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Types of Corrosion 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+ -

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
-

2 H2O + O2 + 4 e 4 OH (cathodic)
-

2 Fe + 4 OH 2 Fe(OH)2 (chemical)
2+ -

Pitting corrosion is a localized form of corrosion by 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 detection often very difficult. A small, narrow pit with minimal overall metal loss can lead to the failure of an entire engineering system.

Galvanic Corrosion Galvanic corrosion refers to corrosion damage 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.

(requires little or no oxygen), such as sulfate reducing bacteria.

Electrochemical impedance spectroscopy (EIS) 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) 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, 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.

linear relationship between the metal dissolution rate or corrosion rate, RM, and the corrosion current icorr:

RM =

M icorr nF

In the above equation E is the applied potential and i the measured current density. The overpotential, , 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 large anodic overpotentials ( / ba >> 1) the Butler-Volmer equation simplifies to the Tafel equation for the anodic reaction:

where M is the atomic weight of the metal, 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 2.303 ba bc i = icorr e +e = E Ecorr

= logicorr + ba logi
Analogously, for large cathodic overpotentials (bc << -1) the Tafel equation for the cathodic reaction is given by:

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

= 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 seawater is shown.

automatically plotted on the Tafel Plot as shown in 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 as shown in Figure 2. The user can specify the equivalent weight, density of the electrode material, the surface area of the electrode and the number of significant digits to use in the calculation as shown in Figure 3.
Figure 3 The working electrode parameters used in the Tafel slope analysis

The Tafel slope analysis tool provides a quick estimation of the corrosion rate and the polarization resistance. The corrosion rate is calculated from the estimated corrosion current, icorr, obtained from the intercept of the two linear segment of the Tafel slope.

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

Selecting the Corrosion Rate Fit analysis tool from the Analysis menu performs a similar analysis as with the Corrosion Rate Tafel Slope tool. The fit tool also performs a curve fit based on the ButlerVolmer expression which allows for a more accurate determination of the corrosion current, polarization resistance and corrosion rate. 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).

Figure 6 NOVA displays the results of the Corrosion rate fit analysis

In choosing the regions for Tafel slope analysis, care must be taken. A correct estimate of the Tafel slopes is possible only if the linear Tafel region (region between markers in Figure 3) covers at least 1 decade in current. In certain cases (e.g., passivation of iron shown in Figure 6) the Tafel slope analysis is not possible.

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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.

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 2.303 ba bc i = icorr e e = E Ecorr

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.

Measurement of chemical methods

RP

using

electroelectro-

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 k.

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 is the applied potential and i the measured current density. The overpotential, , 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 , i.e. for potentials close to corrosion potential, the above equation can be reduced to:

E RP = i E 0
Where, E variation of the applied potential around the corrosion potential and i is the resulting polarization current. Polarization resistance, RP, behaves like a resistor and can be calculated by taking the inverse of the

icorr = 2.303
or

b ab c ba + bc

1 RP

RP = 2.303

b ab c ba + bc

1 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 3 The Randles equivalent circuit

Figure 4 Estimation of R p for corrosion of iron in seawater using EIS

Figure 2 The calculated regression line equation for the corrosion of an iron screw in seawater

Electrochemical scopy (EIS)

Impedance

Spectro Spectro-

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 failed. EIS has been applied, among others, to uniform corrosion, pitting corrosion, corrosion in concrete, and corrosion underneath coatings. In this application note some of the equivalent circuit models that are used to model corrosion systems are described.

Where R is the uncompensated solution resistance, Rp is the polarization resitstance and C or CPE (Constant Phase Element) is the double layer capacitance.

Where R is the uncompensated solution resistance, R1 and R2 are the charge transfer resistance values of the anodic and cathodic reaction, respectively and C or CPE is the double layer capacitance. ZW is the Warburg impedance used to simulate the mass-transport effects.

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 R is the uncompensated solution resistance, Rp is the paint resistance, which is an indication of the coatings porosity. Cp is the paint capacitance, which quantifies the water uptake by the coating. Rct is the charge transfer resistance, 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.

When the coating is intact, in the previous circuit, RP the paint resistance goes to infinity and the circuit reduces to the following equivalent circuit model:

Corrosion in concrete
The following equivalent circuit has been proposed the corrosion of steel in concrete.

Where R 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.

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.

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, cyclohexylamine 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.

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.

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

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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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.

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 direction and a reduction in the anodic current. The corrosion inhibitor also results in the formation of the passive film evidenced by the appearance of the passivation plateau. More details of the analysis can be found in ref. 1.

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.

Reference
1. P. Agarwal and D. Landolt, Effect of Anions on the Efficiency of Aromatic Carboxylic Acid Corrosion Inhibitors in Near Neutral Media: Experimental Investigation and Theoretical Modeling, Corrosion Science, 260 (1998), 673691.

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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.

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.

60
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 temperature ramp. The temperature is controlled through NOVA software or adjusted manually (ramp of 1C/min) using a thermostatic bath and a temperature

25

Figure 1 - PT1000 sensor

Figure 2 - cell setup Figure 3 Polarization curves 304 steel

There are two different ways to measure the CPT: Apply a temperature ramp from 25C to 60C and monitor the current variation at fixed potential. - Apply 5C temperature steps from 25C to 60C and monitor the current for 60 seconds at fixed potential. In both cases a sudden variation of the current will indicate the CPT. Figure 3 shows typical linear polarization curves for 304 steel coupons at 25C (blue line) and at 60C (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.

Critical pitting temperature experiments experiments

To test the CPT we apply a continuous ramp of temperature from 25C to 60C while monitoring the temperature and the current at the same time while keeping the potential fixed.

- Multipotential step chronoamperometry

A second useful test consists of a multi potential step from 100mV to 700mV Chrono amperometry experiment at different temperature.

1st Sample 2nd Sample

60
Figure 6 CPT measurements for different steel samples

100mV

25

50mV

Figure 6 shows two different kinds of steel samples at 100mV above OCP same temperature ramp same conditions but two different CPT. A second type of CPT can be performed with temperature steps instead a temperature ramp protocol. In the figure below temperature steps of 5C from 30C to 60C were applied and the current was measured for 60 seconds until there is a measurable variation.

Figure 5 CPT measurements at different potentials

Figure 4 multipotential steps measurements at different temperature temperature

Figure 5 shows two experiments: (1) at 100 mV above the OCP (blue line) and (2) at 50mV above the OCP (green line) the temperatures where the CPT takes place are very different: one is 49.5C and the other 55.4C.

Figure 4 shows a 60 s measurement with potential steps from 200 mV above the OCP to 700 mV at 25C and 60C. In this case it is possible to recognize an increase of the current at 60C already at 300 mV above the OCP, this current increase is similar to the increment at 700 mV at 25C.

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More information about CPT measurements can be found in ASTM G150-99.

T I

Figure 7 - composite composite analysis graph temperature steps

In red temperature steps every 5 C, 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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