This project was carried out to develop a better understanding of "Electrochemical Chloride Removal (also known as Desalination), a relatively new technique for rehabilitating reinforced concrete structures suffering from chloride induced corrosion. The factors influencing chloride removal were investigated and a mathematical model for predicting the spatial distribution of chloride in the concrete at the end of the treatment was developed. To investigate the factors influencing chloride removal, concrete prisms containing varying levels of admixed sodium chloride and number of steel bars were tested. The amount of chloride removed during the treatment was assessed by analysing the anolyte. It was found that chloride removal increased with increasing applied potential, number of reinforcing bars at a particular depth, water/cement ratio, chloride contamination depth and initial chloride content. Chloride removal was unaffected by concrete strength but decreased with increasing percentage of cement replacement material. A greater percentage of chloride was removed from prisms where the thickness of the chloride bearing layer of concrete was less than the depth of cover to the reinforcement. Where the thickness of the chloride bearing layer exceeded the cover to the reinforcement, the use of an external cathode significantly increased the total amount of chloride removed. Chloride removal from a face remote from the source of the chloride contamination (soffit desalination) was shown to be feasible. In prisms containing 2, 3 and 4% Cl (by weight of cement), it was found that the amount of chloride remaining in the prisms reached a limiting value irrespective of the initial admixed chloride content. This value was believed to be approximately equal to the amount of bound chloride in the concrete. Analysis of ground samples of concrete showed, however, that in a few cases bound chloride was removed locally to the reinforcing bars. Even though significant amounts of chloride remained in the concrete after completion of the treatment, the reinforcement remained passive for periods exceeding 30 months. Towards the second aim of predicting the spatial chloride distribution in the concrete, a mathematical model for electrochemical chloride removal from concrete based on the Nernst-Planck and Laplace equations was developed. The model relies on experimentally derived chloride transport number profiles. The predicted quantities of chloride removed into the anolyte and chloride remaining in concrete correlate well with data obtained by testing prisms containing one bar and dosed with 2, 3 and 4% Cl. The model shows that all parts of the concrete prisms undergo chloride removal albeit at different rates. Concrete directly between the anode and cathode undergoes the highest rate of chloride removal while concrete below the cathode, the lowest. It would appear, therefore, that there are no 'dark spots' in the concrete where chloride removal is prevented.

Since mid-80‟s cathodic protection (CP) has been recognised as the „‟only technique known to stop corrosion regardless of the levels of chloride contamination in concrete‟‟ (FHWA, 1982) and is proved to be the most cost effective means to extend the useful life of the structure. Cathodic protection is an electrochemical technique to stop/mitigate corrosion by supplying „current‟ from an external source in order to suppress the „internally generated‟ current flow due to corrosion processes. The „external‟ current source could be obtained simply by coupling the steel to another electrochemically more active metal, e.g. zinc; alternatively the „external‟ current may be derived from a mains operated low voltage DC power source, viz. transformer/rectifier unit. These two different approaches to supply „external‟ current to stop corrosion are generically termed as: „Sacrificial Anode Cathodic Protection (SACP)‟ system and „Impressed Current Cathodic Protection (ICCP)‟ system, respectively. Both approaches have proved to be feasible, but the impressed current CP system offers greater flexibility with regard to its ability to provide the necessary current in situations where concrete resistivity is relatively high and variable. The sacrificial anode system is most effective if the concrete resistivity is very low or the anode is placed in a very low resistivity environment such as soil with low resistivity, as the inherent driving voltage is low e.g. the potential difference between zinc and corroding steel in concrete is limited to approximately 0.7 volts. Other contra-distinction between the two approaches are that the design life of the sacrificial anode systems are usually range between 10 -15 years; on the other hand the design life of the ICCP systems could be well in excess of 60+ years ( depending on the type of anode system). Page 2 Following the successful application of first CP system, based on impressed current CP (ICCP), on a bridge deck in California, USA 1973, the technology has advanced significantly, particularly the anode systems (which is the main arbiter of a CP system) to deliver the protection current efficiently providing adequate protection (i.e. meeting the criteria recommended in BS EN ISO 12696: 2012 and other International Standards). Most of the CP installations worldwide are operating in ICCP mode. However, due to the escalating cost of anode systems and associated external power supply as well as monitoring/control units for ICCP installation has led researchers to actively pursue different means of developing low cost anode systems. Researchers have mainly focused on sacrificial anode CP (SACP) systems, as SACP does not require an external power supply and control units, but the drawback to this anode system is that it has a shorter life span (usually 10 -15 years compared to 60+ years for ICCP anodes). This work describes the development of an ICCP anode system design utilising commercially available zinc rich paint (ZRP) as a primary anode material offering an innovative but considerably low cost alternative to currently used materials for ICCP anode systems. It also describes the development of a simple and low cost „multifunctional‟ probe for monitoring the performance of the installed CP system, among other functions, such as LPR measurements, macrocell corrosion current measurement, E-log I tests for assessing the current requirements for CP design. For these functions both laboratory investigations and field trial on real life structure were employed.

