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Electrochemical characterization of fluoropolymers and aromatic compounds for corrosion protection applicationsCaldona, Eugene B 25 November 2020 (has links)
The consequences of corrosion are extremely costly and troublesome. In manufacturing companies, for instance, corrosion is considered a chronic problem that causes sudden disruptions in many segments of operation including processing, production, transportation, and containment of commodity products. Protection against corrosion is, therefore, important, as it helps achieve service life extension for metals and reduction in corrosion-related costs. Risk reduction for catastrophic structural failures and accident prevention can also be realized. Broader application of protective coatings and corrosion inhibiting agents remains one of the best technical practices in minimizing the effects of corrosion. This study introduces different classes of polymers and organic compounds and their potential use as new groups of corrosion preventing materials. Firstly, the use of semiluorinated perfluorocyclobutyl (PFCB) aromatic ether polymers as coatings for corrosion prevention was examined. PFCB polymers share several important characteristics with commercial fluoropolymers including chemical resistance, thermal stability, mechanical strength, and low surface energy, but with enhanced processability. Secondly, the use of very small amounts of azole-based aromatic compounds was shown to effectively inhibit corrosion in acidic medium. Compared to other inhibitor agents, these compounds have the advantage of being less complex, inexpensive, environmentally friendly, and synthesized in a one-step approach. Thirdly, the use of a tetradiglycidyl-ether-based epoxy-amine resin as corrosion resistant coating was investigated both in its intact and artificially-damaged forms. This epoxy resin, which can be infused with preform materials, has been used in the development of carbon fiber composites for aircraft applications. Finally, the capability of a superhydrophobic perfluorinated polymer nanocomposite coating to resist corrosion was evaluated. The coating also displayed superoleophilicity, which led to its additional use in separating oil-water mixtures. Standard electrochemical methods such as open circuit potential, electrochemical impedance spectroscopy, and potentiodynamic polarization were used to evaluate the corrosion protection performance. Several other analytical techniques were also employed to characterize the quality and structure of the protective materials and supplement the results acquired from electrochemical analyses.
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DESIGN OF BIOCOMPATIBLE ASPARAGINE-GRAPHENE OXIDE FREE CHLORINE SENSORS FABRICATED USING SOLUTION BASED PROCESSINGSiddiqui, Junaid January 2022 (has links)
Chlorine is used as a powerful disinfectant in water-related industries and in the food industry to
remove bacteria and other harmful contaminants. We present a solution-based fabrication
process for a biodegradable electrochemical free chlorine sensor using asparagine that is
functionalized onto graphene oxide (GO). An ink solution of the GO functionalized with
asparagine was fabricated then deposited onto a screen-printed carbon electrode (SPCE) using a
spin-coater. The sensor showed high a sensitivity of 0.30 μA ppm−1 over a linear range of 0 to 8
ppm with a hysteresis-limited resolution of 0.2 ppm, very high selectivity in the presence of
commonly interfering ions, and an operating voltage well below the reduction potential of
dissolved oxygen. The sensor response time to achieve a steady state was 50 s, and it showed
little change in its drift response over 16 h and over a temperature range of 10 to 45 °C. From the
development of the free chlorine sensor, over 9000 datapoints were collected and used for
training a neural network model to quantify and characterize factors affecting the free chlorine
sensor performance. A readout system was designed with a printed circuit board and an android
app to simplify free chlorine sensing for an end user. / Thesis / Master of Applied Science (MASc) / Free chlorine is used to disinfectant sources of water, and eliminate pathogens. The World
Health Organization (WHO) maintains strict amounts of free chlorine in water due to its
widespread usage owed to its low cost and persistence in water systems. Too little, and it will not
be an effective disinfectant, and too much and the high consumption of free chlorine increases
the risk cancer or the formation of hazardous chemicals. Recently, free chlorine sensors that
measure an electrical response proportional to the amount of free chlorine are gaining interest for
fast, accurate, and repeatable measurements.
