AUTOLAB APPLICATION NOTE

Types of Corrosion
Corrosion
Corrosion: 1. Basic Concepts
Uniform Corrosion
Corrosion refers to a process that involves
deterioration or degradation of metal. The most Uniform corrosion is characterized by corrosive
common example of corrosion is the formation of attack proceeding evenly over the entire surface
rust on steel. Most corrosion phenomena are of area, or a large fraction of the area of the metal
electrochemical nature and consist of at least two under attack. Uniform corrosion results in loss of
reactions on the surface of the corroding metal. material until failure. This is the most widespread
One of the reactions is the oxidation (e.g., form of corrosion that is observed. Crevice Corrosion
dissolution of iron) also referred to as the anodic
partial reaction. The other is a reduction reaction Crevice corrosion is a localized form of corrosion
(e.g., reduction of oxygen), and is referred to as the that occurs in the presence of stagnant solution in a
cathodic partial reaction. The products of the small (micro) crevice. Local chemistry changes in
electrochemical reactions can react with each other crevices (shielded areas) such as those formed
non-electrochemically to form the final product (e.g., under gaskets, washers, insulation material,
rust). For example, the corrosion of iron to form rust fastener heads, surface deposits, disbonded
proceeds according to the overall reaction: coatings, threads, lap joints and clamps, can result
in crevice corrosion.
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+ -

Pitting Corrosion
2 H2O + O2 + 4 e → 4 OH (cathodic)
- -

Pitting corrosion is a localized form of corrosion by

2 Fe + 4 OH → 2 Fe(OH)2 (chemical)
2+ - which pits or "pin holes" are produced in the
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 (requires little or no oxygen), such as sulfate Electrochemical impedance spectroscopy (EIS)
more) dissimilar metals are brought into electrical reducing bacteria.
contact under water. When a galvanic couple In recent years Electrochemical Impedance
forms, one of the metals in the couple becomes the Spectroscopy or EIS has been successfully applied
anode and corrodes faster than it would all by itself, to the study of corrosion systems. One of the
while the other becomes the cathode and corrodes advantages of EIS over DC techniques is the
slower than it would alone. Either (or both) metal in possibility of using very small amplitude signals
the couple may or may not corrode by itself without significantly disturbing the properties being
(themselves) in seawater. 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)

Microbiologically Induced Corrosion (MIC)
Linear sweep voltammetry or LSV is one of the
Microbiologically Induced Corrosion or MIC refers to most commonly used methods for characterising
corrosion caused by biological organisms or corrosion phenomenon. It involves sweeping the
microbes. These microbes are categorized by potential of the working electrode and measuring
common characteristics such as their by-products the current response. With LSV one can obtain
(i.e., sludge producing) or compounds they effect valuable information regarding the corrosion
(i.e. sulfur oxidizing). They all fall into one of two mechanisms, corrosion rate and susceptibility of
groups based upon their oxygen requirements; one specific materials to corrosion in various
being aerobic (requires oxygen) such as sulfur environments.
oxidizing bacteria, and the other being anaerobic,

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Corrosion: 2. Measurement of linear relationship between the metal dissolution In the above equation E is the applied potential and
rate or corrosion rate, RM, and the corrosion current i the measured current density. The overpotential,
Corrosion Rates icorr: η, is defined as the difference between applied
potential and the corrosion potential Ecorr. The
M corrosion potential, Ecorr is the open circuit potential
RM = icorr of a corroding metal. The corrosion current, icorr,
Weight loss measurements nFρ and the Tafel constants ba, and bc can be
measured from the experimental data.
The simplest way of measuring the corrosion rate where M is the atomic weight of the metal, ρ is the
density, n is the charge number which indicates the For large anodic overpotentials (η / ba >> 1) the
of a metal is to expose the sample to the test
number of electrons exchanged in the dissolution Butler-Volmer equation simplifies to the Tafel
medium (e.g. sea water) and measure the loss of
reaction and F is the Faraday constant, (96.485 equation for the anodic reaction:
weight of the material as a function of time.
Although these tests are simple, there is no simple C/mol). The ratio M/n is also sometime referred to
way to extrapolate the results to predict the lifetime as equivalent weight. η = logicorr + ba logi
of the system under investigation. Moreover, some
corrosion processes occur with no significant mass Calculation of corrosion currents Analogously, for large cathodic overpotentials
change (e.g. pitting corrosion) making them difficult (bc << -1) the Tafel equation for the cathodic
to detect by gravimetric methods. Calculation of corrosion rates requires the reaction is given by:
determination of corrosion currents. When reaction
Electrochemical t ests mechanisms for the corrosion reaction are known, η = logicorr − bc log i
the corrosion currents can be calculated using
Tafel Slope Analysis. The Tafel equations predict a straight line for the
As mentioned in the previous application notes, variation of the logarithm of current density with
most corrosion phenomena are of electrochemical The relationship between current density and potential. Therefore, currents are often shown in
nature and consist of reactions on the surface of potential of anodic and cathodic electrode semilogarithmic plots known as Tafel plots. This
the corroding metal. Therefore electrochemical reactions under charge transfer control is given by type of analysis is referred to as Tafel Slope
tests methods can be used to characterise the Butler-Volmer equation: Analysis.
corrosion mechanisms and predict corrosion rates.
  2.303 η   −2.303 η   Calculation of corrosion currents in NOVA
Calculation of corrosion rates i = icorr  e ba 
+ e bc 

