixth (tip of the
arrow).

Figure 5 – The equivalent circuit used for fitting the EIS data.

From the fit results, the pore resistance 𝑅 (Ω) and the
coating capacitance 𝐶 (𝐹) per cycle were extracted and
Figure 3 – Potential vs. time plot taken during the relaxation time. The
plotted versus the cycle number, Figure 6 and Figure 7,
arrow indicates the cycle number, from the first (tail of the arrow) to
respectively.
the sixth (tip of the arrow).

The cathodic polarization applied before the relaxation time

induces imperfections to the coating, such as delamination to
the substrate–coating interface. The sample therefore
reaches the equilibrium at lower, less noble potentials, and in
less time. Repeating the cathodic polarization induces more
disruptions, ageing the coating.
In Figure 4, the Bode plots from the EIS measurements are
shown at different cycles. The arrow indicates increasing of
the cycle number.

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 Application Area: Corrosion
Evaluation of organic coatings on metals using Autolab PGSTAT
based on ISO 17463 – Paints and Varnishes

The impedance spectroscopy data were fitted with a suitable

equivalent circuit, and the values of the pore resistance and
coating capacitance were monitored during the cycles.

Date
December 2019 AN-COR-018

For more information

Additional information about this application note and the
associated NOVA software procedure is available from your
local Metrohm distributor. Additional instrument
Figure 6 – Pore resistance taken before the polarization step (Cycle
specification information can be found at
1), and at other cycles (Cycles 2–7).
www.metrohm.com/en/products/electrochemistry.

Figure 7 – Coating capacitance taken before the polarization step

(Cycle 1) and at other cycles (Cycles 2–7).

Here, it can be seen that the pore resistance decreases after

each cycle while the coating capacitance increases, possibly
due to water intake of the coating during the experiment.

Conclusions
This application note shows the compliance of the Metrohm
Autolab PGSTAT M204 and flat cell with the standard ISO
17463. A coating on a metal substrate was analyzed with
electrochemical impedance spectroscopy, followed by cycles
formed by cathodic polarization, a relaxation time and an
electrochemical impedance spectroscopy.
From the plots of the voltage versus relaxation time and the
Bode plots, it is possible to monitor the ageing of the coating
and evaluate its properties.

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