Electrochemical Impedance Monitoring of Carbon Fiber as an Anode Material in Cathodic Protection

M. Chini, R. Antonsen, B. Arntsen

Norut Teknologi, Narvik, Norway

. Vennesland
Department of Structural Engineering, NTNU, 7491 Trondheim, Norway

J. H. Mork
maxit Group AB, Oslo, Norway

ABSTRACT: In impressed current CP systems, an insoluble anode is used on the surface or within the concrete structure. The most frequently and widely used anode material is titanium covered with noble metal oxides. Meanwhile much work is carried out to replace the anode material or improve the application technique such as using conductive coatings and paintings. In this regard, carbon fiber meshes have been introduced as an alternative for the last decade. Unfortunately, scientific work and publications concerning electrochemical properties of carbon embedded in concrete are scarce. Hence, a series of experiments have been designed and carried out in order to improve knowledge of its behavior as anode. One of these tests is to monitor the behavior of carbon by means of EIS measurements. After carbon was polarized in different potential values, EIS have been done. Also effect of addition of 1 and 3 percent chloride ions has been investigated. 1 INTRODUCTION reinforcement; in this case rebars are acting as cathode and connected with the negative terminal (Pedeferri 1996). The anode material is a critical component of a CP system, because it serves to distribute the protective current across the structure and provides the locations for anodic reactions to take place in lieu of the reinforcing steel. Therefore, while the system is in service, the anode, instead of the reinforcing steel, will degrade. Moreover one of the objectives in CP design is to deliver a fairly uniform current density to protected steel; this will minimize the current required to achieve the protection criterion, thus reducing the cost as well as the life of the system components (Buenfeld 2002). And utilizing good anode material could be very helpful to reach this aim. There are some materials which are used as anode. Although the most frequently used anode material is titanium mesh covered by activated metal oxides, as a more recent anode material the carbon fiber meshes have been used for some years in some countries. Since carbon fiber used as anode material is a new CP system, the published papers about this anode material are scarce (Chini 2007) and very few researchers have work on this theme. Hence, a series of experiments have been designed and applied in order to improve knowledge of its behavior as anode. One of these designed test programs is investigation of electrochemical

Steel- reinforced concrete is widely used in construction. The corrosion of the steel reinforcing bars in the concrete limits the life of concrete structures (Chang 2000). And this causes substantial financial losses. The estimated annual cost of repair of reinforced concrete structures is over 5 billion Euros in Western Europe in the beginning of millennium (Mork et al. 2006). The direct cause of destruction is increase of volume of steel reinforcement as the result of corrosion product formation (Darowicki 2003). Therefore the registered need for rehabilitation and repair and the associated costs is a matter of great concern for those responsible for assessment and maintenance of affected structures. Due to this matter, several protection and prevention methods and technique have been developed (Chini 2008). A corrosion control method for steel reinforced concrete involved cathodic protection (Chang 1995). Cathodic protection (CP) is a widely used and accepted method of corrosion control for reinforced concrete structures (Mork et al. 2006). Cathodic protection (CP) of steel reinforcement in concrete structures is obtained by applying a direct current through the concrete from an anode system which is usually applied on the concrete surface. Anode material is connected with the positive terminal of a low voltage direct voltage source towards

impedance behavior of carbon fibers in electrolyte which is simulated of pore solution of concrete. There are several different test methods in order to investigate the characteristics of a material. One of these methods includes monitoring the electrochemical behavior of the reactions. Among the various electrochemical methods widely developed in the literature, electrochemical impedance spectroscopy (EIS) seems to be the most reliable technique in monitoring the corrosion process (Poupard 2004). Electrochemical impedance is usually measured by applying an AC potential to an electrochemical cell and measuring the current through the cell. In this paper obtained data on electrochemical impedance spectroscopy (EIS) of carbon fibers after polarizing in different potential values in electrolyte would be presented. Also effect of existence of chloride in electrolyte was investigated and obtained data in different amount of chloride ions would be illustrated.