This thesis focuses on the design, fabrication, and evaluation of these sensors made using
biodegradable materials in a solution-based fabrication processes with the aim of working
towards large-scale fabrication of a printable ink. First, we review the results achieved by the
sensors within recent literature. Second, we present the design of a sensor that aims to achieve
environmentally friendly goals and maintain competitive performance characteristics. The, the
sensor is tested under various conditions with its performance quantified under different
conditions. Third, the sensor is characterized using a neural network to measure its performance
and identify sources of improvement for future designs. Finally, we incorporate the sensor with
an android app to measure free chlorine in remote water systems.
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Long Range Surface Plasmon Waveguides for Electrochemical DetectionHirbodvash, Zohreh 04 November 2022 (has links)
An electrochemical detection method based on long range surface plasmon waveguides is proposed and demonstrated in this integrated article thesis. This dissertation uses CYTOP gold (Au) waveguides supporting long range surface plasmon polaritons (LRSPPs) in conjunction with grating couplers as well as Au waveguides embedded on a one-dimensional photonic crystal (1DPC) supporting Bloch LRSPPs integrated grating couplers.
Grating couplers for Au stripe waveguides embedded in Cytop are demonstrated and analyzed. Grating couplers are used in a broadside coupling scheme where a laser beam incident on a stripe of Au on Cytop. The use of gratings for excitation of LRSPPs simplifies optical alignment and does not require high-quality input and output edge facets. Over a broad operating wavelength range, optical experiments are performed to demonstrate coupling loss and determine the efficiency of grating coupling using both a cleaved bow-tie PM fiber and a lensed PM fiber. The coupling loss and grating coupling efficiency of both types of fibers are also calculated numerically.
Fluoropolymers with refractive indices close to water, such as CYTOP, are widely used to make waveguide biosensors today. Due to its low glass transition temperature, CYTOP presents limitations to fabrication processes. A truncated 1D photonic crystal may replace a low-index polymer cladding such as CYTOP to support Bloch LRSPPs within the bandgap of the 1DPC over limited wavenumbers and wavelength range.
As a result of the high sensitivity of Au stripe Bloch LRSPP waveguide biosensors and their compatibility with high levels of integration, microelectrode systems that can be integrated with such optical biosensors are examined. A chip bearing a Au LRSPP waveguide that can also function as a working electrode (WE), a Pt counter electrode (CE), and Pt/Cu electrical contact pads, is used to demonstrate the electrochemical performance of LRSPPs waveguides. The cyclic voltammetry measurements were performed at different scan rates and concentrations of potassium ferricyanide as the redox species on Au LRSPPs waveguides. By fitting our experimental data to the Randles-Sevcik equation, we find the diffusion coefficient of potassium ferricyanide. The results from CV measurements obtained from chips are compared with commercial macroscopic electrodes. The CV measurements are also compared with theoretical results computed using the Butler-Volmer equation to determine the rate constant of the redox species at zero potential.
A waveguide containing a stripe of Au that propagates infrared surface plasmon polaritons (SPPs), acting simultaneously as an electrode in a three-electrode electrochemical cell is also examined. Under SPP excitation, cyclic voltammetry was measured as a function of incident optical power and wavelength (1350 nm). In oxidation and reduction reactions, energetic electrons are separated from energetic holes. Under SPP excitation, redox current densities increase by 10×. With the SPP power, the oxidation, reduction, and equilibrium potentials drop by as much as 2× and separate in correlation with the photon energy. According to electrochemical impedance spectroscopy, charge transfer resistance dropped by almost 2× under SPP excitation. During SPP excitation, the temperature of the working electrode is monitored in situ and independent control experiments are performed to isolate thermal effects. Measurements of chronoamperometry with SPPs modulated at 600 Hz yield a rapid current response modulated at the same frequency, ruling out thermally enhanced mass transport. The observation is attributed to the opening of optically controlled non-equilibrium redox channels associated with the energetic carrier transfer to the redox species. During CV and chronoamperometry measurements, convolutional voltammetry is performed by monitoring the SPP output power versus the applied voltage. Using both experimental and theoretical methods, we demonstrate that the SPP output power is proportional to the electrochemical current convolution. A SPP voltammogram confirms that signal changes are mainly caused by differences in refractive index between reduced and oxidized forms of redox species. In addition, we demonstrate that energetic carriers resulted from SPP absorption significantly improved electrochemical sensitivity.
