AUTOLAB APPLICATION NOTE
Types of Corrosion
Corrosion: 1. Basic Concepts
Corrosion refers to a process that involves
deterioration or degradation of metal. The most
common example of corrosion is the formation of
rust on steel. Most corrosion phenomena are of
electrochemical nature and consist of at least two
reactions on the surface of the corroding metal.
One of the reactions is the oxidation (e.g.,
dissolution of iron) also referred to as the anodic
partial reaction. The other is a reduction reaction
(e.g., reduction of oxygen), and is referred to as the
cathodic partial reaction. The products of the
electrochemical reactions can react with each other
non-electrochemically to form the final product (e.g.,
rust). For example, the corrosion of iron to form rust
proceeds according to the overall reaction:
2 Fe + 2 H2O + O2 → 2 Fe(OH)2
This reaction includes the dissolution of iron, the
reduction of oxygen and formation of rust:
Fe → Fe + 2 e (anodic)
2+ -
2 H2O + O2 + 4 e → 4 OH (cathodic)
- -
2 Fe + 4 OH → 2 Fe(OH)2 (chemical)
2+ - which pits or "pin holes" are produced in the
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Corrosion
Uniform Corrosion
Uniform corrosion is characterized by corrosive
attack proceeding evenly over the entire surface
area, or a large fraction of the area of the metal
under attack. Uniform corrosion results in loss of
material until failure. This is the most widespread
form of corrosion that is observed. Crevice Corrosion
Crevice corrosion is a localized form of corrosion
that occurs in the presence of stagnant solution in a
small (micro) crevice. Local chemistry changes in
crevices (shielded areas) such as those formed
under gaskets, washers, insulation material,
fastener heads, surface deposits, disbonded
coatings, threads, lap joints and clamps, can result
in crevice corrosion.
Pitting Corrosion
Pitting corrosion is a localized form of corrosion by
material. Pitting is considered to be more
dangerous than uniform corrosion damage because
it is more difficult to predict and design against.
Corrosion products often cover the pits making the Galvanic Corrosion
detection often very difficult. A small, narrow pit with
minimal overall metal loss can lead to the failure of Galvanic corrosion refers to corrosion damage
an entire engineering system. induced when two dissimilar materials are coupled
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in a corrosive electrolyte. It occurs when two (or
more) dissimilar metals are brought into electrical
contact under water. When a galvanic couple
forms, one of the metals in the couple becomes the
anode and corrodes faster than it would all by itself,
while the other becomes the cathode and corrodes
slower than it would alone. Either (or both) metal in
the couple may or may not corrode by itself
(themselves) in seawater.
Microbiologically Induced Corrosion (MIC)
Microbiologically Induced Corrosion or MIC refers to
corrosion caused by biological organisms or
microbes. These microbes are categorized by
common characteristics such as their by-products
(i.e., sludge producing) or compounds they effect
(i.e. sulfur oxidizing). They all fall into one of two
groups based upon their oxygen requirements; one
being aerobic (requires oxygen) such as sulfur
oxidizing bacteria, and the other being anaerobic,
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AUTOLAB APPLICATION NOTE
(requires little or no oxygen), such as sulfate Electrochemical impedance spectroscopy (EIS)
reducing bacteria.
In recent years Electrochemical Impedance
Spectroscopy or EIS has been successfully applied
to the study of corrosion systems. One of the
advantages of EIS over DC techniques is the
possibility of using very small amplitude signals
without significantly disturbing the properties being
measured.
Electrochemical Noise (ECN)
During localized corrosion electrochemical noise is
generated by a combination of stochastic (random)
processes, such as breakdown of passive films and
repassivation. ECN involves the measurement of the
current and/or potential noise and analysis of the
data using Fast Fourier Transform (FFT).
Electrochemical Characteri
Charac terisation
terisation
methods
Linear sweep voltammetry (LSV)
Linear sweep voltammetry or LSV is one of the
most commonly used methods for characterising
corrosion phenomenon. It involves sweeping the
potential of the working electrode and measuring
the current response. With LSV one can obtain
valuable information regarding the corrosion
mechanisms, corrosion rate and susceptibility of
specific materials to corrosion in various
environments.
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Corrosion: 2. Measurement of
Corrosion Rates
Weight loss measurements
The simplest way of measuring the corrosion rate
of a metal is to expose the sample to the test
medium (e.g. sea water) and measure the loss of
weight of the material as a function of time.
Although these tests are simple, there is no simple
way to extrapolate the results to predict the lifetime
of the system under investigation. Moreover, some
corrosion processes occur with no significant mass
change (e.g. pitting corrosion) making them difficult
to detect by gravimetric methods.
Electrochemical t ests
As mentioned in the previous application notes,
most corrosion phenomena are of electrochemical
nature and consist of reactions on the surface of
the corroding metal. Therefore electrochemical
tests methods can be used to characterise
corrosion mechanisms and predict corrosion rates.
Calculation of corrosion rates
The corrosion rate depends on the kinetics of both
anodic (oxidation) and cathodic (reduction)
reactions. According to Faraday's law, there is a
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linear relationship between the metal dissolution
rate or corrosion rate, RM, and the corrosion current
icorr:
M corrosion potential, Ecorr is the open circuit potential
RM = icorr
nFρ
where M is the atomic weight of the metal, ρ is the
density, n is the charge number which indicates the
number of electrons exchanged in the dissolution
reaction and F is the Faraday constant, (96.485
C/mol). The ratio M/n is also sometime referred to
as equivalent weight.
Calculation of corrosion currents
Calculation of corrosion rates requires the
determination of corrosion currents. When reaction
mechanisms for the corrosion reaction are known,
the corrosion currents can be calculated using
Tafel Slope Analysis.
The relationship between current density and
potential of anodic and cathodic electrode
reactions under charge transfer control is given by
the Butler-Volmer equation:
  2.303 η   −2.303 η  
i = icorr  e ba 
+ e bc 

