FABRICATION OF NANOPOROUS GOLD AND BIOLOGICAL APPLICATIONS By Badharinadh Uppalapati A Dissertation submitted in partial fulfillment of the requirements for the degree of Master of Science at Virginia Commonwealth University. Virginia Commonwealth University, 2014 Major Director: Maryanne M. Collinson, Professor, Department of Chemistry Fabrication of nanoporous gold electrodes by dealloying Au:Ag alloys has attracted much attention in sensing applications. In the first part of this work, the electrochemical response of the redox active molecule, potassium ferricyanide, in a solution of bovine serum albumin in buffer, serum or blood was studied using nanoporous gold and comparisons made to planar gold. Nanoporous gold electrodes with different surface areas and porosity were prepared by dealloying Au:Ag alloy in nitric acid for different dealloying times, specifically, 7.5, 10, 12.5, 20 minutes. Characterization was done using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), and cyclic voltammetry (CV). Using cyclic voltammetry, planar gold electrodes exposed to bovine serum albumin in buffer showed a decrease in Faradaic peak current and an increase in peak splitting for potassium ferricyanide. The time required for the peak Faradaic current to drop to one-half of its original value was 3 minutes. At nanoporous gold electrodes, however, no significant reduction in Faradaic peak current or increase in peak splitting was observed. Nanoporous gold electrodes having the smallest pore size and largest surface area showed ideal results to biofouling. These electrodes are believed to impede the mass transport of large biomolecules while allowing small redox molecules to exchange electrons effectively with the electrode. In the second part of this work, the open circuit potential (OCP) of biologic solutions (e.g., blood) was measured using nanoporous gold electrodes. Historically, the measurement of blood redox potential has been hindered due to significant fouling and surface passivation of the metal electrodes. As nanoporous gold electrodes retained electrochemical activity of redox probes like potassium ferricyanide in human serum and rabbit blood, they were used to measure the OCP of blood and plasma from various animals like pig, rabbit, rat, monkey and humans. Comparisons were made to planar gold electrodes. The OCP values at both the planar gold and nanoporous gold electrodes were different from each other and there was variability due to different constituents present in blood and plasma. The OCP of rabbit blood and crashed rabbit blood was measured and the values were found to be different from each other indicating that ORP helps in measuring the animal condition. Ascorbic acid was added to rabbit and sheep blood and OCP measured at the nanoporous electrodes. Addition of reducing agent to blood at different intervals and different concentrations showed a change in potential with concentration.

According to the National Institute of Occupational Safety and Health (NIOSH), about 100 million rock anchors were installed in the USA mining industry during 1999 (Dolinar, 2000). The rock bolt usage in US coal mining industry fell from 85 million in the year 1988 to 68 million by 2005 (Tadolini, 2006), and is assumed to be close to that number of rock anchors consumed currently since, the tonnage from underground is almost the same. Most underground coal mines have conditions such as moisture in the atmosphere, ground water with different chemical contents that are conducive for corrosion of rock anchors and ancillaries (such as plates), and the effects of this on the performance of the anchors had been researched in the US to an extent from the past research at Southern Illinois University Carbondale (SIUC). In addition to the general corrosion like pitting and crevice, stress corrosion adds to the process a potentially serious threat and results in material failure underground due to stress corrosion cracking (SCC) yet the effects are not fully understood in the USA. The results of this research therefore will have a positive and direct effect on rock related safety. During this research project in situ specific tests were conducted with bolts to try and determine the corrosion potential in a specific coal-mining region. The coal mining areas were divided into three regions and were named as East, Mid-West and West respectively. To enhance the value/importance of the field data collected from the mines, a metal mine and a salt mine (two non-coal mines) were included in the plan and the data analysis proved that the methodology developed for determining the corrosion potential underground is applicable to any underground mines. The Insitu studies include water samples collection and analysis and open circuit potential (OCP/Eoc) testing and analysis. Open Circuit Potential (OCP) data were recorded to estimate probability of active corrosion. Hypothetically, probability of active corrosion is lower if the actual OCP of roof bolts in the mine is less than the characteristic OCP of the steel grade, and vice versa. The effects of certain factors such as the roof condition, reference distance (distance between bolt and reference electrode) on the open circuit potential data during the measurements were studied to ensure its impact on the corrosion potential determination technique developed. The findings from this research helps standardize the corrosion potential determination methodology. The preliminary study of stress corrosion cracking of the subject test sample (Grade 60 rebar roof bolt) was conducted in this research work. The experimental study invloves testing a complete roof bolt in the mine simulated environment. The mine simulated environment in the test cell consists of the roof strata material collected from the mine site with continuous flow of water at slower and varaible flow rate (0 to 3 ml/minute) with pH in the range of 7.5 to 9.0. The results showed that stress corrosion could be very serious problem when it comes to long term mining applications. The stress corrosion test cell developed and tested was proved to be significant in conducting the long term stress corrosion tests. The strength results of the Grade 60 rebar roof bolt tested had a significant strength loss after 3 months of testing in the stress corrosion cell. Hence, more SCC studies are deemed necessary to evaluate the seriousness of the problem and if possible eliminate it.