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Chloride ion migration was studied under accelerated cathodic protection conditions using 6" x 6" x 6" mortar blocks of varying initial chloride content and water to cement ratios. An iron mesh embedded parallel to one face in the blocks acted as the cathode and zinc was thermally sprayed on the opposite face to form an anode. First, the potential response of two blocks was studied at a current density of 3 mA/ft��. One block was outfitted with a heat sink and moisture barrier while the other block was periodically wetted. Second, eight blocks were polarized at various current densities for a period of one year. In both sets of experiments, the blocks were maintained in controlled humidity and temperature. The potential across the blocks was recorded at periodic intervals and mortar samples were drilled to measure the chloride content as a function of aging. Based on observations of the first study a theoretical model was constructed which indicates that zinc based electrochemical products form at the zinc-concrete interface. The effect of the electrochemical product on raising the resistance across a cathodic protection set-up may be of consequence and should be further studied. Blocks polarized at 6 mA/ft�� exhibited similar behavior as the blocks polarized at 3 mA/ft��, but the response was twice as fast. This result indicates that studying cathodic protection under accelerated conditions is valid. The chloride content of samples obtained from one set of blocks over the course of the experiment was normalized against the initial chloride profile. The normalized profiles were calculated as a function of aging and they supported the hypothesis that chloride ions would move away from the rebar and towards the sprayed zinc anode under cathodic protection. / Graduation date: 2001

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As an important technique for corrosion control in marine environment, Cathodic Protection (CP) should be applied with a full understanding of environmental conditions and a good consideration of current requirements. Early studies on different kinds of steel specimens in the intertidal zone show severe corrosion losses. Nevertheless, there is evidence that CP can work in these regions of a steel structure because electrolyte pathway can remain some time on thin wetted surfaces when tides recede. This research aims to study corrosion activities and their behaviour under the influence of CP in a thin layer of electrolyte as a simulation of the inter-tidal zone. By means of a mechanical vibrating probe, Scanning Vibrating Electrode Technique (SVET) may be used to study local activities at coating defects in a thin electrolyte layer. The effect of CP on the local currents at the defect site was confirmed by SVET and, significantly, the development of calcareous films under these conditions in seawater was also observed. Such films are found to be effective in the absence of cathodic polarisation and only failed after damage. In order to explore the performance of applying CP, a Finite Element (FE) model of electrically connected zinc and steel samples beneath a specific thickness of electrolyte has been created, with full polarisation curves implemented for each metal based on experimental results obtained. The influence of the electrolyte conductivity and the geometry of the electrodes has also been considered. A comparison can then be made between experimental investigation and computational modelling of this corrosion cell. Epoxy-coated and uncoated mild steel samples obtained in the simulated tidal facility were also investigated. The formation of calcareous films was confirmed. Calcareous films were protective under these intermittent wetting conditions. Techniques used to understand the performance include optical observation, Scanning Electron Microscopy (SEM) together with Energy Dispersive X-ray (EDX) and X-ray Diffraction (XRD) analysis.