 
 
η = E − Ecorr
In the above equation E is the applied potential and
i the measured current density. The overpotential,
η, is defined as the difference between applied
potential and the corrosion potential Ecorr. The
of a corroding metal. The corrosion current, icorr,
and the Tafel constants ba, and bc can be
measured from the experimental data.
For large anodic overpotentials (η / ba >> 1) the
Butler-Volmer equation simplifies to the Tafel
equation for the anodic reaction:
η = logicorr + ba logi
Analogously, for large cathodic overpotentials
(bc << -1) the Tafel equation for the cathodic
reaction is given by:
η = logicorr − bc log i
The Tafel equations predict a straight line for the
variation of the logarithm of current density with
potential. Therefore, currents are often shown in
semilogarithmic plots known as Tafel plots. This
type of analysis is referred to as Tafel Slope
Analysis.
Calculation of corrosion currents in NOVA
The NOVA software provides a convenient
interface for making Tafel plots, calculating Tafel
slopes and corrosion rates. In Figure 1 the current
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potential curve for an iron screw immersed in automatically plotted on the Tafel Plot as shown in
seawater is shown. Figure 4 and the results are tabulated as shown in
Figure 5.

Figure 2 – Tafel plot

plot for iron screw immersed in seawater

Figure 1 – Current potential curve for iron screw immersed

in seawater Figure 4 – The linear parts of the Tafel plot are identified by
placing markers

Selecting the Corrosion Rate Tafel Slope analysis

tool from the Analysis menu, a Tafel plot is added The Tafel slope analysis tool provides a quick
as shown in Figure 2. estimation of the corrosion rate and the polarization
resistance. The corrosion rate is calculated from
The user can specify the equivalent weight, density Figure 3 – The working electrode parameters used in the the estimated corrosion current, icorr, obtained from
of the electrode material, the surface area of the Tafel slope analysis the intercept of the two linear segment of the Tafel
electrode and the number of significant digits to slope.
use in the calculation as shown in Figure 3.
The user, with the help of markers, needs to
specify the anodic and cathodic Tafel region. Once
the regions are selected the NOVA software
automatically calculates the Tafel slopes and the
corrosion currents. The Tafel slopes are then

