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(1 - 3 of 3)
- Title
- CORROSION-RESISTANT ELECTRO-CATALYSTS AND SUPPORTS FOR ELECTROCHEMICAL ENERGY CONVERSION
- Creator
- Wang, Guanxiong
- Date
- 2016, 2016-12
- Description
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Polymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power...
Show morePolymer electrolyte fuel cells (PEFCs) convert chemical energy of fuels (eg. Hydrogen) directly to electrical energy with excellent power density, high efficiency, and zero emissions. Several challenges have delayed the commercialization of fuel cells with one being the high cost and durability of the carbon-supported-platinum-based (Pt/C) electrocatalysts. The lifetime/durability issue is critical as insufficient durability/reliability of the catalysts affects the lifetime and economical viability of these devices. Carbon support corrosion is a major durability issue since the corrosion reaction is thermodynamically favorable but kinetically sluggish under normal operating conditions. The potential transients that occur during start and stop in automotive applications can lead to electrode potential excursions of up to 1.5 V and contribute to carbon corrosion. The best way to mitigate support corrosion in PEFCs is to replace the carbon supports with alternatives having high electronic conductivity, surface area and porosity. This dissertation investigates the following carbon alternatives: (i) tin doped indium oxide (ITO) and (ii) 1:1 mixed oxides of ruthenia and silica (RSO). Microstructure characterization and electrochemical evaluations, including accelerated stress tests (start-up/shut-down and load cycling protocols) were performed to evaluate ORR activity, fuel cell performance, and electrochemical stability under PEFC operating conditions. The ITO support and 40%Pt/ITO catalysts demonstrated exceptional electrochemical stability (and reasonable ORR activity) in rotating disk electrode (RDE) experiments under accelerated potential cycling that mimicked automotive drive cycles. However, Pt/ITO exhibited poor performance and stability during MEA evaluation in a PEFC. X-ray photoelectron spectroscopy (XPS) was employed to reveal the degradation modes of Pt/ITO during PEFC operation and it was found that the increase in the surface hydroxide concentration generates a passivating In(OH)3 layer that increases electrode resistance and undermines PEFC performance. The influence of the catalyst support on PEM degradation during PEFC operation was also studied. Rotating ring-disk electrode (RRDE) experiments were employed to estimate the fraction of H2O2 generated during the ORR on the supports (C and RSO) and catalysts (benchmark Pt/C and Pt/RSO). The percentage of H2O2 generated on C and Pt/C was 50% higher than that on RSO and Pt/RSO thus explaining the observed oxidative degradation resistance of the PEM with the latter supports/catalysts.
Ph.D. in Chemical Engineering, December 2016
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- Title
- AN INTRINSICALLY CONDUCTING POLYMER-BASED COATING SYSTEM FOR CORROSION PROTECTION OF STEELS
- Creator
- Yu, Qifeng
- Date
- 2016, 2016-12
- Description
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Among the various corrosion protection strategies for structural steels, coating techniques provide the most cost-effective protection and...
Show moreAmong the various corrosion protection strategies for structural steels, coating techniques provide the most cost-effective protection and have been used as the primary mode for corrosion protection. Existing coating techniques have been used mainly for their barrier capability and all have a limited service life. In this research work, a waterborne two-strand polyaniline: poly (acrylic acid) complex was synthesized and utilized to fabricate the primer layer of a two-layer coating system. The techniques of Scanning Kelvin Probe Force Microscopy (SKPFM) and Electrochemical Impedance Spectroscopy (EIS) were used to evaluate the anti-corrosion capability of the polymeric complex when mixed in an epoxy matrix and coated on steel samples as the primer layer. The evaluation results show that coating systems including a PANi-based primer has measurable anticorrosion capability and the anti-corrosion capability of PANi-based primer depends on the usage of PANi and the type of matrix material of the primer layer. In the laboratory condition, a prototype two-layer coating system including the PANi-based primer and a polyurethane topcoat was manufactured. The ASTM Salt-Spray Test and EIS were used to prove the anti-corrosion performance of the prototype using a two-layer, polyurethane-over-epoxy system (no PANi) as the control system. After the proof of concept, a non-waterborne epoxy was used to fabricate a different PANi-based primer. The two types of primers and two other commercial primers (a zinc-rich primer and an epoxy-only primer) were used to make a total of eight two-layer coating systems using two widely used topcoats. Salt-Spray Test, Cyclic Salt Fog/UV Exposure Test, Pull- Off Adhesion Test, and the techniques of EIS, SKPFM, and Scanning Electron Microscope (SEM) were used to evaluate the long-term performance of the eight systems. Based on the laboratory-based recommendations, six groups of two-layer coating systems were then subjected to the outdoor-exposure test to evaluate their anti-corrosion durability at two testing sites. The field durability of the coating systems was evaluated in terms of their surface gloss reduction, color change, adhesion change and surface deteriorations. The matrix material in which the PANi is mixed plays an important role in the longterm anti-corrosion performance of coatings. The waterborne epoxy is effective in dispersing PANi nano-particles and has zero VOC; however, it does not bond to the steel surface as strongly as the regular non-waterborne epoxy. The topcoat material also plays an important role in the long-term anti-corrosion performance of coatings; polyurethane has higher durability than epoxy as a topcoat material. The PANi-based systems possess long-term corrosion protection comparable to the performance of the conventional zincrich three-layer system based on the one-year field evaluation.
