For applications of MoS2 in batteries, supercapacitors, electrocatalysts, solar cells and water quality sensors, a substantially increased conductivity is required in order to achieve reasonable currents. Popularly, the metallic 1T-MoS2 phase is used, which can be prepared via a lithium intercalation process, requiring inert atmosphere processing and safety procedures. In this thesis, I demonstrate a safer and more efficient process to yield conductive MoS2 (c-MoS2). This simple and effective way to prepare few layer c-MoS2 utilizes ambient conditions and 0.06 vol% aqueous hydrogen peroxide. Part of the research effort has been to enhance the conductivity of MoS2 using the idea of green solvents (like pure water). The bulk conductivities of both peroxide and water exfoliated MoS2 are up to seven orders of magnitude higher than that of the semiconducting 2H-MoS2 phase. The samples were characterized with Hall measurements, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Trace amounts of hydrogen molybdenum bronze (HxMoO3-y) and sub stoichiometric MoO3-y were shown to help tune the conductivity of the nanometer-scale thin films without impacting the sulfur-to-molybdenum ratio. c-MoS2 was further functionalized with thiols to determine the number of residual reactive sites. I also studied the mechanism of surface functionalization of MoS2 with diazonium molecules (both direct and in-situ approach) to understand the surface properties of our material and tune the chemical and mechanical properties of conductive MoS2. An important goal of my work is to control the conductivity of the MoS2 thin films in safe and facile ways that enable their application in low-cost chemiresistive sensors for liquid environments. I fabricated chemiresistive sensors with centimeter channel lengths while maintaining low measurement voltages for pH sensing. I further measured the catalytic activity of c-MoS2 films in 0.5 M H2SO4 electrolyte solution using linear sweep voltammetry (LSV) which showed a lower Tafel value at 10 mA/cm2 current density. The lower Tafel value demonstrated that c-MoS2 has potential to use as catalyst for hydrogen evolution reaction. My study furthers the understanding of conductive forms of MoS2 and opens up a new pathway for next generation electronic and energy conversion devices. / Thesis / Doctor of Philosophy (PhD) / For applications of MoS2 in batteries, supercapacitors, electrocatalysts, solar cells and water quality sensors, a substantially increased conductivity is required in order to achieve reasonable currents. Popularly, the metallic 1T-MoS2 phase is used, which can be prepared via a lithium intercalation process, requiring inert atmosphere processing and safety procedures. In this thesis, I demonstrate a safer and more efficient process to yield conductive MoS2 (c-MoS2). This simple and effective way to prepare few layer c-MoS2 utilizes ambient conditions and 0.06 vol% aqueous hydrogen peroxide. Part of the research effort has been to enhance the conductivity of MoS2 using the idea of green solvents (like pure water). The bulk conductivities of both peroxide and water exfoliated MoS2 are up to seven orders of magnitude higher than that of the semiconducting 2H-MoS2 phase. The samples were characterized with Hall measurements, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Trace amounts of hydrogen molybdenum bronze (HxMoO3-y) and sub stoichiometric MoO3-y were shown to help tune the conductivity of the nanometer-scale thin films without impacting the sulfur-to-molybdenum ratio. c-MoS2 was further functionalized with thiols to determine the number of residual reactive sites. I also studied the mechanism of surface functionalization of MoS2 with diazonium molecules (both direct and in-situ approach) to understand the surface properties of our material and tune the chemical and mechanical properties of conductive MoS2. An important goal of my work is to control the conductivity of the MoS2 thin films in safe and facile ways that enable their application in low-cost chemiresistive sensors for liquid environments. I fabricated chemiresistive sensors with centimeter channel lengths while maintaining low measurement voltages for pH sensing. I further measured the catalytic activity of c-MoS2 films in 0.5 M H2SO4 electrolyte solution using linear sweep voltammetry (LSV) which showed a lower Tafel value at 10 mA/cm2 current density. The lower Tafel value demonstrated that c-MoS2 has potential to use as catalyst for hydrogen evolution reaction. My study furthers the understanding of conductive forms of MoS2 and opens up a new pathway for next generation electronic and energy conversion devices.