  The NOVA software provides a convenient
 
The corrosion rate depends on the kinetics of both interface for making Tafel plots, calculating Tafel
anodic (oxidation) and cathodic (reduction) η = E − Ecorr slopes and corrosion rates. In Figure 1 the current
reactions. According to Faraday's law, there is a

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

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. The rates of the cathodic reactions can be reduced afford the degree of protection provided by
by the use of cathodic poisons. However, cathodic chromates and nitrites, however, they are very
Corrosion Inhibitors poisons can also increase the susceptibility of a useful in situations where non-toxic additives are
metal to hydrogen induced cracking since required.
hydrogen can also be absorbed by the metal
A corrosion inhibitor is a substance when added in during aqueous corrosion or cathodic charging.
a small concentration to an environment reduces Volatile Corrosion Inhibitors
the corrosion rate of a metal exposed to that The corrosion rates can also be reduced by the
environment. Inhibitors often play an important role use of oxygen scavengers that react with dissolved Volatile Corrosion Inhibitors (VCI), also called Vapor
in the oil extraction and processing industries oxygen. Sulfite and bisulfite ions are examples of Phase Inhibitors (VPI), are compounds transported
where they have always been considered to be the oxygen scavengers that can combine with oxygen in a closed environment to the site of corrosion by
first line of defence against corrosion. to form sulfate. volatilization from a source. In boilers, volatile basic
compounds, such as morpholine or hydrazine, are
transported with steam to prevent corrosion in the
Types of corrosion inhibitors Mixed Inhibitors condenser tubes by neutralizing acidic carbon
dioxide or by shifting surface pH towards less
Mixed inhibitors work by reducing both the acidic and corrosive values. In closed vapor
Anodic inhibitors
cathodic and anodic reactions. They are typically spaces, such as shipping containers, volatile solids
film forming compounds that cause the formation such as salts of dicyclohexylamine, cyclo-
Anodic inhibitors usually act by forming a protective of precipitates on the surface blocking both anodic hexylamine and hexamethylene-amine are used.
oxide film on the surface of the metal causing a and cathodic sites indirectly.
large anodic shift of the corrosion potential. This When these inhibitors come in contact with the
shift forces the metallic surface into the passivation Hard water that is high in calcium and magnesium metal surface, the vapor of these salts condenses
region. They are also sometimes referred to as is less corrosive than soft water because of the and is hydrolyzed by any moisture to liberate
passivators. Chromates, nitrates, tungstate, tendency of the salts in the hard water to protective ions. It is desirable, for an efficient VCI,
molybdates are some examples of anodic precipitate on the surface of the metal forming a to provide inhibition rapidly while lasting for long
inhibitors. protective film. periods. Both qualities depend on the volatility of
these compounds; fast action wanting high
Cathodic inhibitors The most common inhibitors of this category are volatility while enduring protection requires low
the silicates and the phosphates. Sodium silicate, volatility.
Cathodic inhibitors act by either slowing the for example, is used in many domestic water
cathodic reaction itself or selectively precipitating softeners to prevent the occurrence of rust water.
on cathodic areas to limit the diffusion of reducing In aerated hot water systems, sodium silicate
species to the surface. 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