Ph.D. in Civil Engineering, December 2016
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- Title
- ELECTROCHEMICAL BEHAVIOR OF ADDITIVELY MANUFACTURED NON-SPHERICAL TI-6AL-4V POWDER IN 3.5 WT. % NACL SOLUTION
- Creator
- Bagi, Sourabh Dilip
- Date
- 2021
- Description
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In laser powder bed fusion (LPBF), also known as selective laser melting (SLM), the feedstock powder and processing parameters affect the...
Show moreIn laser powder bed fusion (LPBF), also known as selective laser melting (SLM), the feedstock powder and processing parameters affect the properties of additively manufactured parts. Limited research has been conducted on non-spherical Ti6Al4V feedstock powder prepared by Hydride-Dehydride process. Significant progress in metal powder additive manufacturing (AM) requires the inter-linking of multiple variables, which includes starting materials, process settings, and post-treatment to achieve desired resultant properties. Owing to the rapid emergence of metal 3D-printing, process-property relationships, and appropriate post-treatment conditions have not been as extensively characterized as for conventional materials, thus requiring significant attention. Over the years, spherical powders were used in powder bed AM machines and there have been various concerns related to powder as well as processing parameters leading to defects formation, poor part quality, and unsatisfactory performance. It is critical to keep the cost of manufacturing low for large-scale production which results in significant interest in low-cost powder, making it vital to understand the effect of microstructural defects on corrosion behavior. Recently, economical powder attracted attention in AM, thus, making it is necessary to understand the role of possible microstructural defects on corrosion behavior. In powder bed additive manufacturing, feedstock and processing affect final microstructure and properties of the 3D printed parts. While numerous studies have evaluated 3D-printing of spherical powder, very limited research has examined the processing of the non-spherical feedstock. In this research, parts are manufactured by SLM of hydride-dehydride (HDH) Ti6Al4V powder. heat treatment and hot isostatic pressing are applied on SLM parts. The microstructures, potentiodynamic curves, and electrochemical impedance spectroscopy are characterized for SLM processed, heat treated, and hot isostatically pressed HDH Ti6Al4V specimens. Results indicate although the as-built specimen has anisotropic microstructure (i.e., lamellar α + acicular α’ + β phases), the heat treatment and hot isostatic pressing result in homogenized grain structures and enhanced corrosion behavior. Results indicate that type of constituent phase, grain size, and morphology directly determine corrosion resistance. This research is beneficial for the manufacturing of low-cost titanium alloys. In the current research, we evaluate non-spherical powder processing by hydride-dehydride (HDH) method and selective laser melted in powder bed AM machine followed by heat treatment and hot isostatic pressing to alter microstructure and electrochemical behavior. If successful, the usage of non-spherical morphology in conjunction with the newer powder dispensing method of double smoothing will enable remarkable improvements in the quality and performance of additively manufactured products. This method will also cut down costs associated with a greener powder production method and enhance the fabrication rate. It is a well-established fact that corrosion behavior is drastically affected by heterogeneous microstructure and defects. Thus, it is paramount to conduct a systematic study on the role of processing parameters and post process heat treatment, which can enhance our understanding of possible defect formation in micro and macro scale and their impact on electrochemical behavior.
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