This thesis presents: 1) literature review on adhesive bonding technologies in aviation industry including surface pretreatments (pre-preparation), surface quality assurance, and surface chemistry analysis methods; and 2) development and study of a novel solid-state electrochemical sensor for surface chemistry analysis of composite surfaces. The performance of an adhesive bonding is greatly determined by the adherend?s surface pretreatments which could increase surface tension, surface roughness, and change surface chemistry thereby increasing bond strength and durability of polymer composite adhesive joints. The primary goal of the surface pretreatments is to increase the surface roughness, surface energy, chemical activity, and cleanliness of the composite adherend as much as possible. Methods of surface pretreatments are reviewed in this paper, including: (1) abrasion/solvent cleaning; (2) grit blasting; (3) peel-ply; (4) tear-ply; (5) acid etching/anodizing; (6) corona discharge treatment; (7) plasma treatment; (8) flame treatment; (9) laser treatment; (10) others. One of the critical issues in aviation industry for an adhesive bonding is to analyze the prepared composite surfaces using a nondestructive inspection (NDI) or nondestructive test (NDT) method to determine whether the quality of surfaces are ready for the following bonding processes. Existing NDI methods include: (1) Near-Infrared; (2) Electrical potential; (3) Transient thermal NDT; (4) Electrical Impedance Spectroscopy (EIS); (5) Neutron radiography; and (6) X-ray Photoelectron Spectroscopy (XPS). However, up till now, these methods cannot provide definitive analysis or online and in-field analysis. Because of the non-availability of an on-line, in-field NDI method for surface chemistry analysis, excess or inadequate surface treatment and quality control processes may exist in the current aircraft manufacture processes incurring either a high cost or potentially weak adhesive bonds. Electrochemical reactions usually occur in liquid electrolyte or on conducting electrode but not on non-conducting composite. Conventional electrochemical sensors involve liquid electrolytes which will cause contamination on composite surfaces when they are used for surface chemistry analysis. In this work, we explore an all solid-sate electrochemical sensor technology. Redox pairs or mediators are combined into a solid-state electrolyte, NafionTM. The mediators can pass electrons to or from the composite surfaces causing slight reduction or oxidation of the composite surfaces. The output current in response to cyclic polarization (cyclic potential scanning) is used as the indication of the surface contamination level. The sensors included a working or sensing electrode with mediated Nafion clusters, Nafion membrane, Pt catalyzed carbon counter electrode, and Ag|AgCl reference electrode. The working electrode and counter electrode were attached to the Nafion membrane from different sides. The sensors were tested on different kinds of surfaces: original, polished, and sulfuric acid treated acrylic samples and pristine peel ply prepared, polished, and sulfuric acid treated composite laminate surface samples. The sensors showed a high sensitivity to the surface contamination. The performances and possible mechanisms related to the electrochemical sensors are discussed.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2017-02-01T18:32:19Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DM Henrique Patriota Alves.pdf: 2961953 bytes, checksum: cd856b581753170ffb1c56ff445144f8 (MD5) / Made available in DSpace on 2017-02-01T18:32:19Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DM Henrique Patriota Alves.pdf: 2961953 bytes, checksum: cd856b581753170ffb1c56ff445144f8 (MD5) Previous issue date: 2016-07-22 / CNPQ / Esta dissertação apresenta uma modelagem computacional da dinâmica de rugosidade de superfície gerada durante o processo de corrosão de um elemento transdutor metálico do sensor à fibra óptica. Tal modelagem é implementada num software dedicado de simulação multifísica que faz uso do Método dos Elementos Finitos. Considerando que a rugosidade de superfície pode ser definida por geometria fractal, que pode ser complexa, é proposta nesta dissertação uma forma alternativa e simples para modelar a superfície rugosa e a sua dinâmica sob corrosão. Para a modelagem computacional, é definida uma função periódica, chamada de função rugosidade, onde seus parâmetros são ajustados com dados experimentais do processo de corrosão. Os resultados da simulação computacional são comparados com um modelo analítico, que faz uso das equações de Fresnel. Nos resultados da simulação, é observado o acoplamento do sinal óptico na superfície rugosa do filme metálico. Esse acoplamento observado é explicado pelo fenômeno de Ressonância de Plásmon de Superfície. A modelagem proposta nesta dissertação apresenta excelente ajuste aos resultados experimentais. / This dissertation presents a computer modeling of the surface roughness dynamics generated during the corrosion process of a metallic element transducer of the fiber-optic sensor. This modeling is implemented in dedicated software that uses the Finite Element Method. Since the surface roughness can be defined by the fractal geometry, which can be complex, it is proposed in this dissertation an alternative and simple way to model the surface roughness and its dynamics under corrosion. The proposed modeling uses a roughness function that is defined by a periodic function, where their parameters are obtained from experimental data of the corrosion process. The computer simulation results are compared to an analytical model, which uses the Fresnel’s equations. In the simulation results, it is observed the optical signal coupling with the rough surface of the metallic film. This observed coupling is explained by the phenomenon of Surface Plasmon Resonance. The proposed modeling and simulations presents excellent fitting to the experimental results.

