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<P> A study has been made of the transformation of deoxidation products in the Fe-V-0 system in the temperature range 1545 -1640°C, using galvanic cells with solid electrolytes. The cells used were in the form of Zr02 (caO) immersion probes and Th02(Y2o2) crucible assemblies. The fields of study of Fev2o4(spinel) and v2o3 were established with respect to oxygen activity and temperature. </p> / Thesis / Master of Engineering (MEngr)

This study focused on the kinetic data measurements, such as diffusion coefficient D and exchange current density i_0 of the electrochemical reactions of corrosion products (Fe, Cr and Ni ions) and corrosive species (OH-), and corrosion studies of structural materials (SS 316H and Alloy 617), including static corrosion and galvanic corrosion, in molten MgCl2-NaCl-KCl and/or NaF-KF-UF4-UF3 salts in a temperature range of 600 to 800C. The study applied the semi-differential (SD) analysis method and innovative fitting method for the kinetic property data measurements in the multicomponent system of NaF-KF-UF4-UF3 salts. In molten MgCl2-NaCl-KCl salts, the measured D_(OH^- ) has the largest value followed by D_(〖Cr〗^(2+) ), D_(〖Fe〗^(2+) ), D_(〖Cr〗^(3+) ) and D_(〖Ni〗^(2+) ) at the studied temperatures, and none of the diffusion coefficients depends on the ion concentration in the studied concentration range and all of them followed the Arrhenius law. At the same temperature, the measured D_(Fe^(2+) ) and D_(〖Cr〗^(2+) ) values in molten NaF-KF-UF4-UF3 salts were slightly smaller than those obtained in molten MgCl2-NaCl-KCl salts. The non-linear curve fitting technique was applied to determine the exchange current density i_0, charge transfer coefficient α, limiting current density i_L and standard rate constant k^0 values. i_0 and k^0 followed the Arrhenius law. The obtained fundamental data can be applied to corrosion models which make the corrosion rate prediction possible in a static system from the experimental kinetic data. Corrosion studies of SS 316H and Alloy 617 in thermal purified molten NaF-KF-UF4-UF3 salts were performed for 120 hours. Based on the post-test analysis, the major metal species corrosion products were Cr, Fe and Mn in SS 316H tests, and Cr, Co, Ni in Alloy 617 tests. The measured UF4/UF3 ratio increased after corrosion tests because some of the U3+ was oxidized to U4+ by corrosive impurities and corrosion products during tests. Cr depletion and salt penetration were observed at grain boundaries (GBs) for both SS 316H and Alloy 617. For Alloy 617 specimens, the corroded area could be divided into two parts: the first part (near the surface) where Cr was completely depleted, and the second part (underneath the first part) where Cr was partially depleted. For SS 316H specimens, the average attack depth was larger than that of Alloy 617. Mo segregation was observed in the matrix of SS 316H specimens but was found to be enriched at GBs in the second part of Alloy 617 specimens. The corrosion study of Alloy 617 with time was also conducted for 72 hours and 32 hours, respectively. A thin layer composed of Fe, Co, Ni and Mo was found on the surface of the specimen, which was different from the previous 120-hour tests. In the salt, the concentration of Cr kept increasing with time, while for the other identified corroded elements, i.e., Fe, Co, Ni and Mo, their concentrations increased first, then decreased until becoming zero or stable. In the galvanic corrosion study of Alloy 617/graphite in molten NaF-KF-UF4-UF3 salts, the galvanic corrosion rate of Alloy 617 at 750C was about four times of that at 650C in the 2-hour tests, which indicated that temperature has a significant effect on the galvanic effect. In the 120-hour galvanic corrosion test, the galvanic corrosion rate became slightly larger with time in the studied system. Similar to the previous 120-hour Alloy 617 corrosion test, the corroded area of the post-test specimen was divided into two parts. The measured attack depth in both parts were much smaller compared with that in the 120-hour Alloy 617 test. This was because of the lower corrosive impurity concentrations in the salt used in the test. The salt in the galvanic corrosion test has been used in the previous corrosion test, during which the corrosive impurities were consumed, which made the salt less corrosive. Finally, it is necessary to point out that all the salts used in the present work were only thermally purified, which is effective in the removal of moisture but not in the removal of oxide impurities. Therefore, further studies are needed to understand the oxides' impacts on the corrosion behavior, especially on the salt penetration. / Doctor of Philosophy / Molten salt is a promising candidate that can be used as fuel and coolant in the molten salt reactors (MSRs). Besides, it can also be used as thermal energy storage, heat transfer fluid in the concentrated solar power plants, because it has high heat capacity, low vapor pressure, and high thermal conductivity. However, materials corrosion is a key concern of molten salt applications, and it is known that the corrosion by molten salts is mainly impurity driven. The impurities, such as moisture in the salts, can make the salt more oxidized, thus becoming more corrosive to corrode the structural materials. The present work focus on the kinetic property of metal specie corrosion products and non-metal impurity in the molten fluoride and chloride salts, which were directly related to the mass transfer and charge transfer process during the corrosion. Especially in the measurements of fluoride salts, innovative methods were applied which were confirmed to perform well in the multicomponent system (Fe and Cr ions coexisted). The static corrosion tests of SS 316H and Alloy 617 were conducted in molten fluoride salt at high temperatures. The main purpose was to study their corrosion behavior and understand the corrosion mechanisms. The corrosion rate of SS 316H was also estimated, which could be a crucial criterion in the material selection. In addition, the corrosion of Alloy 617 with time was also investigated. The metal specie corrosion product concentration change trends were obtained, and the corrosion behavior over the different corrosion stages was analyzed. Different corrosion phenomenon was observed in different corrosion test. Thus, they shed lights on the study of how the corrosion was developed during the corrosion process. Moreover, galvanic corrosion was another major corrosion type when two or more dissimilar materials were electrically contacted. The galvanic corrosion of Alloy 617/graphite was studied in the molten fluoride salts. The galvanic corrosion rate increased with the rise of temperature, which verified that temperature was a key factor that affected the galvanic corrosion. And the galvanic effect was also turned out to increase with time in the present study.

