Yes / To interpret nitrogen sintering of chromium and manganese steels without the formation of deleterious oxides, but with manganese and carbon modifying the local microclimate, the role of the volatile Mn and carbothermic reactions were considered. Reduction of Cr2O3 by Mn vapour is always favourable. CO is an effective reducing agent, however, whereas at atmospheric pressure it will reduce FeO at ~730°C, temperatures some 500 and 700°C higher, i.e. above those for conventional sintering, are necessary for reducing Cr2O3 and MnO, respectively. Accordingly partial pressures must be considered and the sintering process is modelled at a conglomerate of several surface oxidised alloy particles surrounding a pore with graphite present and a tortuous access to the nitrogen-rich atmosphere containing some water vapour and oxygen. The relevant partial pressures were calculated and reduction reactions become thermodynamically favourable from ~200°C. Kinetics, however, dictates availability of CO and the relevant reactions are the water-gas, C + H2O = CO + H2 from ~500°C and the Boudouard, C + CO2 = 2CO, from ~700°C. Discussion of sintering mechanisms is extended to processing in semi-closed containers, also possessing specific microclimates.

The demand for Lithium-ion batteries (LIBs) has been growing exponentially in recent years due to the proliferation of electric vehicles (EV). A large amount of lithium-ion batteries are expected to reach their end-of-life (EOL) within five to seven years. The improper disposal of EOL lithium-ion batteries generates enormous amounts of flammable and explosive hazardous waste. Therefore, cost-effectively recycling LIBs becomes urgent needs. Lithium nickel cobalt manganese oxides (NCM) are one of the most essential cathode materials for EV applications due to their long cycle life, high capacity, and low cost. In 2008, 18.9% of Lithium-ion batteries used NCM cathode material worldwide while this number increased to 31% six years later. An environment–friendly and low-cost direct recycling process for NCM has been developed in this project. The goal of this project is to recycle the EOL NCM and yield battery-grade NCM with equivalent electrochemical performance compared to virgin materials. In order to achieve this goal, four different heat treatment conditions are investigated during the direct recycling process. From the experimental results, the charge and discharge capacities of the recycled material are stable (between 151-155 mAh/g) which is similar to that of the commercial MTI NCM when sintered at 850 °C for 12 hours in the air. In addition, the cycling performance of recycled NCM is better than the commercial MTI NCM up to 100 cycles. / Master of Science / The demand for Lithium-ion batteries has been growing exponentially in recent years due to the proliferation of electric vehicles. A large amount of lithium-ion batteries are expected to reach their end-of-life within five to seven years. The improper disposal of end-of-life lithium-ion batteries generates enormous amounts of flammable and explosive hazardous waste. Therefore, cost-effectively recycling Lithium-ion batteries becomes urgent needs. Lithium nickel cobalt manganese oxides are one of the most essential cathode materials for electric vehicles applications due to their long cycle life, high capacity, and low cost. In 2008, 18.9% of Lithium-ion batteries used Lithium nickel cobalt manganese oxides cathode material worldwide while this number increased to 31% six years later. An environment–friendly and low-cost direct recycling process for Lithium nickel cobalt manganese oxides material has been developed in this project. The goal of this project is to recycle the end-of-life manganese oxides cathode material. In order to achieve this goal, four different heat treatment conditions are investigated during the direct recycling process. From the experimental results, the cycling performance of recycled NCM is better than the commercial MTI NCM.