<p>Osnovni cilj teze bio je razvoj nove i inovativne senzorske metode za merenje neorganskih parametara u površinskim vodama i vodama zatvorenih bazena. Kolorimetriski fiber-optički senzor (KFOS) je osposobljen za merenje pet parametara u površinskoj vodi (ortofosfata, ukupnog hlora, hroma (VI), nitrita i sulfata) i za merenje dva parametra u bazenskim vodama (rezidualnog hlora i ukupnog hlora). Pored prilagođavanja nove metode urađena je i analiza kvaliteta reke Dunav u Novom Sadu na osnovu čega su odabrani parametri za merenje sa KFOS metodom.</p> / <p>The main goal of the thesis was to develop a new and innovative sensor method for measuring inorganic parameters in surface waters and waters of indoor pools. The Colorimetric Fiber Optic Sensor (CFOS) is capable for measuring five parameters in surface water (orthophosphate, total chlorine, chromium (VI), nitrite and sulfate) and for measuring two parameters in pool water (residual chlorine and total chlorine). In addition to adjusting the new method, an analysis of the quality of the Danube River in Novi Sad was performed and based on which parameters for measuring with the KFOS method were selected.</p>

<p>The study and understanding of molecular interactions is fundamentally important in today's field of life sciences and there is a demand for well designed surfaces for biosensor applications. The biosensor has to be able to detect specific molecular interactions, while non-specific binding of other substances to the sensor surface should be kept to a minimum.                                                                                                                                                                                The objective of this master´s thesis was to design sensor surfaces based on self-assembled monolayers (SAMs) and evaluate their structural characteristics as well as their performance in Biacore systems. By mixing different oligo (ethylene glycol) terminated thiol compounds in the SAMs, the density of functional groups for bimolecular attachment could be controlled.  Structural characteristics of the SAMs were studied using Ellipsometry, Contact Angle Goniometry, IRAS and XPS. Surfaces showing promising results were examined further with Surface Plasmon Resonance in Biacore instruments.<p>Mixed SAM surfaces with a tailored degree of functional COOH groups could be prepared. The surfaces showed promising characteristics in terms of stability, immobilization capacity of biomolecules, non-specific binding and kinetic assay performance, while further work needs to be dedicated to the improvement of their storage stability. In conclusion, the SAM based sensor surfaces studied in this thesis are interesting candidates for Biacore applications.</p></p>

The study and understanding of molecular interactions is fundamentally important in today's field of life sciences and there is a demand for well designed surfaces for biosensor applications. The biosensor has to be able to detect specific molecular interactions, while non-specific binding of other substances to the sensor surface should be kept to a minimum.                                                                                                                                                                                The objective of this master´s thesis was to design sensor surfaces based on self-assembled monolayers (SAMs) and evaluate their structural characteristics as well as their performance in Biacore systems. By mixing different oligo (ethylene glycol) terminated thiol compounds in the SAMs, the density of functional groups for bimolecular attachment could be controlled.  Structural characteristics of the SAMs were studied using Ellipsometry, Contact Angle Goniometry, IRAS and XPS. Surfaces showing promising results were examined further with Surface Plasmon Resonance in Biacore instruments.Mixed SAM surfaces with a tailored degree of functional COOH groups could be prepared. The surfaces showed promising characteristics in terms of stability, immobilization capacity of biomolecules, non-specific binding and kinetic assay performance, while further work needs to be dedicated to the improvement of their storage stability. In conclusion, the SAM based sensor surfaces studied in this thesis are interesting candidates for Biacore applications.