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Evaluation of Corrosion inhibitors

inhibitors The linear sweep voltammetry (LSV) experiments
were conducted using an AUTOLAB PGSTAT302N
Electrochemical methods are used routinely for the controlled by the NOVA software. The potentials
evaluation of the efficiency of corrosion inhibitors. were scanned from - 1.2V to 0.6V (vs. Ag/AgCl).
The advantages of electrochemical methods are Beginning the experiments at cathodic potentials
short measurement time and mechanistic ensured that any oxide layer present prior to the
information that they provide which help not only in start of the experiments was reduced. A 2.5 mV
the design of corrosion protection strategies but potential step and a slow scan rate of 2 mV/s were
also in the design of new inhibitors. used.

In the following figure, polarization curves for

Electrochemical Characterisation of solutions with and without inhibitor are shown. The
anodic inhibitor anodic part of the polarization curve without
inhibitor is typical for active metal dissolution.
Benzoic acid was chosen as an example anodic The results shown in the figure illustrate when an
inhibitor to illustrate the use of electrochemical anodic inhibitor is added to the solution there is a
methods for the characterization of inhibitors. A shift of the corrosion potential in the anodic Reference
polished 3 mm diameter CK 45 steel rod direction and a reduction in the anodic current. The
embedded in epoxy was used as the working corrosion inhibitor also results in the formation of
electrode. The AUT-RDE (rotating disc electrode) 1. P. Agarwal and D. Landolt, “ Effect of Anions on
the passive film evidenced by the appearance of the Efficiency of Aromatic Carboxylic Acid
system was used to maintain a constant rpm of the passivation plateau. More details of the
800 for the experiments. The experiments were Corrosion Inhibitors in Near Neutral Media:
analysis can be found in ref. 1. Experimental Investigation and Theoretical
conducted in the AUTOLAB Corrosion Cell.
Modeling,” Corrosion Science, 260 (1998), 673-
691.
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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sensor placed in the measurement cell. The test Preliminary

Preliminary measurements
solution used to run all experiments was 1M NaCl and
a Metrohm PT1000 (6.1110.100) connected to the
PX1000 module (Figure 1).
- Polarization resistance measurement

The cell used for the experiment is shown in Figure 2. To arrange proper measurement condition for CPT
The counter electrode is a glassy carbon rod determination, we measured the linear polarization
Metrohm (6.1248.040), the reference electrode is a curves at different temperatures in order to determine
Ag/AgCl 3M KCl Metrohm (6.0726.100). The stirrer a suitable temperature range.
has been use during the stabilization temperature
before and after all the experiments.
All solutions were not deareated.
60º 25º

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 Figure 1 - PT1000 sensor Figure 2 - cell setup
specimen. Figure 3 – Polarization curves 304 steel
There are two different ways to measure the CPT:
The method is suitable for characterizing the pitting Figure 3 shows typical linear polarization curves for
corrosion resistance of stainless steel and related - Apply a temperature ramp from 25ºC to 60ºC 304 steel coupons at 25ºC (blue line) and at 60ºC (red
alloys. This measurement technique can be used in and monitor the current variation at fixed line)
research and development studies, production test potential.
and acceptance, materials control. - Apply 5ºC temperature steps from 25ºC to From the above graph we can see the change of the
60ºC and monitor the current for 60 seconds corrosion potential with increasing temperature and a
The Critical pitting corrosion consists in a Chrono at fixed potential. rapid increase of the current on the anodic side of the
amperometric experiment combined with a In both cases a sudden variation of the current will curve even though the final current value reached is
temperature ramp. The temperature is controlled indicate the CPT. similar.
through NOVA software or adjusted manually (ramp of
1ºC/min) using a thermostatic bath and a temperature

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From the Figure 3 it is possible to recognize the Critical pitting temperature experiments
experiments
change in potential where the corrosion occurs.
To test the CPT we apply a continuous ramp of
- Multipotential step chronoamperometry temperature from 25ºC to 60ºC while monitoring the
temperature and the current at the same time while
A second useful test consists of a multi potential step keeping the potential fixed.
from 100mV to 700mV Chrono amperometry
experiment at different temperature.
1st Sample
2nd Sample

60º
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.
25º
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
Figure 4 – multipotential steps measurements at different (green line) the temperatures where the CPT takes variation.
temperature
temperature place are very different: one is 49.5ºC and the other
55.4ºC.
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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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.

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