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Figure 5 – NOVA displays the results of the Tafel S lope

analysis Figure 6 – NOVA displays the results of the Corrosion rate fit
analysis
Selecting the Corrosion Rate Fit analysis tool from
the Analysis menu performs a similar analysis as In choosing the regions for Tafel slope analysis,
with the Corrosion Rate Tafel Slope tool. The fit care must be taken. A correct estimate of the Tafel
tool also performs a curve fit based on the Butler- slopes is possible only if the linear Tafel region
Volmer expression which allows for a more (region between markers in Figure 3) covers at
accurate determination of the corrosion current, least 1 decade in current. In certain cases (e.g.,
polarization resistance and corrosion rate. passivation of iron shown in Figure 6) the Tafel
slope analysis is not possible.
The Corrosion Rate Fit tool works in the same
fashion as the Corrosion Rate Tafel Slope tool.
Using markers the linear Tafel region can be
identified. After the markers have been placed on
the plot, the software performs the curve fit and
calculates the characteristic corrosion values using
the specified density, equivalent weight and
surface area (see figure 6).

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Corrosion: 3. Measurement of
Polarization Resistance
In the previous application note, the procedure for
estimating corrosion rates was outlined. The
calculations were valid under the assumption that
the corrosion reactions were under charge transfer
control and that the mechanisms of the reactions
were known. In real life, often, corrosion is a result
of several reactions and it is not possible to a priori
determine the reaction mechanism. In such cases
Polarization Resistance, RP, can be used to
determine the resistance of the metal under
investigation against corrosion.
Polarization Resistance, RP
An electrode is polarized when its potential is forced
away from its value at open circuit or corrosion
potential. Polarization of an electrode causes
current to flow due to electrochemical reactions it
induces at the electrode surface. The polarization
resistance or RP is defined by the following equation:
 ∆E 
RP =  
 ∆i ∆E → 0
Where, ∆E variation of the applied potential around
the corrosion potential and ∆i is the resulting
polarization current.
slope of the current potential curve at open circuit
or corrosion potential.
During the polarization of an electrode, the
magnitude of the current is controlled by reaction
kinetics and diffusion of reactants both towards and
away from the electrode. In the previous application
note, the Butler-Volmer equation was introduced as:
  2.303 η   −2.303 η  
i = icorr  e − e  Measurement of
ba  bc 
 
 
η = E − Ecorr
E is the applied potential and i the measured current
density. The overpotential, η, is defined as the
difference between applied potential and the
corrosion potential Ecorr. The corrosion potential, Ecorr
is the open circuit potential of a corroding metal.
The corrosion current, icorr, and the Tafel constants
ba, and bc can be measured from the experimental
data.
For small η, i.e. for potentials close to corrosion
potential, the above equation can be reduced to:
b ab c  1 
icorr = 2.303  
ba + bc  RP 
or
If the Tafel slopes are known, one can calculate the
corrosion currents from the polarization resistance
using the above equations. If the Tafel slopes are
not known (e.g. when corrosion mechanism is not
known), the RP can still be used as a quantitative
parameter to compare the corrosion resistance of
metals under various conditions. High RP of a metal
implies high corrosion resistance and low RP implies
low corrosion resistance.
RP using electro-
electro-
chemical methods
Linear Sweep Voltammetry(LSV)
In Figure 1 the results of a LSV experiment
performed on an iron screw immersed in seawater
are shown. The slope of the curve at corrosion
potential (- 0.319 V) can be calculated by
performing a linear regression on data from
- 0.329 V to - 0.309 V (i.e. 10 mV cathodic and 10
mV anodic relative to the corrosion potential). The
results of the regression are shown in Figure 2. The
polarization resistance RP is calculated from inverse
of the slope (1/slope) and is found to be 9.442 kΩ.

Polarization resistance, RP, behaves like a resistor b ab c  1 

and can be calculated by taking the inverse of the RP = 2.303  
ba + bc  icorr 

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semi circle, a Randles equivalent circuit shown in

Figure 3 can be used to estimate RP. In Figure 4
Nyquist plot of experimental data for the corrosion
of iron in sulfate solution is shown. The solid line
represents the regression of the Randles circuit to
calculate the polarization resistance, RP.