As a complementary electrochemical technique, convolutional voltammetry is useful since the signal is related directly to the concentration of electroactive species on the working electrode (WE) and independent of the scan rate. As a probe of electrochemistry taking place in waveguides, surface plasmon polaritons (SPPs) propagating along one are sensitive. In such a waveguide, the optical output power is proportional to the time convolution of the electrochemical current density, eliminating the need to calculate the latter a posteriori via numerical integration. It is demonstrated that a waveguide WE provide an optical response that can be experimentally validated by chronoamperometry and cyclic voltammetry measurements under SPP excitation for a few potassium ferricyanide (redox species) concentrations in potassium nitrate (electrolyte) and various scan rates. Cyclic voltammetry measurements taken under increasing SPP power produce a regime where SPPs no longer act solely as the probe, but also act as a pump, producing energetic electrons and holes via their absorption in the WE. The energetic carriers enhance (10×) redox current densities as well as the convolution signal measured directly as the optical output power over time.
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A STUDY OF POROUS ELECTRODES FOR DNA ELECTROCHEMICAL DETECTION AND THE DEVELOPMENT OF A HYBRIDIZATION EFFICIENCY CHARACTERIZATION TECHNIQUEFung, Barnabas January 2016 (has links)
Point-of-care DNA diagnostics for resource-limited settings require high sensitivity and low limits of detection but is constrained by a limitation on the complexity of instrumentation and resource consumption. To assist in the research and development of such technology, rapid-prototyping offers quick turnaround times from ideation to proof-of-concept testing at reduced costs.
All-solution processed electrodes which exhibit micro/nano-scale wrinkling and porosity were rapidly-prototyped. Probe density was shown to be tunable with these electrodes and densities were greater than planar electrodes due to a surface area enhancement. Such electrodes also demonstrated favorable characteristics for the electrocatalytic detection of DNA hybridization.
Characterization of hybridization efficiency for DNA biosensors often require the determination of probe and target DNA densities in separate experiments, relying on averaged measurements which lose device specificity. A new method to quantify hybridization efficiency was developed which allows the label-free, sequential determination of probe DNA and target DNA density in one experiment, allowing electrode-specific characterization of hybridization efficiency. / Thesis / Master of Applied Science (MASc)
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Studies of Used Fuel Fluorination and U Extraction Based on Molten Salt Technology for Advanced Molten Salt Fuel FabricationDavis, Brenton Conrad 14 December 2023 (has links)
This study focuses on techniques that can be used to fuel next generation reactors. The first two studies are new techniques for recycling used nuclear fuel (UNF) and the third is a method of separating uranium (U) from lithium fluoride (LiF) and thorium fluoride (ThF4) salt also known as FLiTh for a thorium (Th) fuel cycle.
The first technique proposed for UNF recycling was to use the cladding as an anode to oxidize the zircaloy and dissolve it into a LiF, sodium fluoride (NaF), zirconium fluoride (ZrF4) salt. Zirconium (Zr) was also reduced and deposited on a tungsten (W) cathode at the same time transporting the Zr through the salt. As commercial zircaloy would be contaminated with UNF oxides, and the oxides will not oxidize as part of the electrochemical process, they would be left at the anode as the Zr is dissolved away. This means the deposited Zr, on the cathode, can be disposed of as low-level waste (LLW) or recycled back into the nuclear industry instead of being stored as high-level waste (HLW).