TEST PREPARATION

EXPERIMENTAL PROGRAM

To investigate impedance on carbon in order to clarify its behavior as anode in CP system, EIS test has been done on carbon after polarizing it in different potential values. Therefore, after carbon was polarized anodically from open circuit corrosion potential (OC potential) as 20, 40, 60, 100, 150, 300, 500, 750, 1000, 1500, 2000, 2500, 3500, 5000 mV, impedance applied. Afterwards the impedance amplitude of 10 mV versus polarization value was applied to carbon electrode while the system kept on the polarization potential. These measurements were operated by Impedance analyzer 1260 from Solartron Company. Also this cooperated with Electrochemical Interface 1287; by using Solartron 1287 the potentials were continuously applied and the data was stored. A titanium MMO was used as counter electrode and the reference electrode was SCE (Hg/Hg2Cl2 in saturated KCl). Since it is believed that existence of chloride ion plays an important role in corrosion process, effect of different amount of chloride were also investigated. Therefore measurements were also made in chloride contents of 0, 1 and 3 percent of solution volume in the same polarization potentials as above.

In CP system the carbon is used as mesh. The applied anode material is a continuous, highly flexible mesh woven of carbon fibers. This makes the anode easy to install. The threads may consist of thousands of filaments with a thickness of 7 m of each filament. In a common industrial product, a thread consists of approximately 6000 or 24000 filaments which make a very narrow thread (Vennesland 2005, Mork et al. 2006). Since it was impossible to find a carbon rod from industry, it is very difficult to measure the corrosion current density among longitude of fibers, due to the fact that it is impossible to measure the exact surface area of exposed fibers. Although some techniques have been introduced (Mork et al. 2006), there are still uncertainties on measurement of surface area. Hence, in order to have more accurate active surface area after various experiments, the cross section corrosion monitoring was designed. In this method 10 bundles of 24000-filament thread were cast in a non-conductive transparent epoxy. Transparent pipe was used as mold in order to monitor the accuracy of the procedure. After molding, the specimen was cut and ground to have a smooth and clear cross section. This method gives a surface area of around 10 mm2. A chamber was also designed for this method. It was filled by solution. The more detailed setup was described in previous work (Chini 2008). New samples were made by cutting 4 to 5 millimeters from the head of the used specimen. Therefore 20 cm length specimen could be used for several experiments. To reach a stable status in polarization the following procedure was applied. First, system was run in open circuit condition until stabilizing the carbon in this alkaline solution. After that anode was polarized between 30 minutes and 150 minutes, depends on polarization potential value. All testing process was monitored and saved by Solartron 1287. After polarization, electrochemical impedance spectroscopy test was applied and monitored by Solartron 1260. Impedance measurements were in frequency range of 0.1 Hz to 32 MHz. To simulate the concrete pore solution, a mixture of sodium, potassium and calcium hydroxide was used. pH of the solution was 13.2 and the measurements made in room temperature between 22 and 25 centigrade. Chloride ions were added as NaCl to make 1% and 3% chloride solutions.