Figure
Figure 1 – LSV data for the corrosion of an iron screw in sea
water Figure 4 – Estimation of R p for corrosion of iron in
seawater using EIS
Figure 3 – The Randles equivalent circuit

Figure 2 – The calculated regression line equation for the

corrosion of an iron screw in seawater

Electrochemical Impedance Spectro

Spectro-
scopy (EIS)

Polarization resistance can also be measured with

electrochemical impedance spectroscopy. For
simple systems where the Nyquist plot shows one

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Corrosion: 4.
Equivalent circuit models
In recent years Electrochemical Impedance
Spectroscopy or EIS has been successfully applied
to the study of corrosion systems. EIS has been
used effectively to measure the polarization
resistance for corrosion systems and for the
determination of corrosion mechanisms for
systems where DC electrochemical methods have Where RΩ is the uncompensated solution
failed. resistance, Rp is the polarization resitstance and C
or CPE (Constant Phase Element) is the double Where RΩ is the uncompensated solution
EIS has been applied, among others, to uniform layer capacitance. resistance, R1 and R2 are the charge transfer
corrosion, pitting corrosion, corrosion in concrete, resistance values of the anodic and cathodic
and corrosion underneath coatings. In this reaction, respectively and C or CPE is the double
application note some of the equivalent circuit layer capacitance. ZW is the Warburg impedance
models that are used to model corrosion systems used to simulate the mass-transport effects.
are described.

Uniform Corrosion

The most common equivalent circuit used to model

corrosion of bare metal in aqueous electrolyte is
the Randles circuit. The model can be used to
estimate the polarization resistance RP from the
impedance data.

For corrosion of low carbon steel in NaCl solution,

the following equivalent circuit has been proposed.

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Coatings

Impedance spectroscopy has been used

extensively to characterize the corrosion protection
of metals by coatings. The following equivalent
circuit is often used to model a coating.

Where RΩ is the uncompensated solution Corrosion in concrete

resistance, Rp is the paint resistance, which is an When the coating is intact, in the previous circuit,
indication of the coating’s porosity. Cp is the paint RP the paint resistance goes to infinity and the
capacitance, which quantifies the water uptake by circuit reduces to the following equivalent circuit The following equivalent circuit has been proposed
the coating. Rct is the charge transfer resistance, model: the corrosion of steel in concrete.
which provides a value of the protection of the
substrate. Cdl is the double layer capacitance,
which can be correlated to the delamination of the
coating. ZW quantifies the mass-transport related
contributions.

Where RΩ is the uncompensated solution

resistance, RF is the resistance at the
concrete/stainless steel interface, CF is the
concrete/stainless interfacial capacitance, Rct is the
charge transfer resistance of the corrosion
reaction, Cdl is the double layer capacitance and ZW

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is the Warburg impedance related to the diffusion

of oxygen to steel.