The next technique was fluorination of UNF oxides using ZrF4. Using the same LiF-NaF-ZrF4 salt, uranium oxide (UO2), lanthanum oxide (La2O3), and yttrium oxide (Y2O3) were fluorinated into uranium fluoride (UF4), lanthanum fluoride (LaF3), and yttrium fluoride (YF3). By sampling and recording the change in concentration over time, the reaction rate of all three oxides was determined and a temperature dependent reaction rate was reported from 500°C to 650°C. A zirconium oxide (ZrO2) product layer developed on UO2, but it only slowed down the fluorination process but did not stop it. UO2 and Y2O3 fluorinated entirely but La2O3 did not. The solubility limit of LaF3 in the salt was determined to be the reason the reaction did not go to completion.
The last technique was the electrochemical separation of U from FLiTh, to simulate irradiated Th that decays to protactinium (Pa). A constant, albeit small current, was used to deposit U on a W electrode without Th depositing with it. A liquid metal bismuth (Bi) electrode was used as well, and a constant current resulted in Th depositing with the U. To get just U to deposit, the current needed to be applied for a time and then no current applied for a time so the system could reach equilibrium. By cycling these two steps it was possible to get U to deposit in Bi without Th. / Doctor of Philosophy / This study focused on techniques useful to the fabrication of next generation reactor fuels. The first focus was on new techniques for recycling used nuclear fuel (UNF). Nuclear waste currently needs to be stored for hundreds of thousands of years to reach background radiotoxicity levels. If plutonium (Pu) is removed from the waste this time is limited to ten thousand years and if the other transuranics (TRU) are removed the waste only needs to be stored for 300 years to reach background radiotoxicity levels. As recycling UNF can make such a drastic difference, developing techniques for this are of utmost importance.
The first technique studied was to show that the zirconium (Zr) in zircaloy cladding could be oxidized and transported through salt. This was done by applying a current between a zircaloy anode and tungsten (W) cathode, dissolving the cladding into the salt. The salt used was lithium fluoride (LiF), sodium fluoride (NaF), and zirconium fluoride (ZrF4) salt called FLiNaZr. This transported Zr through the salt and then deposited it on W. If this process was done with zircaloy contaminated with used nuclear fuel (UNF) oxides, the oxides would not dissolve into the salt as part of the process and would be left behind at the anode as Zr is transported through the salt, effectively separating the two. This alone leads to a 25% reduction in the weight of the UNF that needs to be stored.
The next technique studied was converting the UNF oxides into fluorides. This was done by having it react with ZrF4 to make zirconium oxide (ZrO2) and UNF fluorides. The oxides studied here were uranium oxide (UO2), yttrium oxide (Y2O3), and lanthanum oxide (La2O3). UO2 and Y2O3 reacted until no material was left but La2O3 did not. This was due to lanthanum fluoride (LaF3) having a solubility limit in the salt that made it impossible for more to be made and stopping the reacting. The reaction rate for each oxide was found and the order of the reaction rates was Y2O3>UO2>La2O3. This process was a success and should be studied more to ensure it will work with all oxides found in UNF.
The last technique studied was electrochemically separating uranium (U) from lithium fluoride and thorium fluoride (ThF4) salt. Thorium (Th) is another nuclear material, and while it cannot fission in a reactor it can be turned into an isotope of U, U-233, that can. To do this Th must be irradiated so it turns into protactinium (Pa) which can then be separated from the salt. In this study U was a surrogate for Pa as it is too radioactive to handle in this lab. First, an inert W electrode was used to deposit U metal, and once it was successful a liquid metal bismuth (Bi) electrode was used. A small constant current was able to deposit U on W without co-deposition of Th. For a Bi electrode, an alternating time of applying current and then letting the system rest was needed to deposit U without co-deposition of Th.