The EPA Lead and Copper Rule set Action Limits for lead and copper concentrations in potable water, but accelerated corrosion of lead in potable water systems due to a galvanic connection to copper remains a significant health risk to consumers. In addition to elevated lead release due to galvanic corrosion of lead-tin solder and leaded brass fixtures, partial lead service line replacements with copper pipe present long-term health concerns. Prior research has demonstrated that the effects of galvanic corrosion can be controlled by water chemistry, and the interplay between alkalinity, natural organic matter (NOM), and orthophosphate (added as corrosion inhibitor) may have a significant influence on corrosion of common lead plumbing materials. Results of bench-scale experiments demonstrate that in some waters galvanic corrosion can multiply lead release from lead pipe by up to 60 times, but other waters curtail the galvanic current and alleviate the effects of galvanic corrosion. Measurements of pH at the lead surface demonstrate that a corrosive micro-environment forms during stagnation in which the local pH drops to 3.0 or lower, demonstrating that the worst-case scenario for galvanic corrosion of lead occurs during long stagnation periods. In addition to water chemistry, flow pattern also has an impact on galvanic corrosion of lead. Conventional wisdom regarding lead release indicates that continuous flow results in the greatest mass of lead release, but reports of anomalously high lead concentrations after long periods of stagnation point to the contrary. In this experiment, continuous flow of chlorinated water through a Pb-Cu galvanic couple promoted Pb(IV) formation and resulted in potential reversal that caused lead pipe to become cathodic to copper and minimized lead release to water. In contrast, intermittent flow resulted in sustained galvanic attack, and a mass balance of Pb release indicated that a greater total mass of lead was released with intermittent flow. These results have important implications for assessing lead risk at the tap, especially considering long stagnation periods at facilities such as schools and increasing efforts for water conservation. Elevated copper release in potable water can cause aesthetic problems and mild health concerns and often occurs in new plumbing systems prior to the formation of a protective scale layer on the pipe surface. While solubility in new copper pipes tends to be controlled by an amorphous solid of high solubility, over time, the natural copper aging process results in the formation of a protective scale of much lower solubility, but the transition can be inhibited in waters with high levels of NOM. Experiments demonstrated that GAC treatment to remove NOM accelerates the aging process to a protective scale that provides a long-term reduction in copper release even after GAC treatment is terminated. Therefore, compared to pH adjustment and orthophosphate addition, which must be continued perpetually, GAC treatment may be a more holistically pleasing method of copper corrosion control. This approach could be useful in the commissioning of new buildings to facilitate rapid aging and avoid potential long-term copper corrosion problems. / Master of Science