The oxidation of soluble manganese (Mn(II)) to insoluble manganese dioxide (MnO_x(s)) is fairly well understood; however, the role of ferric hydroxide/oxides (Fe(OH)₃_(s)) in catalyzing the oxidation of Mn(II) by oxidants such as free chlorine (HOCI) is one specific aspect of manganese removal via oxidation that requires further investigation. Data collected in this study indicate that the rate of Mn(II) oxidation may be beneficially catalyzed by the presence of previously formed Fe(OH)₃_(s) particles. The mechanistic means by which this enhanced oxidation is accomplished was the focal point of this research. Specifically, the research objectives were as follows: (1) To study all possible Mn(ID) removal mechanisms for a typical groundwater system to determine the necessary experimental conditions required to isolate the study of Mn(II) oxidation in the presence of ferric hydroxides/oxides (Fe(OH)₃_(s)). (2) To investigate the means by which ferric hydroxides/oxides (Fe(OH)₃_(s)) may enhance the removal of Mn(II) during water treatment by interacting with HOCI; and (3) To develop an engineered system that captures the observed catalyzing effect iron oxides have on Mn(II) oxidation by HOCI citing key system design parameters. To complete these objectives a combination of batch and continuous flow bench-scale experiments were utilized. Batch study results indicated that the primary Mn(II) removal mechanism was a combination of adsorption and oxidation, specifically, adsorption of Mn(II) onto the iron oxide surface where Mn(II) is subsequently oxidized. A continuous flow system was developed to utilize this removal mechanism under water treatment plant conditions to improve the efficiency of iron and manganese removal. The results from experimentation with the continuous flow system indicated the following: ∙ Sufficient free chlorine residual in effluent insures consistent system performance, ∙ Initial iron oxide concentration within reactor system must have adequate adsorption capacity for initial adsorption-oxidation step to occur, ∙ Removal efficiency and reactor stability increase with the accumulation of manganese oxides, and ∙ Solution pH and reactor hydraulics affect system performance significantly. The results suggest that this technology has the potential to change the look of conventional groundwater treatment systems that practice iron and manganese removal. / Master of Science

This study was conducted to examine the kinetics of manganese sorption on oxide-coated filter media. Initial experimentation confirmed the findings of other investigators, the Mn²⁺ sorption capacity of oxide-coated media increases as solution pH increases. Further study revealed that uptake rate kinetics could be described by first order kinetics and also increased with increasing solution pH. The addition of free chlorine (HOCl) to solution greatly enhanced Mn²⁺ uptake rate kinetics. Later studies indicated that the oxide coating had very little impact on the physical properties of the media tested. Actual data from a water treatment plant filter confirmed laboratory experimental results by showing that sorption of soluble manganese does indeed occur on oxide-coated filters. The water treatment plant data also suggested that the sorption kinetics were relatively rapid, again upholding laboratory findings. Results from the manganese kinetics and sorption experiments were combined to formulate a theoretical model which would predict manganese breakthrough in a filter, given a known set of loading parameters. Preliminary use of the model indicated that oxide-coated filters could sorb significant quantities of soluble manganese before detectible levels of manganese appear in the effluent. / Master of Science

Manganese is typically found in all water supplies in the United States. Manganese concentrations are usually higher in water obtained from groundwater sources or resei:voir hypolinutlons. This is because manganese is more soluble in the reducing conditions normally found in these waters. Although manganese is not known to cause any health related problems, the secondary drinking water MCL for manganese is 0.05 mg/L. This standard was set to eliminate aesthetic problems associated with manganese bearing waters. In this study continuous-flow filters were operated in both pre-oxidative (oxidized Mn applied to filters) and auto-oxidative (soluble Mn applied) modes. The oxidants used were dllorine (HOCl/OCl⁻) , potassium permanganate (KMnO₄), chlorine dioxide (ClO₂), and ozone (O₃). Other experimental parameters included: filter media type - manganese coated or non-coated, filter loading rate --2 to 5 gpm/f², operating pH -- pH 6 to pH 9, and temperature --5 to 25℃. The most important experimental parameter was whether or not the filter media had a prior oxidized coating of manganese. If this was the case the filter produced an effluent concentration of manganese below the MCL under all pre-oxidative conditions and under auto-oxidative conditions when the pH was above neutral. Increased flow rate through the filter caused deeper penetration of manganese into the filter bed. This should not prove to cause an effluent breakthrough problem for filter depths typically used in water treatment plants. Temperature and pH effected the reaction rate of manganese oxidation in both the pre- and auto-oxidative modes. In most cases th.is did not effect the effluent quality from manganese coated filter media. However, when non-coated media was used and no oxidant was added, a decrease in pH or temperature usually adversely effected effluent quality. / M.S.