IMPEDANCE SPECTROSCOPY

Nowadays, electrochemical techniques are widely used as a non-destructive method in order to monitor and investigate the corrosion of materials. The alternating current (AC) impedance spectroscopy technique is a powerful method used in determining many of electrical properties of materials and their interfaces in solid physics. It is often used to investigate the kinetics of electrochemical reactions, liquid-solid interface properties, metal corrosion and the behavior of batteries etc (Gu & Beaudoin 1998). The early literature in the 1940s and 1950s provides the fundamental basis of the impedance theory and its application (Cole & Cole 1941, Randles 1947, Macdonald 1953). Electrochemical impedance is usually measured by applying an AC potential to an electrochemical cell and measuring the current through the cell. When an external voltage signal is imposed on an electrochemical system, the system shows a transient response in current. The response consists of a faradic part which is related to the electrochemical reaction itself, and a capacitive part which has to do with charging or discharging of the electrical double layer at the solution-metal interface. The faradic part of the response can be considered as purely resistive response with a linear relationship between the voltage and the current, as long as the imposed signal is low in amplitude (in order of mV). The capacitive part corresponds to the response of a condenser with an exponential decay of the current with time (Sigurdsson 1986). An electrochemical system can thus be thought of as a simple electrical circuit. The simplest model, which is applicable to a purely activation controlled reaction, corresponds to a resistor and a condenser in parallel (which is known as Randle model). The resistor corresponds to a charge transfer resistance which is inversely proportional to the reaction rate, while the condenser corresponds to the double layer capacitance which is a property of the materialsolution interface (Sigurdsson 1986). By studying the impedance characteristics of an electrochemical system at different frequencies, the details of the system can be studied assuming that a reasonably representative electrical model or equivalent circuit is available. Various models based on the use of electrical equivalent circuits were used in the data interpretation. Determining the corrosion polarization resistance using AC impedance technique, two main factors should be considered: the validation of the electrical equivalent circuit, which should represent the steel-concrete interface properly and the requirement that each circuit

parameter has a corresponding physical meaning (Gu & Beaudoin 1998). The equivalent circuit data fitting is common practice in AC impedance spectra interpretation. The usefulness of such an approach depends on whether the assigned parameters have the appropriate physical meaning for the actual system studied. Many different equivalent circuits can be similar mathematically; however, only the one that possesses terms having reasonable physical meaning can provide reliable data for sensible interpretation. Therefore there is a challenge to find a suitable and reliable equivalent circuit model in data interpretation. Also other disadvantages of impedance spectroscopy (IS) are primarily associated with possible uncertainties in interpretation. An important complication of analyses based on an equivalent circuit is that ordinary ideal circuit elements represent ideal lumped-constant properties. Inevitably, all electrolytic cells are distributed in space, and their microscopic properties may be also independently distributed. Under these conditions, ideal circuit elements may be inadequate to describe the electrical response (Barsoukov & Macdonald 2005).

RESULTS AND DISCUSSION

Impedance spectra recorded over a wide range of frequencies (from MHz to Hz). The expression for impedance is composed of a real and an imaginary part. A typical way to illustrate impedance spectrum for a system is that plotting in the real versus imaginary plane in a complex system. If the real part (Z) is plotted on the X-axis and the imaginary part (Z) is plotted on the Y-axis of a chart, we get a Nyquist Plot. Another popular presentation method is the Bode Plot. In this way, the impedance is plotted with log frequency on the X-axis and both the absolute values of the impedance and the phaseshift on the Y-axis. Unlike the Nyquist Plot, the Bode Plot does show frequency information. In this regard, following the results of impedance data on carbon fiber is presented in Nyquist plot for different amount of chloride content (Figs 1-3a,b). The plots scale is in a way to show all different polarization curves in a one figure; thus the low polarized curves are cut to fit in the figures. The plots are divided in two parts due to different amount of resistance which leads to have different scaled system. In addition, showing the effect of existence of chloride ions on characteristics of carbon fiber, the