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Corrosion: 5.
Corrosion Inhibitors
A corrosion inhibitor is a substance when added in
a small concentration to an environment reduces
the corrosion rate of a metal exposed to that
environment. Inhibitors often play an important role
in the oil extraction and processing industries
where they have always been considered to be the
first line of defence against corrosion.
Types of corrosion inhibitors
Anodic inhibitors
Anodic inhibitors usually act by forming a protective
oxide film on the surface of the metal causing a
large anodic shift of the corrosion potential. This
shift forces the metallic surface into the passivation
region. They are also sometimes referred to as
passivators. Chromates, nitrates, tungstate,
molybdates are some examples of anodic
inhibitors.
Cathodic inhibitors
Cathodic inhibitors act by either slowing the
cathodic reaction itself or selectively precipitating
on cathodic areas to limit the diffusion of reducing
species to the surface.
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The rates of the cathodic reactions can be reduced
by the use of cathodic poisons. However, cathodic
poisons can also increase the susceptibility of a
metal to hydrogen induced cracking since
hydrogen can also be absorbed by the metal
during aqueous corrosion or cathodic charging.
The corrosion rates can also be reduced by the
use of oxygen scavengers that react with dissolved
oxygen. Sulfite and bisulfite ions are examples of
oxygen scavengers that can combine with oxygen
to form sulfate.
Mixed Inhibitors
Mixed inhibitors work by reducing both the
cathodic and anodic reactions. They are typically
film forming compounds that cause the formation
of precipitates on the surface blocking both anodic
and cathodic sites indirectly.
Hard water that is high in calcium and magnesium
is less corrosive than soft water because of the
tendency of the salts in the hard water to
precipitate on the surface of the metal forming a
protective film.
The most common inhibitors of this category are
the silicates and the phosphates. Sodium silicate,
for example, is used in many domestic water
softeners to prevent the occurrence of rust water.
In aerated hot water systems, sodium silicate
protects steel, copper and brass. However,
protection is not always reliable and depends
heavily on pH. Phosphates also require oxygen for
effective inhibition. Silicates and phosphates do not
afford the degree of protection provided by
chromates and nitrites, however, they are very
useful in situations where non-toxic additives are
required.
Volatile Corrosion Inhibitors
Volatile Corrosion Inhibitors (VCI), also called Vapor
Phase Inhibitors (VPI), are compounds transported
in a closed environment to the site of corrosion by
volatilization from a source. In boilers, volatile basic
compounds, such as morpholine or hydrazine, are
transported with steam to prevent corrosion in the
condenser tubes by neutralizing acidic carbon
dioxide or by shifting surface pH towards less
acidic and corrosive values. In closed vapor
spaces, such as shipping containers, volatile solids
such as salts of dicyclohexylamine, cyclo-
hexylamine and hexamethylene-amine are used.
When these inhibitors come in contact with the
metal surface, the vapor of these salts condenses
and is hydrolyzed by any moisture to liberate
protective ions. It is desirable, for an efficient VCI,
to provide inhibition rapidly while lasting for long
periods. Both qualities depend on the volatility of
these compounds; fast action wanting high
volatility while enduring protection requires low
volatility.
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Evaluation of Corrosion inhibitors
inhibitors
Electrochemical methods are used routinely for the
evaluation of the efficiency of corrosion inhibitors.
The advantages of electrochemical methods are
short measurement time and mechanistic
information that they provide which help not only in
the design of corrosion protection strategies but
also in the design of new inhibitors.
Electrochemical Characterisation of
anodic inhibitor
Benzoic acid was chosen as an example anodic
inhibitor to illustrate the use of electrochemical
methods for the characterization of inhibitors. A
polished 3 mm diameter CK 45 steel rod
embedded in epoxy was used as the working
electrode. The AUT-RDE (rotating disc electrode)
system was used to maintain a constant rpm of
800 for the experiments. The experiments were
conducted in the AUTOLAB Corrosion Cell.
The efficiency of the inhibitor was studied by
adding 0.5 M benzoic acid to 0.1 M Na2SO4
solution. The electrolyte was deaerated for
30 minutes by N2 purging prior to the start of the
experiment. Reference measurements were done
on 0.1 M Na2SO4 solution without inhibitor. The pH
of the solution was adjusted to 6.5 with NaOH and
H2SO4 prior to the start of the experiment. A
platinum sheet electrode (6.0305.100) was used as
the counter electrode and Ag/AgCl (6.0733.100)
was used as the reference electrode.
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The linear sweep voltammetry (LSV) experiments
were conducted using an AUTOLAB PGSTAT302N
controlled by the NOVA software. The potentials
were scanned from - 1.2V to 0.6V (vs. Ag/AgCl).
Beginning the experiments at cathodic potentials
ensured that any oxide layer present prior to the
start of the experiments was reduced. A 2.5 mV
potential step and a slow scan rate of 2 mV/s were
used.
In the following figure, polarization curves for
solutions with and without inhibitor are shown. The
anodic part of the polarization curve without
inhibitor is typical for active metal dissolution.
The results shown in the figure illustrate when an
anodic inhibitor is added to the solution there is a