Soluble manganese (Mn) is a common water contaminant which can cause discoloration of water and staining if not treated properly in a water treatment plant. The "natural greensand effect" is one of the proven methods for efficient removal of Mn from water. Therefore, research is ongoing to develop different ways to effectively create the natural greensand effect in a post-filtration sorptive contactor for application at water treatment facilities. The research reported by Zuravnsky (2007) focused on the use of oxide-coated media in a post-filtration contactor and served as a starting point for the research reported in this thesis. As a part of the work conducted by Zuravnsky (2007), a preliminary model was formulated to predict soluble Mn removal via adsorption and oxidation onto large-size MnOx(s)-coated media. A major part of the current research was to calibrate the proposed model in predicting the soluble Mn removal performance by incorporating a statistical non-linear regression method to estimate a best-fit value for the fitting parameter kr, the rate constant associated with Mn oxidation by free chlorine. The research work included an 18-week pilot-plant study conducted at a water treatment facility in Newport News, VA. A contactor column loaded with 27â of pyrolucite media was operated at varying applied water conditions. Hydraulic loading rate (HLR), temperature, pH and influent free chlorine concentration were the operational parameters that were varied and their effect on the Mn removal performance evaluated. The resulting data were then used in the model to aid in its calibration and to obtain the best-fit kr values corresponding to effective Mn removal for the various operating conditions. Soluble Mn removal in the contactor column was directly dependent on solution pH and initial free chlorine concentration. The applied water temperature and HLR also had a small impact on the Mn removal profiles observed. On analyzing the results obtained from the model, it was noted that the best-fit kr values for the pilot plant data increased with increasing solution pH (When temperature = 200C and the initial Cl levels were below 1.5mg/L). Also, the Mn uptake capacity of the pyrolucite media increased with both an increase in initial Mn concentration and solution temperature. Long-term operation of the contactor also resulted in significant head loss accumulation in the upper portion of the contactor column, most probably due to MnOx(s) deposition on the media and partial blockage of contactor void spaces. Media fluidization was necessary to address this operational issue. / Master of Science

Manganese is a metal of strategic importance which is vital to the steel industry. In the production of steel, the two main uses of manganese are as a deoxidizer and as an alloying constituent. Approximately 13 pounds of manganese are used for each ton of steel, and for this use alone, the requirement of the United States in 1956 will approach two million tons of ferromanganese ore. In 1954, the United States imported over 90 percent of its manganese requirements and if these sources become unavailable, this nation will be dependent to a great extent upon abundant low-grade ores. A sample of the head ore from the Betty Baker Mine, Great Gossan Lead, Carroll County, Virginia, analyzed 0.82 percent acid soluble manganese. An analysis of the tailings from flotation of this complex sulfide ore revealed a total manganese content of approximately three percent of which two-thirds is acid soluble. The remaining one percent is in the form of a silicate-aluminate gangue which is acid insoluble. Mechanical methods such as froth flotation, sink float, and magnetic separation have not been too effective in upgrading the ore from Carroll County. Chemical procedures, such as roasting, leaching, and electrodeposition, were thought to offer a better means for the recovery of manganese from the beneficiated ore or tailings. It was the purpose of this investigation to evaluate procedures for chemically converting the manganese compounds in the tailings, from bulk sulfide flotation of the Carroll County ore, to soluble salts from which the manganese could be recovered electrolytically. / Master of Science