obtained data on different chloride contents are illustrated after 750 mV, 1000 mV and 1500 mV polarization (Figs 4a-c). The reason to choose these polarization values is that in these values the corrosion mechanism is changed. As it is illustrated in figures 1-3a, up to 500 mV polarization carbon distributes the current properly and the system is diffusion control. It means that the system is control by diffusion on oxide layer on carbon and therefore the carbon stable at this points and this behavior is the same in different chloride contents. And after that the shape of plot starts to be like a semicircle (Randle equivalent circuit). In this point which is the same for different chloride contents carbon starts to be corroded. This is also observed in previous experiments by the authors (Chini 2008). Above 1 volt polarization, the Warburg part which is look like a line after semicircle part appears in low frequencies. It is good to remind that Warburg line indicates mass transfer control systems. In other words, the shape of plot is due to a combination of kinetic and diffusion processes. Unfortunately above 2000 mV polarization, the results were so disturbed that even positive readings came for imaginary part which is meaningless. This phenomenon could be due to that the system and carbon was not stable anymore or some other oxidation products covered the working electrode. This behavior is more apparent in higher amount of chloride in the system. But in 3% chloride content, in 2500 mV and 3500 mV (figure 3b), one could observe that the system is two or even more time constant. One reason -in authors opinion- could be due to formation of more stable oxidation products on carbon fibers which leaded to have multi materials system. This was also observed in previous tests (Chini 2008). In addition, in those cases which charge transfer or combination of kinetic and diffusion were observed, the center of semicircles were displaced below the real axis. This tilting of center could be because of overlapping of different circles or the dielectric relaxation time of basic material. Displacement of center of a semicircle to the below of real axis is because of the presence of distributed elements in the system. In this case, the angle of depression of semicircle arc below the real axis is related to the width of relaxation time distribution. As mentioned before, although carbon follows the same concept behavior in different amount of chloride, existence of chloride ions has an important role in kinetic of the reactions. It is clearer on figures 4a-c. As it gets from figures, addition of chloride increases the rate of oxidation (lower polarization

resistance or smaller circle-diameter); however the amount of chloride does not affect very on the results. So adding chloride into solution does not affect carbon behavior but increase the kinetic of reactions.

CONCLUSION

The aim of this research is to clarify some of electrochemical behavior of carbon fiber in anodic polarization. In this regard, several test setups has been done by authors. In this paper oxidation of carbon is monitored by means of EIS measurements. Results indicate that carbon has not affected a lot by anodic polarization up to 750 mV and it shows a diffusion control behavior. In contrary, above 750 mV, corrosion of carbon starts and more than 1500 mV polarization one could observe mass transfer control (Warburg line) in its corrosion mechanism. More than 2 volt the system seems to change and formation of new products disturb the monitoring, as well as reach to a stable system is difficult. This behavior is more apparent in higher polarization potentials. In addition, the centers of semicircles were displaced below the real axis. This tilting of center could be because of overlapping of different circles or the dielectric relaxation time of basic material. Existence of chloride ions in the electrolyte affect the kinetic of oxidation and increase the corrosion rate or decrease the polarization (corrosion) resistance of the system. But it was observed that the amount of chloride did not play an important role in this regard. Also disturbing of data started in lower potentials in 1% chloride compared with 3%; and in the Nyquist plot for 3% chloride content shows multi time constant system. Authors think that it could be due to formation of more stable oxidation products and accumulation of them on the surface of working electrode. Reaching a better explanation needs more tests on by-products of oxidation of carbon in alkaline solution.

ACKNOWLEDGMENT

A part of this work is financed by the Norwegian Research Council through the strategic research program RECON at Norut Teknologi in Narvik, Norway. Additionally the support from maxit Group AS is highly appreciated both by sharing their scientific and practical experience and financing part of this work.

Figure 1a. Nyquist plot in 0% chloride content solution after different polarization values (0 to 1000 mV)

Figure 1b. Nyquist plot in 0% chloride content solution after different polarization values (1500 to 2500 mV)

Figure 2a. Nyquist plot in 1% chloride content solution after different polarization values (0 to 750 mV)

Figure 2b. Nyquist plot in 0% chloride content solution after different polarization values (1000 to 1500 mV)

Figure 3a. Nyquist plot in 3% chloride content solution after different polarization values (0 to 750 mV)

Figure 3b. Nyquist plot in 3% chloride content solution after different polarization values (1000 to 2500 mV)

Figure 4a. Nyquist plot in different chloride contents solution after 750 mV polarization

Figure 4b. Nyquist plot in different chloride contents solution after 1000 mV polarization

Figure 4c. Nyquist plot in different chloride contents solution after 1500 mV polarization

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