A numerical model for the cathodic protection of steel in reinforced concrete is developed. Parameters are set to represent a three-dimensional section of a bridge beam exposed to the atmosphere and coated with a thermally sprayed zinc anode. Both diffusion of oxygen and conduction of charge within the concrete are considered explicitly through a two-dimensional finite element model. The diffusivity and conductivity are represented as functions of concrete moisture content. Electrochemical reactions considered at the rebar-concrete interface are reduction of oxygen, oxidation of iron, and evolution of hydrogen in a constant-potential cathodic protection circuit. Reaction-kinetic parameters for actively corroding steel (not passivated steel) are used. Reactions at the zinc-concrete interface are not considered explicitly. The effectiveness of protection is found to vary significantly with both concrete moisture content and position on the rebar. For spatially uniform pore saturation, the drier the concrete is, the greater the corrosion current and the greater the non-uniformity. Protection is significantly more effective at the "front" of the rebar (closest to the zinc anode) than at the "back" (closest to the center of the beam). Corrosion current is greater under drying conditions than under wetting conditions. The numerical model is applied towards interpretation of the "100-mV polarization decay criterion" that is often used to assess the effectiveness of cathodic protection. It is found that the polarization decay predicted from relaxation of oxygen concentration gradients was comparable in magnitude to that observed experimentally, but depends on location on the rebar. A numerical model for the transport of ions in porous concrete under cathodic protection is presented. In this initial model, transport of the ions zinc, calcium, chloride and hydroxide is described by a one-dimensional Nernst-Planck equation at constant current density with generation of zinc ions at the anodic interface, generation of hydroxide ions at the cathodic interface, and no chemical reactions in the bulk of the concrete. The equations are solved numerically by two methods: the point method, in which concentrations and electric potentials are solved for directly through finite-difference approximations of the differential equations and the box method, in which the domain is divided into discrete volume elements with flux balances for each chemical component and for charge. A base grid of 41 nodes is used. Results for the system after 96 and 9600 days of cathodic protection are discussed. Both numerical methods yielded concentration profiles that are virtually indistinguishable. Numerical noise in the box method leads to values in the first and second derivatives of the electric potential that tend to oscillate around the central values represented by the same smooth curve of the point method. In contrast, the point method shows greater apparent numerical deviation from electroneutrality which is largest near the boundaries and decays towards the center in damped oscillations. The deviations decrease with smaller size of grid elements and higher order difference approximations. The magnitude of the charge density in the bulk of the concrete calculated from the second derivative of the electric potential through Poisson's equation is shown to be negligible compared to the overall electroneutrality calculated from the concentrations of ions. At 96 days, the relative contributions of migration and diffusion to the overall flux are shown to vary widely with position and species; migration can neither be neglected nor can a "corrected" Fick's law approach be used. Zinc ions are found to have moved approximately 15 mm into the bulk of the concrete at 96 days. / Graduation date: 2006

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Metallic additives, also known as anticorrosive pigments, can provide sacrificial cathodic protection and complement the barrier protection afforded by heterogeneous organic coatings to metallic substrates. The unique systematic study of the corrosion resistance of an epoxy coating reinforced with different sizes (80nm, 500nm, 10um) and continuous multiple pigment volume concentration (0, 2%, 10%, 20%, 45%) below global critical pigment volume concentration of zinc particles were studied. The thesis is developing the fundamental understanding to optimize corrosion protection and predicting the protection with time. The properties of these cathodic coatings were investigated by a single-frequency electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) measurements that can be used as to understand cathodic protective state. Finite Element Analysis (FEA) has been applied here for modeling and simulating part of actual experiments. This thesis will help understanding the sensitivity and efficiency to various size and loading of metallic additives for corrosion protection.