The application of Ag/AgCl electrodes as chloride sensors in cementitious materials

Determination of the chloride content in a reinforced concrete structure is important for evaluation of the risk of chloride-induced corrosion of reinforcement. The traditional techniques for chloride determination in concrete are laborious, time-consuming and cannot be used for continuous monitoring of the chloride content. The investigation on the use of Ag/AgCl electrodes as chloride sensors in cement-based materials dates back to 1990s. Interpretation of the sensor’s response in cementitious materials requires the knowledge of chloride sensor’s characteristics and the interaction between the sensor and the surrounding medium. Hence, the stability of the chloride sensor’s response in cementitious materials depends on the properties of Ag/AgCl interface, AgCl/cement paste interface and the pore solution composition of cementitious materials. The influence of these factors on the stability of the sensor’s response was studied in this thesis. In Chapter 1 the background and motivation for the thesis were presented. In Chapter 2 the advantages and drawbacks of available test methods for determination of the chloride content in cementitious materials were explained.Materials and Environmen

Polarization Behaviour of Silver in Model Solutions

When studying chloride-induced corrosion in reinforced concrete structures, essential information of interest is the concentration of chloride ions in the system. The absence of a reliable method for monitoring the free chloride ions justifies the attempts towards establishing a feasible practice in the application of the already known Ag/AgCl electrode, as a chloride sensor. To identify the governing mechanism and cognition of causes for instability of the chloride sensors in highly alkaline medium (as concrete), it is necessary to study the polarization behaviour of silver in different aqueous solutions resembling the concrete environment. Following expectations and well-known fundamental background, the results from this work confirm that in the presence of chloride ions, silver chloride is the predominant reaction product, forming on the silver surface. Whereas, in the absence of chloride ions and/or presence of interfering ions, such as hydroxide ions, the oxidation process of AgCl formation is significantly dependent on the chloride concentration in the medium. Therefore, the formation of a stable AgCl layer on a Ag substrate (as would be required for sensors application for example) is a function of the presence and amount of interfering ions, together with the chloride concentration in the medium.Materials and Environmen

Potentiometric response of chloride sensors in cementitious materials of varying chemical composition and water-to-cement ratio

Free chloride ions are the main cause of steel corrosion in reinforced concrete structures. Ag/AgCl electrodes, as chloride sensors, are predominantly sensitive to chloride ions and respond electrochemically to the chloride ion activity in the environment. This is reflected by changes of the open circuit potential (OCP) of the sensors. To investigate the effect of the cement-based matrix on OCP readings, this paper presents the electrochemical responses of chloride sensors, embedded in cement paste specimens of hydrated pure cement phases of different water-to-binder ratios. The specimens were immersed in alkaline solutions with various chloride concentrations. The results show dependency of the OCP of the sensor on the surrounding hydrated cement-based matrix. This effect was more pronounced when the specimens were immersed in solutions of lower chloride concentration. In contrast, these effects were negligible at high (> 500 mM) chloride concentrationsMaterials and Environmen

Potentiometric response of Ag/AgCl sensor in Portland and slag cement pastes

Determination of the free chloride content in a concrete structure is important for evaluation of the risk of corrosion of reinforcing steel. The Ag/AgCl sensor is sensitive to chloride ions and exhibits an open circuit potential (OCP) that depends on the chloride ions activity in the environment. The interference of hydroxide and sulfide ions in the pore solution of cementitious materials with the sensor affects the stability of the sensor’s OCP. In this paper, the sensor’s OCP (i.e. sensor reading) in Portland and slag cement pastes is monitored over 300 days of immersion in solutions with different chloride concentration. The results show the applicability of the chloride sensor for continuous and non-destructive determination of the free chloride content in Portland cement paste. The significantly different OCP of the sensor in slag cement paste was attributed to the interference of sulfide ions and formation of Ag2S on the sensor’s surface. Hence, the content of free chloride ions in slag cement paste could not be determined from the sensor’s OCP. The acid-soluble chloride and water-soluble chloride in the cement pastes were also determined after 300 days of immersion of specimens in the solutions. In case of Portland cement paste, the measured acid and water-soluble chlorides were compared to the sensor reading. The acid and water-soluble chlorides were higher than sensor reading. The release of physically and chemically bound chlorides into the acid and water solvents were the main cause for this trend. The results show the importance of cement type and chloride binding ability of hydration products for the sensor’s response and the acid and water-soluble chloride contents. Materials and Environmen

Determination of chloride content in cement-based materials: Comparison of results derived by conventional methods and chloride sensor readings

In this paper the potentiometric response of a Ag/AgCl electrode as a chloride sensor in cementitious materials of different mix design was studied. The chloride sensor’s response was discussed with respect to the presence of hydration products around the sensor. The free chloride content inferred from the sensor’s response was compared to the one obtained from destructive water and acid soluble chlorides. The measured free chloride content, obtained via sensor’s reading, was lower than the obtained water and acid soluble chlorides. The results indicated the influence of the cementitious mix design on the correlation between the free chloride content obtained via sensor’s reading, water and acid soluble chlorides.Materials and Environmen

Determination of Chloride Content in Cementitious Materials: From Fundamental Aspects to Application of Ag/AgCl Chloride Sensors

