At Forsmark, several cases of suspected galvanic corrosion have been detected and believed to be caused by an inappropriate use of graphite gaskets in brackish water. This report studies the likelihood of galvanic corrosion between the graphite gasket and stainless steels and aims to be a reference when investigating galvanic corrosion in the future. To evaluate galvanic corrosion, several electrochemical experiments were studied, such as galvanic series, polarization curves, and galvanic current measurements with a ZRA. The electrochemical results showed that when immersing the stainless steel (254 SMO) and the graphite gasket (Novatec) into brackish water, there was a current flowing between the electrodes. However, the current was very small, which could be explained by the protection from a passive film on the stainless steel. The difference in corrosion potential between the two materials was measured and compared to results from polarization curves. It appeared that 254 SMO would be protected by a passive film at the measured potential. Galvanic current measurements also indicated the presence of a passive film under the investigated conditions. The results indicate that galvanic corrosion itself should not have caused the corrosion attacks at Forsmark. The found corrosion is more likely due to crevice corrosion that was accelerated by the combination of a crevice, a welded flange surface, chlorides in water and possibly a graphite gasket.

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As stagnant water contacts copper pipe and lead solder (simulated soldered joints), a corrosion cell is formed between the metals in solder (Pb, Sn) and copper. If the resulting galvanic current exceeds about 2 µA/cm², a highly corrosive microenvironment can form at the solder surface, with pH <2.5 and chloride concentrations 11 times higher than bulk water levels. Waters with relatively high chloride tend to sustain high galvanic currents, preventing passivation of the solder surface and contributing to lead contamination of potable water. If the concentration of sulfate increased relative to chloride, galvanic currents and associated lead contamination could be greatly reduced, and solder surfaces were readily passivated. Mechanistically, at the relatively high concentrations of lead and low pH values that might be present at lead surfaces, sulfate forms precipitates while chloride forms soluble complexes with lead. Considering net transport of anions in water, a chloride-to-sulfate mass ratio (CSMR) above 0.77 results in more chloride than sulfate transported to the lead anode surface, whereas the converse occurs below this CSMR. Bicarbonate can compete with chloride transport and buffer the pH, providing benefits to lead corrosion. Although orthophosphate is often an effective corrosion inhibitor, tests revealed cases in which orthophosphate increased lead and tin release from simulated soldered joints in potable water. Phosphate tended to increase the current between lead-tin and copper when the water contained less than 10 mg/L SO₄²⁻ or the percentage of the anodic current carried by SO₄²- ions was less than 30%. Additionally, nitrate in the potable water range of 0-10 mg/L N dramatically increased lead leaching from simulated soldered pipe joints. Chloramine decay and the associated conversion of ammonia to nitrate during nitrification could create much higher lead contamination of potable water from solder in some cases. In practical bench-scale studies with water utilities, the CSMR was affected by the coagulant chemical, blending of desalinated seawater, anion exchange, and sodium chloride brine leaks from on-site hypochlorite generators. Consistent with prior experiences, increasing the CSMR in the range of 0.1 to 1.0 produced dramatic increases in lead leaching from lead-tin solder connected to copper. / Ph. D.

Analysis of corrosion in marine and acid environments is a complicated task, involving the interaction of thermodynamic, kinetic and geometrical factors. Two mathematical models which predict corrosion behaviour have been implemented for personal computers. The first program uses an assumption of unidirectional current flow to simplify the prediction of potential distributions for systems of essentially cylindrical geometry containing natural seawater-based electrolytes of differing strength. Using experimentally determined electrochemical and flow rig data, experimental and theoretical results were compared. The correlation between the two was shown to be poor, and this is attributed to the unrepresentative nature of the electrochemical data input to the model. The second model involves the synthesis of polarization curves. Several algorithms to model passivating behaviour have been studied, and one was selected and incorporated into the calculation routine. A number of kinetic and thermodynamic parameters are used in algorithms describing such behaviour, along with activation, concentration and solution polarization effects, for a number of redox reactions, which are then combined to produce an overall potential-log current density curve. Experimentally determined data for pure iron and different stainless steels in marine and acid environments of differing dissolved oxygen content and temperature were obtained. Theoretical models were constructed for each system, and compared to experimental data. Excellent correlation between experimental and theoretical data was obtained for potential ranges in excess of 2 V. Trends in parameter values were discussed, and compared to published data. The transition between stable and unstable passivity of stainless steels was shown to be dependent on the oxygen reduction diffusion limited current density and the iron dissolution reaction free corrosion current density, which in turn was linked to the dissolved oxygen content and temperature of the electrolyte. A new model for the behaviour of stainless steels in the transpassive region was proposed.

Scanning electrochemical microscopy is a method that incorporates an ultramicroelectrode capable of facilitating electrochemical reactions paired with an XYZ positioning system capable of micron-level movements. This study investigates the corrosion behavior of structural transition joint clad material that contains steel, pure aluminum, and an aluminum alloy blast welded into a single joint. This study will characterize the corrosion response of the structural transition joint and identify the galvanic activity measured between its layers. High-temperature coatings in this study are designed to be used effectively up to 1400?F. In this study, we characterized several commercial high-temperature coatings exposed to different levels of heat. General trends of decreasing barrier performance were observed with the exception when these coatings are exposed to their rated temperature limit of 1400?F, at which the barrier increased slightly, indicated by their low-frequency impedance modulus. The cause is a combination of sintering and oxide formation.