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Nanomaterials-based electrochemical sensors for health and environmental monitoringAli, Md Younus January 2023 (has links)
Bisphenol A (BPA), an endocrine disruptor, requires monitoring in water for health safety. Glutamate, H2O2, and glucose are vital biomarkers for various diseases. However, lab-based methods are expensive, time-consuming, and require skilled personnel, making them unsuitable for point-of-care (POC) devices. The electrochemical sensor enables POC device development. However, it suffers from low sensitivity and selectivity. This thesis focuses on the use of nanomaterials to enhance the sensitivity and selectivity of electrochemical sensors to monitor BPA in water, along with glutamate, H2O2, and glucose in bio-fluids.
A BPA sensor was developed using chemically modified MWCNTs with βCD on a screen-printed carbon electrode (SPCE). The MWCNTs-βCD/SPCE exhibited high sensitivity, attributed to the catalytic activity of MWCNTs and the host-guest interaction ability of βCD. It provided a linear range (LR) of 125 nM −30 µM, with a limit of detection (LOD) of 13.76 nM (SNR = 3). We improved the performance by curing the MWCNTs-βCD/SPCE with CTAB. The sensor demonstrated a dynamic range of 500 fM to 10 μM, with a LOD of 96.5 fM, surpassing the Canada-assigned PNEC of BPA in water (0.77 nM).
We fabricated a nonenzymatic glutamate sensor using CuO nanostructures and MWCNTs on SPCE. The sensor showed irreversible oxidation of glutamate involving one electron and one proton, and an LR of 20 μM−200 μM with LOD of 17.5 μM and sensitivity of 8500 μAmM−1cm−2. The sensor is promising to detect glutamate in blood.
We developed a nonenzymatic glucose sensor using green synthesized gold nanoparticles and CuO-modified SPCE. The LR offered by the sensor (2 µM to 397 µM) is suitable for quantifying saliva glucose. We also created nonenzymatic H2O2 sensor by green synthesized silver nanoparticles modified SPCE which offers LR of 0.5- 161.8 µM with LOD 0.3 µM which is capable of H2O2 monitoring in urine. / Thesis / Doctor of Philosophy (PhD) / Bisphenol A (BPA) is a plastic pollutant and an endocrine-disrupting chemical that causes reproductive and neurodevelopmental disorders, and many diseases including obesity, diabetes, and cardiovascular disease. In addition, glutamate, hydrogen peroxide (H2O2), and glucose are vital biomarkers for various acute and chronic diseases. These diseases impose significant burdens on individuals, healthcare systems, and the economy. Therefore, they must be monitored. In this thesis, we developed a BPA sensor using chemically modified multiwall carbon nanotubes (MWCNTs) with β-cyclodextrin (βCD) and cetrimonium bromide (CTAB) which can detect BPA at very low concentration beyond Canada-assigned predicted-no-effect-concentrations (PNEC) of BPA. We also developed a glutamate sensor using MWCNTs and wet chemically synthesized copper oxide (CuxO) nanostructure which offers a linear range related to blood glutamate level. Moreover, we fabricated nonenzymatic H2O2 and glucose sensors using green synthesized gold (AuNPs) and silver (AgNPs) nanoparticles (using orange peel extraction as a reducing and stabilizing agent) which are useful to quantify urine H2O2 and saliva glucose respectively.
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The electrochemical determination of oxygen and combustible components in hot gasesMakovos, Edward Boris January 1991 (has links)
No description available.
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Surface science studies of electrochemical energy storage devicesWang, Kuilong January 1992 (has links)
No description available.
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Development of a Thick-Film Printed Ir/C Biosensor for the Detection of Liver Disease Related BiomarkersBartling, Brandon Alan January 2010 (has links)
No description available.
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ELECTROCHEMICAL REDUCTION OF MUNITIONS WASTEWATER-BENCH SCALE AND PILOT SCALE STUDIESDOPPALAPUDI, RAJESH BABU 08 November 2001 (has links)
No description available.
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