There is emerging concern about the potential for elevated lead in water after water utilities conduct EPA mandated (or voluntary) partial replacements of existing lead service lines. Connections between dissimilar metals results in the accelerated corrosion of the less noble metal via galvanic attack, increasing metal concentrations in water and posing potential public health risks. Many practical problems associated with stopping galvanic attack between copper:galvanized iron and copper:lead via use of dielectrics have also been raised. Galvanic corrosion can be effectively stopped by isolating the dissimilar metals; however, completely eliminating electrical continuity may not always be practical or allowed by code. Instead, increasing separation distance between the two metals was hypothesized to considerably reduce galvanic corrosion. Galvanic corrosion and lead leaching were evaluated for lead:copper connections with varying separation distances while maintaining electrical continuity. Increased distance between lead and copper pipe dramatically reduced the galvanic current and the magnitude of lead release. Galvanized iron and copper connections were also investigated using various commercial fittings, and results verified that a controlling factor was separation distance between the two dissimilar metals. When considering the long-term behavior of partially replaced lead service lines, detrimental effects from galvanic corrosion worsened with time. Even when water was sampled consistently at moderate flow rate, the condition representing traditional partial service line replacement was 40% worse than a full lead service line. At elevated flowrates, lead concentrations and variability increased for partly replaced lead pipe versus full lead pipe due to reservoirs of lead rust formed via galvanic corrosion. At low flowrates, these negative impacts were not observed. Finally, crevices formed by the use of commercial couplings increased lead release. Overall, the results enhance practical understanding of galvanic corrosion impacts and use of dielectrics in water service lines and premise plumbing. / Master of Science

The ban on lead plumbing materials in the Safe Drinking Water Act (1986) and the EPA Lead and Copper Rule (1991) have successfully reduced lead contamination of potable water supplies. The success of these regulations gave rise to a belief that serious lead contamination was an important past problem that had been solved, and that additional fundamental research was therefore unnecessary. This work carefully re-examined the lead contamination issue from the perspective of 1) new regulations causing a shift from chlorine to chloramine disinfectant, 2) assumptions guiding sampling strategies, 3) existing performance standards for brass, and 4) galvanically driven corrosion of lead bearing plumbing materials. The results were instrumental in uncovering and understanding a serious problem with lead contamination in Washington, D.C. A critical reading of the literature indicates that chloramines can accelerate corrosion of lead bearing materials and increase lead contamination of water. When a new sampling protocol was conceived and used in Washington homes to assess the nature of the problem, hazardous levels of lead were found to be present in some drinking water samples. Contrary to the conventional wisdom, lead was not always highest in first draw samples, but often increased with flushing. This has several important implications for monitoring and public health. For instance, well-intentioned public education materials were causing consumers to drink water containing very high levels of lead in some circumstances. Laboratory and field-testing proved that chloramines were causing serious lead corrosion problems. That testing also discovered that, unbeknownst to scientists and utilities, free chlorine itself can act as a corrosion inhibitor, reducing lead solubility and contamination of water. The net result is that changing disinfectant from free chlorine to chloramine can sometimes trigger serious lead contamination of water. While the worst problems with lead in Washington, D.C. came from the lead services, significant levels of lead were occasionally sampled from homes with solders or brass as the lead source. This prompted re-evaluation of the ANSI/NSF 61, Section 8 standard, which is relied on to protect public health from in-line brass plumbing devices that might leach excessive lead to potable water. In-depth study of the standard revealed serious flaws arising from use of a phosphate buffer in the test waters and a failure to control carbonate dissolution from the atmosphere. Due to these deficiencies, small devices made of pure lead could actually pass the performance test. The public therefore has no assurance that devices passing NSF Section 8 testing are safe and reforms to the standard are obviously needed. Other problems arise from connecting copper pipe to lead bearing plumbing in practice. The copper is cathodic and dramatically accelerates corrosion of the lead anode via a galvanic current. Corrosion and hydrolysis of released Pb²⁺ can lower pH near the surface of the lead and increase its solubility. A similar galvanic effect can arise from cupric ions present in the water via deposition corrosion mechanism. In cases where part of a lead service line is replaced by copper pipe, the galvanic corrosion effect can create a serious long-term problem with lead contamination. Such partial lead service line replacements are occurring in many US cities and the practice should be stopped. Lead contamination of potable water is not only a problem of the past but also of the present. While additional research is necessary before regulators, utilities and homeowners can anticipate and mitigate such problems with confidence, this work provides sound fundamental basis for future progress. / Master of Science

This study investigated the effects of environmental consequences and data 'collection in a behavior contracting procedure for obesity. Also, a validity study examined the GSR as a subject-independent-monitoring technique. Sixteen subjects matched on sex and percent overweight were assigned to one of three contract conditions or to a no-treatment condition. The Data Only Contract Group received consequences for data collection. The With Consequences Contract Group received consequences for data collection and behaviors relevant to weight loss. The Without Consequences Contract Group received no consequences for data collection or behaviors relevant to weight loss. The With Consequences Contract Group lost significantly more weight ( p ≤ .05) than the No Treatment Group. Specific effects were not determined. The results of the validity study suggest that the GSR may not be a valid instrument as a subject-independent-monitoring technique. Factors affecting the galvanic skin response's- effectiveness were discussed.