This paper reports on the advantages and drawbacks of available test methods for the determination of chloride content in cementitious materials in general, and the application of Ag/AgCl chloride sensors in particular. The main factors that affect the reliability of a chloride sensor are presented. The thermodynamic behaviour of silver in the presence or absence of chloride ions is described and kinetic restrictions are addressed. The parameters that can affect the activity of chloride ions in the medium and/or the rate of ion exchange and dissolution/precipitation processes at the sensor’s surface are also considered. In this regard, the contribution of morphology and microstructure of the AgCl layer, binding of chloride ions and the compactness of hydration products around the chloride sensor are highlighted. The important parameters for a reliable sensor’s response are discussed and the possible causes of inaccuracies are evaluatedMaterials and Environmen

Microstructure, surface chemistry and electrochemical response of Ag|AgCl sensors in alkaline media

Characterization of the Ag/AgCl electrode is a necessary step toward itsapplication as a chloride sensor in a highly alkaline medium, such as concrete.The nucleation and growth of AgCl on Ag in 0.1 M HCl was verified throughcyclic voltammetry. Ag anodization was performed at current densities, determinedby potentiodynamic polarization in the same (0.1 M HCl) medium. Themorphology and microstructure of the AgCl layers were evaluated via electronmicroscopy, while surface chemistry was studied through energy-dispersivespectroscopy and X-ray photoelectron spectroscopy. At current density above2 mA/cm2, the thickness and heterogeneity of the AgCl layer increased. In thiscondition, small AgCl particles formed in the immediate vicinity of the Agsubstrate, subsequently weakening the bond strength of the Ag/AgCl interface.Silver oxide-based or carbon-based impurities were present on the surface of thesensor in amounts proportional to the thickness and heterogeneity of the AgCllayer. It is concluded that a well-defined link exists between the properties of theAgCl layer, the applied current density and the recorded overpotential duringAg anodization. The results can be used as a recommendation for preparation ofchloride sensors with stable performance in cementitious materials.Materials and Environmen

Non-destructive evaluation of chloride-induced corrosion in reinforced concrete: Electrochemical impedance spectroscopy sheds new light on generally applied sensors performance

Service life of reinforced concrete structures exposed to chloride enriched environment is well known to be mainly determined by steel passivity breakdown in the event of chloride-induced corrosion initiation and propagation. Since Cl- induced (localized) corrosion is caused by the free (water-soluble) chloride, present in the pore network of a reinforced concrete structure, quantifying the level of free chloride locally, e.g. via embedded Ag/AgCl electrodes (chloride sensors), is a generally accepted and applicable approach to monitor the time to corrosion initiation. The measurement is essentially a potential (voltage) reading over time and as such logically depends, among other factors, on the electrical and microstructural properties of the surrounding medium. Therefore, an accurate determination of the time to corrosion initiation significantly depends on the properties of relevant interfaces, such as the steel|cement paste interface and/or the Ag|AgCl|cement paste interface. In this paper, steel rods were coupled with Ag/AgCl sensors and embedded in cement paste cylinders. The specimens were immersed in simulated pore solution, containing 855 mM chloride concentration. Electrochemical impedance spectroscopy (EIS) was employed for quali-/quantification of the corrosion process on the steel surface (medium to low frequency response), while simultaneously providing information for the electrical properties of the bulk cement-based matrix through the high frequency response. The open circuit potential (OCP) values of both sensors and steel rods were recorded for more than 30 days. The results show a good agreement between sensor readings and steel electrochemical response i.e. time to corrosion initiation was recorded via steel OCP readings, whereas the relevant chloride content was estimated via the sensors’ OCP readings.Materials and Environmen

The importance of chloride sensors stability in monitoring ageing phenomena in concrete structures: Ag/AgCl electrodes performance in simulated pore-water environment

One of the reported problems associated with the performance of Ag/AgCl electrodes in alkaline environment, as concrete pore water, has been their poor stability. Open circuit potentials are typically observed to be stable for a time period of a few minutes to some days depending on the thickness and microstructure of the sparingly soluble AgCl and the subsequently developed mixed potentials at the electrode/solution interface. In this paper the open circuit potential of the chloride sensors were monitored over time in simulated pore solution with and without chloride and their electrochemical response recorded via electrochemical impedance spectroscopy (EIS). The alterations in response of the sensors can be denoted to transformation of the AgCl layer to Ag2O in chloride-free high pH environment as in concrete pore water. Recovery of the AgCl layer takes place in chloridecontaining medium, where establishing of sensor stability is determined by the chloride concentration.Structural EngineeringCivil Engineering and Geoscience

Potentiometric Response of Ag/AgCl Chloride Sensors in Model Alkaline Medium

The stability and reproducibility of an Ag/AgCl sensors’ response in an alkaline medium are important for the application of these sensors in cementitious materials. The sensors’ response, or their open circuit potential (OCP), reflects a dynamic equilibrium at the sensor/environment interface. The OCP response in an alkaline medium is affected by the presence of hydroxide ions. The interference of hydroxide ions leads to inaccuracies or a delay in the sensors’ response to a certain chloride content. In this article, the potentiometric response (or OCP evolution) of the chloride sensors is measured in model solutions, resembling the concrete pore water. The scatter of the sensors’ OCP is discussed with respect to the interference of hydroxide ions at varying chloride concentration in the medium. The deviation of the sensor’s response from its ideal performance (determined by the Nernst law) is attributed to dechlorination of the AgCl layer and the formation of Ag2O on the sensor’s surface. Results from the surface XPS analysis of the AgCl layer before and after treatment in alkaline medium confirm these observations in view of chemical transformation of AgCl to Ag2O.Materials and Environmen