<p> </p><p>Control of protein immobilization at sensor surfaces is of great interest within various scientific fields, since it enables studies of specific biomolecular interactions. To achieve this, one must be able to immobilize proteins with retained native structure, while minimizing non-specific protein binding. The high affinity interaction between streptavidin (SA) and biotin is extensively used as a linker between a surface, where SA is immobilized, and the (biotinylated) molecule of interest. Self- assembled monolayers (SAMs) of poly- and oligo ethylene glycol (PEG and OEG) derivatives have been proven in literature to minimize non-specific protein binding, and biotin-exposing SAMs have been shown efficient for immobilization of SA.</p><p>The aim of this master's thesis project was to develop biotinylated gold surfaces for quartz crystal microbalance with dissipation monitoring (QCM-D) applications through the self-assembly of mixed monolayers of thiolated OEG (or PEG) derivatives with or without a terminal biotin head group. For this, different thiol compounds were to be compared and evaluated. For the systems under study, the required biotin density for maximum specific SA immobilization was to be established, while keeping the non-specific serum adsorption at a minimum. Model experiments with biotinylated proteins immobilized to the SA-functionalized surfaces were to be performed to evaluate the possibilities for commercialization.</p><p>A protocol for the preparation of a novel biotinylated surface was developed based on the immersion of gold substrates in an ethanolic incubation solution of dithiols with OEG chains (SS-OEG and SS-OEG-biotin, 99:1) and found to give reproducible results with respect to low non-specific protein binding and immobilization of a monolayer of SA. The modified surfaces allowed for subsequent immobilization of biotinylated bovine serum albumin (bBSA) and biotinylated plasminogen (bPLG). PLG was the subject of a challenging case study, using a combination of QCM-D and surface plasmon resonance (SPR), where the immobilized protein was subjected to low molecular weight ligands that were believed to induce conformational changes. The high control of the surface chemistry allowed for the interpretation of the increased dissipation shift upon ligand binding in terms of conformational changes.</p><p>An obstacle before commercialization of the described biotinylated surfaces is that they do not seem stable for storage > 7 days. The reasons for this have to be investigated further.</p>

Control of protein immobilization at sensor surfaces is of great interest within various scientific fields, since it enables studies of specific biomolecular interactions. To achieve this, one must be able to immobilize proteins with retained native structure, while minimizing non-specific protein binding. The high affinity interaction between streptavidin (SA) and biotin is extensively used as a linker between a surface, where SA is immobilized, and the (biotinylated) molecule of interest. Self- assembled monolayers (SAMs) of poly- and oligo ethylene glycol (PEG and OEG) derivatives have been proven in literature to minimize non-specific protein binding, and biotin-exposing SAMs have been shown efficient for immobilization of SA. The aim of this master's thesis project was to develop biotinylated gold surfaces for quartz crystal microbalance with dissipation monitoring (QCM-D) applications through the self-assembly of mixed monolayers of thiolated OEG (or PEG) derivatives with or without a terminal biotin head group. For this, different thiol compounds were to be compared and evaluated. For the systems under study, the required biotin density for maximum specific SA immobilization was to be established, while keeping the non-specific serum adsorption at a minimum. Model experiments with biotinylated proteins immobilized to the SA-functionalized surfaces were to be performed to evaluate the possibilities for commercialization. A protocol for the preparation of a novel biotinylated surface was developed based on the immersion of gold substrates in an ethanolic incubation solution of dithiols with OEG chains (SS-OEG and SS-OEG-biotin, 99:1) and found to give reproducible results with respect to low non-specific protein binding and immobilization of a monolayer of SA. The modified surfaces allowed for subsequent immobilization of biotinylated bovine serum albumin (bBSA) and biotinylated plasminogen (bPLG). PLG was the subject of a challenging case study, using a combination of QCM-D and surface plasmon resonance (SPR), where the immobilized protein was subjected to low molecular weight ligands that were believed to induce conformational changes. The high control of the surface chemistry allowed for the interpretation of the increased dissipation shift upon ligand binding in terms of conformational changes. An obstacle before commercialization of the described biotinylated surfaces is that they do not seem stable for storage &gt; 7 days. The reasons for this have to be investigated further.