shift of the corrosion potential in the anodic Reference
direction and a reduction in the anodic current. The
corrosion inhibitor also results in the formation of
1. P. Agarwal and D. Landolt, “ Effect of Anions on
the passive film evidenced by the appearance of the Efficiency of Aromatic Carboxylic Acid
the passivation plateau. More details of the
Corrosion Inhibitors in Near Neutral Media:
analysis can be found in ref. 1. Experimental Investigation and Theoretical
Modeling,” Corrosion Science, 260 (1998), 673-
691.
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Corrosion 6. Critical Pitting
Temperature measurement with
PX1000
Critical pitting temperature (CPT) is the lowest
temperature on the test surface at which stable
propagating pitting occurs under specified test
conditions indicated by a rapid increase beyond a set
limit of the measured anodic current density of the
specimen.
The method is suitable for characterizing the pitting
corrosion resistance of stainless steel and related
alloys. This measurement technique can be used in
research and development studies, production test
and acceptance, materials control.
The Critical pitting corrosion consists in a Chrono
amperometric experiment combined with a In both cases a sudden variation of the current will
temperature ramp. The temperature is controlled
through NOVA software or adjusted manually (ramp of
1ºC/min) using a thermostatic bath and a temperature
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sensor placed in the measurement cell. The test
solution used to run all experiments was 1M NaCl and
a Metrohm PT1000 (6.1110.100) connected to the
PX1000 module (Figure 1).
The cell used for the experiment is shown in Figure 2.
The counter electrode is a glassy carbon rod
Metrohm (6.1248.040), the reference electrode is a
Ag/AgCl 3M KCl Metrohm (6.0726.100). The stirrer
has been use during the stabilization temperature
before and after all the experiments.
All solutions were not deareated.
Figure 1 - PT1000 sensor Figure 2 - cell setup
There are two different ways to measure the CPT:
- Apply a temperature ramp from 25ºC to 60ºC
and monitor the current variation at fixed
potential.
- Apply 5ºC temperature steps from 25ºC to
60ºC and monitor the current for 60 seconds
at fixed potential.
indicate the CPT.
Preliminary
Preliminary measurements
- Polarization resistance measurement
To arrange proper measurement condition for CPT
determination, we measured the linear polarization
curves at different temperatures in order to determine
a suitable temperature range.
60º 25º
Figure 3 – Polarization curves 304 steel
Figure 3 shows typical linear polarization curves for
304 steel coupons at 25ºC (blue line) and at 60ºC (red
line)
From the above graph we can see the change of the
corrosion potential with increasing temperature and a
rapid increase of the current on the anodic side of the
curve even though the final current value reached is
similar.
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From the Figure 3 it is possible to recognize the
change in potential where the corrosion occurs.
- Multipotential step chronoamperometry
A second useful test consists of a multi potential step
from 100mV to 700mV Chrono amperometry
experiment at different temperature.
60º
25º
Figure 4 – multipotential steps measurements at different
temperature
temperature
Figure 4 shows a 60 s measurement with potential
steps from 200 mV above the OCP to 700 mV at
25ºC and 60ºC.
In this case it is possible to recognize an increase of
the current at 60ºC already at 300 mV above the
OCP, this current increase is similar to the increment
at 700 mV at 25ºC.
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Critical pitting temperature experiments
experiments
To test the CPT we apply a continuous ramp of
temperature from 25ºC to 60ºC while monitoring the
temperature and the current at the same time while
keeping the potential fixed.
1st Sample
2nd Sample
Figure 6 – CPT measurements for different steel samples
Figure 6 shows two different kinds of steel samples at
100mV 100mV above OCP same temperature ramp same
50mV
conditions but two different CPT.
A second type of CPT can be performed with
Figure 5 – CPT measurements at different potentials temperature steps instead a temperature ramp
protocol. In the figure below temperature steps of 5ºC
Figure 5 shows two experiments: (1) at 100 mV above from 30ºC to 60ºC were applied and the current was
the OCP (blue line) and (2) at 50mV above the OCP measured for 60 seconds until there is a measurable
(green line) the temperatures where the CPT takes variation.
place are very different: one is 49.5ºC and the other
55.4ºC.
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More information about CPT measurements can be

found in ASTM G150-99.

Figure 7 - composite
composite analysis graph temperature steps

In red temperature steps every 5 ºC, then in green the

increment of the temperature between the steps. The
other colored lines are the current vs time graphs.

From these graphs it is possible to see that the

current increment at the last two temperature steps is
increasing dramatically since the temperatures were
higher then the Critical pitting temperature of the
material tested.

Conclusions

This application note has illustrated the use of the

PX1000 module for temperature monitoring and
setting in linear polarization and pitting corrosion.

All experiments are easy to manage with Autolab

PGSTAT equipments and NOVA software.
RS232 Control of the water bath directly through the
software allows automatic programming of
temperature steps or ramps.

APPLICATION NOTE 51 AUTOLAB INSTRUMENTS ARE DEVELOPED AND PRODUCED BY METROHM AUTOLAB B.V. IN THE NETHERLANDS WWW.METROHM-AUTOLAB.COM