Chloride levels are increasing in some water supplies around the country due to use of road salts and seawater intrusion, which can increase the chloride-to-sulfate mass ratio (CSMR) and trigger serious water lead contamination from galvanic lead solder: copper pipe corrosion. Previous attempts to control this problem through simple water chemistry modifications were unsuccessful, but in this work a combination of zinc orthophosphate and moderate alkalinity mitigated lead release in testing at two utilities. Either zinc alone or phosphate alone were irrelatively ineffective, but the combination of zinc orthophosphate reduced lead leaching by 54-99% (compared to the control without inhibitors) if alkalinity was above about 55 mg/L as CaCO3. These results may help mitigate future lead in water contamination events. / MS

Lead corrosion in premise plumbing systems from materials, such as lead pipes, soldered joints, and brass, can cause elevated lead in drinking water. This work examined mechanisms by which galvanic corrosion of lead solder:copper joints is accelerated by high chloride, low sulfate, and high nitrate in the water. Galvanic corrosion studies conducted using simulated copper plumbing joints showed lowered pH and concentrated anions at the lead solder surface. A combination of low pH and high chloride can prevent passivation of the solder surface, indefinitely sustaining high corrosion rates and lead contamination of potable water supplies. The mass of lead leached to water correlated with predictions based on Faraday's law, although a portion of the oxidized lead remained attached to solder in a scale layer. When the level of sulfate in water increased relative to chloride, galvanic currents and associated lead contamination could be greatly reduced. The impact of chloride-to-sulfate mass ratio (CSMR) on lead leaching from 50:50 lead:tin solder galvanically coupled to copper was examined at the bench scale.The CSMR can be affected by coagulant changeover, use of desalinated water, anion exchange, brine leaks, and other treatment changes. Consistent with prior experiences, increasing the CSMR in the range of 0.1 to 1.0 produced dramatic increases in lead leaching from this source. Above this range, while lead leaching was generally very high, there was little correlation between lead release and CSMR. The impact of nitrate was tested at the bench scale using synthesized water. Results consistently showed that increasing nitrate in the range of 0 to 10 mg/L NO??N, could dramatically increase lead leaching from simulated soldered pipe joints. Although higher nitrate slightly increased the galvanic current, the main factor affecting lead release appears to be initiation of non-uniform corrosion, with small pieces of solder detaching into the water. Under some circumstances, the decay of chloramine after it leaves the treatment plant, and formation of nitrate via nitrification, can markedly increase corrosivity of distributed water to lead solder. The bench scale experiments conducted in this work illuminated many issues related to accelerated lead corrosion of solder. However, future research is necessary to further elucidate the mechanisms behind nitrate-accelerated corrosion, as well as methods for inhibition of corrosion due to chloride and nitrate. / Master of Science

The EPA Lead and Copper Rule set action limits for lead and copper concentrations in drinking water, but accelerated corrosion of lead in distribution systems due to a galvanic connection to copper. Prior research has demonstrated that the effects of galvanic corrosion can be controlled by water chemistry. This study not only investigated the main effects of alkalinity, natural organic matter (NOM), nitrate, disinfectant and inhibitor to galvanic corrosion, but also the interplay between these factors. A 2-level factorial (2v5-1) design was adopted which resulted in 16 testing conditions. Results of bench-scale experiments using static pipes with lead and copper segments demonstrated that alkalinity, disinfectant, inhibitor and alkalinity-inhibitor interaction had a significant impact on galvanic current. The significant factors affecting total lead release were alkalinity, NOM, disinfectant, alkalinity-inhibitor interaction, NOM-nitrate interaction, NOM-disinfectant interaction, NOM-inhibitor interaction, nitrate-disinfectant interaction and disinfectant-inhibitor interaction.

The EPA Lead and Copper Rule set action limits for lead and copper concentrations in drinking water, but accelerated corrosion of lead in distribution systems due to a galvanic connection to copper. Prior research has demonstrated that the effects of galvanic corrosion can be controlled by water chemistry. This study not only investigated the main effects of alkalinity, natural organic matter (NOM), nitrate, disinfectant and inhibitor to galvanic corrosion, but also the interplay between these factors. A 2-level factorial (2v5-1) design was adopted which resulted in 16 testing conditions. Results of bench-scale experiments using static pipes with lead and copper segments demonstrated that alkalinity, disinfectant, inhibitor and alkalinity-inhibitor interaction had a significant impact on galvanic current. The significant factors affecting total lead release were alkalinity, NOM, disinfectant, alkalinity-inhibitor interaction, NOM-nitrate interaction, NOM-disinfectant interaction, NOM-inhibitor interaction, nitrate-disinfectant interaction and disinfectant-inhibitor interaction.

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