<p dir="ltr">High exposure to manganese (Mn) through the inhalation of welding fumes has been shown to have a toxic effect to the human brain, leading to parkinsonian-like symptoms such as changes in mood, cognition, and motor function. Oxidative stress and GABAergic dysfunction, two proposed mechanisms implicated in Mn neurotoxicity, can be measured by edited MR spectroscopy (MRS). Previous animal studies have found depleted levels of glutathione, the brain’s antioxidant, and GABA in response to exposure to Mn. Past welder studies have shown altered GABA levels in highly exposed welders. However, GSH has not yet been measured in welders. Recent advances in edited MRS allow for the simultaneous measurement of GABA and GSH, however, one sequence does not ‘fit all’. Thus, there is a need to ensure accurate and reproducible measurements of these metabolites in the study of neurological disorders, such as Mn neurotoxicity.</p><p dir="ltr">The overall goal of this dissertation is to establish a reproducible edited MRS protocol and ensure accurate measurement of metabolites in the context of Mn neurotoxicity. This work has been accomplished in three steps. First, we developed an optimized and reproducible HERMES sequence that allows for the consistently reliable measurement of GABA and GSH at 3T. Second, we investigated whether toenail concentrations of manganese (Mn) and iron (Fe) serve as biomarkers for levels of GABA, GSH, and Glx in the brains of welders exposed to these metals. This aim explores the potential for toenails to be used as a risk assessment tool by evaluating correlations between toenail metal levels and brain metals and metabolites. Lastly, we examined whether excessive accumulation of metals in the brain has an impact on the relaxation times of metabolites. Due to its paramagnetic properties, brain accumulation of two major components of welding fumes, Mn and iron (Fe), may be measured noninvasively through increased magnetic resonance imaging (MRI) relaxation rates, R1 and R2*, respectively. This aim delves into the potential effects of metal exposure on the physical properties of brain metabolites, which could shed light on the accuracy of quantification.</p><p dir="ltr">Overall, the dissertation is a successful step towards establishing reproducible edited MRS acquisitions, and the accurate quantification in the application of Mn neurotoxicity. This work focused on developing methodologies and assessing physical properties for accurate GABA and GSH measurements and investigating risk-assessment methods for metal-induced neurotoxicity.</p>

Hydrogen is a component of spacecraft fuel that is explosive at atmospheric concentrations of four percent or higher. A study was undertaken to determine potential systems for use in tow types of hydrogen sensors that will be useful for real time hydrogen detection, both in ground storage and utilization facilities and in spacecraft. Quantitative detection demands a small, highly sensitive, and highly selective sensor. These detectors will be useful in areas such as the vicinity of joints, couplings, and stress points in the hydrogen storage and plumbing system of the space shuttle. Qualitative detection requires the other sensor to cover large areas, use no power, and be easily monitored visually or with a camera. Such a sensor will serve two purposes: it will allow general detection of hydrogen in a large space where poorly positioned point sensors would fail; it will also aid in locating and repairing any hydrogen leaks that might occur. A manganese (IV) oxide film was produced on the surface of a quartz crystal microbalance and this system was investigated for use as a small, quantitative hydrogen sensor. A reproducible response to hydrogen in the form of an increase in the frequency of vibration of the quartz crystal under an applied voltage was demonstrated. Other coatings were also investigated. A number of indicator compounds were screened for response to hydrogen to serve as large area sesnors. The metallochromic indicator, calmagite, produced a noticeable darkening upon exposure to hydrogen, demonstrating its potential for use as a qualitative, large area hydrogen sensor.

No / Metal ion acquisition and homeostasis are essential for bacterial survival, growth and physiology. A family of metal ion, ABC-type import systems have been identified in Gram-positive bacteria, in which the solute-binding proteins are predicted to be membrane-anchored lipoproteins. The prediction that the MtsA protein of Streptococcus agalactiae A909 is a lipoprotein was confirmed. The expression of MtsA was co-ordinately regulated by the presence of both manganese and ferrous ions suggesting that MtsA may be involved in the uptake of both these ions. MtsA was shown to be expressed at levels of ferrous ions known to be present in amniotic fluid, a growth medium for S. agalactiae during neonatal infection.