Thesis (Ph.D.)--Ohio University, November, 2006. / Title from PDF t.p. Includes bibliographical references.

Thesis (M.S.)--Ohio University, March, 2007. / Title from PDF t.p. Includes bibliographical references.

Biomining technologies have been developed to use acidophilic microorganisms and the reactions that they catalyze to extract metals from ores in the mining industry. This biological processing through hydrometallurgy is responsible for the production of a significant portion of the world’s copper and gold supplies. Acidithiobacillus ferrooxidans is one of the better-studied and important chemolithotrophic bacterial species that is a part of the natural consortia found in mines across the world. This acidophile is unique in the array of redox reactions it participates in as it is capable of oxidizing both iron and reduced inorganic sulfur species, enabling dissolution of metal from minerals. As the transition to renewable energy continues and the demand for electronic devices grows, more copper and other valuable metals will need to be extracted from increasingly low-grade ores, such as chalcopyrite. Additionally, there has been a growing interest in further developing this biotechnology for the leaching and the recovery of valuable metals from scrap alloys and electronic waste as these feedstock streams can contain rare metals at concentrations above those found in the earth. However, the challenge in deploying biomining to these applications involves understanding the interactions that can potentially inhibit the extraction of these metals. In this dissertation, we expanded the genetic toolbox for A. ferrooxidans by using a transposition technique for the chromosomal integration of exogenous genes. The ability to permanently modify the genome enables engineering of strains that can be used in industry without the need of maintaining selective pressure for plasmid-based expression. Next, we investigated the potential role of A. ferrooxidans in microbially influenced corrosion. We focused on finding conditions that would enable the corrosion of stainless steel, which is resistant to the medium typically used for the growth of the bacterium. Additionally, the further optimization of the corrosive environment and the introduction of genetically engineered cells led to additional corrosion of a higher-grade stainless steel. Then, we explored how altering the bioavailability of sulfur in different formulations could shift the population phenotypes in A. ferrooxidans. We found that a unified description with a few parameters could describe the wide range of behaviors observed in the presence of iron and sulfur. Thus, using this improved understanding of A. ferrooxidans, we are able to engineer phenotypes of interest to generate robust strains that can modulate leaching conditions.

Research has focused on the influences of flowing fluid on the corrosion of bare metals, but there is little emphasis on the degradation of metal-protective coating. Evaluating the metal-protective coating usually uses the Electrochemical Impedance Spectroscopy (EIS) method. This paper presents a new impedance-based wireless sensor network for metal-protective coating evaluation. This wireless sensor network consists of two parts: impedance-based wireless sensor nodes and a wireless data base that are equipped with a network analyzer (AD5933) and a RF transceiver (CC1111/CC1110). In the experiment, three coating panels are immersed in flowing deionized water (DI water) and one coating panel immersed in stationary DI water. Experimental results demonstrate that this wireless sensor network is capable of evaluating the coating degradation.

Sulfur adsorbed on metallic and oxide surfaces, whether originating from gaseous environments or segregating as an impurity to metallic interfaces, is linked to the deterioration of alloy performance. This research dealt with investigations on the interactions between sulfur and iron or iron alloy metallic and oxide surfaces under ultrahigh vacuum conditions. Sulfur was either intentionally dosed from a H2S source on an atomically clean metal surface, or segregated out as an impurity from the bulk to the metal surface by annealing at elevated temperatures.

This study was intended to provide a fuller understanding of the surface chemical processes which result in the corrosion of ferrous materials.

Layered double hydroxides (LDH) are a class of anionic clay with alternating layers of positive and negative charge. A metal hydroxide layer with divalent and trivalent metals with a positive charge is complemented by an interlayer region containing anions and water with a negative charge. The anions can be exchanged under favorable conditions. Hydrotalcite (Mg6Al2(OH)16[CO3]·4H2O) and other variations are naturally occurring minerals. Synthetic LDH can be prepared as a powder or film by numerous methods. Synthetic LDH is used in electrode materials, adsorbents, nuclear waste treatment, drug delivery systems, water treatment, corrosion protection coatings, and catalysis. In this dissertation Zn-Al-NO3 derivatives of zaccagnaite (Zn4Al2(OH)12[CO3]·3H2O) are electrochemically synthesized as films and applied to sensing and corrosion resistance applications. First, Zn-Al-NO3 LDH was potentiostatically electrosynthesized on glassy carbon substrates and applied to the electrochemical detection of gallic acid and caffeic acid in aqueous solutions. The modified electrode was then applied to the detection of gallic acid in green tea samples. The focus of the work shifts to corrosion protection of stainless steel. Modified zaccagnaite films were electrodeposited onto stainless steel in multiples layers to reduce defects caused by drying of the films. The films were deposited using a step potential method. The corrosion resistance of the films in a marine environment was investigated while immersed in 3.5 wt.% NaCl environments. Next modified zaccagnaite films were potentiostatically electrodeposited onto stainless steel followed by a hydrophobization reaction with palmitic acid in order to prepare superhydrophobic (>150° contact angle) surfaces. Each parameter of the film synthesis was optimized to produce a surface with the highest possible contact angle. The fifth chapter examines the corrosion resistance of the optimized superhydrophobic film and a hydrophobic film. The hydrophobic film is prepared using the same procedure as the superhydrophobic film except for a difference in electrodeposition potential. The corrosion resistance of these films is investigated in a simulated marine environment (3.5 wt.% NaCl) for short and extended durations. The last chapter summarizes the previous chapters and suggests future directions for this work.

M.S.

No description available.

N-type GaAs is a potentially useful semiconductor in liquid junction type solar cells. Corrosion and corrosion suppression on an n-type GaAs semiconductor in both light and dark has been studied. The application of non-electroactive layers for corrosion suppression on semiconductor electrodes is a relatively new field. GaAs corrodes to form Ga(III) and As(III) solution species during photocurrent generation. The corrosion rate is determined electroanalytically in acidic media by measuring As(III) using differential pulse polarography (DPP). In neutral electrolytes a rotating ring-disc experiment measured the efficiency of hole-transfer to a redox couple. Two protecting processes have been utilized. Silanization and electrochemical polymerization of divinylbenzene and phenol were used to deposit non-electroactive layers on the electrode surface. The polyphenylene oxide coating partially suppressed corrosion in acid electrolytes. However, the coatings did not improve hole transfer efficiency in neutral electrolytes. / Master of Science