No description available.

Apesar de toda a atenção dada à eletro-oxidação do íon boroidreto, pela possibilidade de seu uso em células a combustível, pouco se tem discutido a respeito das instabilidades cinéticas associadas a esse processo. A maioria das pesquisas tem como foco o estudo da cinética dos processos na região de baixos sobrepotenciais, numa região relativamente próxima ao estado de equilíbrio termodinâmico. Em uma região afastada do equilíbrio, diferentes mecanismos regem o sistema e desta forma diferentes informações podem ser obtidas. O objetivo da presente dissertação consiste na investigação sistemática da cinética complexa associada aos processos de adsorção, oxidação e interação do íon boroidreto em superfícies policristalinas de platina. As investigações foram realizadas em condições afastadas do equilíbrio utilizando-se técnicas eletroquímicas convencionais, incluindo: voltametria cíclica, cronoamperometria, experimentos quase estacionários sob controle potenciostático utilizando diferentes valores de resistência total e transientes de circuito aberto. Dentre os resultados obtidos pode-se destacar: a alta velocidade na redução dos óxidos de platina em transientes de circuito aberto (i.e. 0,5 s), sendo esta mais alta do que para álcoois ou hidrogênio; dois processos auto-catalíticos no perfil de potencial de circuito aberto, que podem ser relacionadas com uma biestabilidade do sistema; as oscilações de corrente obtidas em experimentos quase estacionários utilizando diferentes valores de resistência externa; e as oscilações de baixa frequência obtidas na ausência de resistência externa presentes em uma ampla faixa de potencial. Estes resultados apresentam aspectos tecnológicos, como a relação direta entre o baixo tempo de redução de óxido e a perda de desempenho de células a combustível por conta de difusão de combustível, e fundamentais, como a emergência de oscilações e a caracterização do sistema como N-NDR, que podem contribuir para um maior entendimento sobre o uso deste combustível. Esses são resultados ainda não explorados na literatura e o presente trabalho propõe o preenchimento desta lacuna. / Despite all attention given to the electro-oxidation of the ion borohydride, for its applicability in fuel cells, few discussions have been made on the kinetical instabilities possibly present on this process. Most researches focuses on the kinetical study of these processes at a low overpotential range, relatively close to the thermodynamic equilibrium. Under far from thermodynamic condition, different mechanisms rule the system and different information can be obtained. The present dissertation aims at a systematic investigation of the complex kinetic associated to the adsorption, oxidation and interaction processes of the borohydride ion over polycrystalline platinum surface. The investigations were realized under far from thermodynamic equilibrium conditions using conventional electrochemical techniques, including: cyclic voltammetry, chronoamperometry, quasi-steady experiments under potentiostac control using different values of external resistance and open circuit transients. Among the results it is possible to highlight: the fast reduction of platinum oxides in open circuit transients (i.e. 0.5s), which is faster than when alcohol or hydrogen is used; two auto-catalytic processes in the open-circuit profile, which can be related to a bistability of the system; current oscillations in quasi-steady experiments using different values of external resistances; and the low frequency oscillations obtained without external resistance under a large potential range. These results show technological aspects, such as the direct relationship of the short time for oxide reduction and the performance loss of a fuel cell by crossover, and fundamental, such as the emergency of oscillations and the characterization of the system as a N-NDR, which can contribute to a better understanding of this fuel. These are yet not explored results in literature and the present research propose filling the gap.

Increased equipment failures and the resultant increase in unplanned downtime as the result of process optimization programs continue to plague pulp mills. The failures are a result of a lack of understanding of corrosion in the different pulping liquors, specifically the parameters responsible for its adjustment such as the role and identification of inorganic and organic species. The current work investigates the role of inorganic species, namely sodium hydroxide and sodium sulfide, on liquor corrosivity at a range of process conditions beyond those currently experienced in literature. The role of sulfur species, in the activation of corrosion and the ability of hydroxide to passivate carbon steel A516-Gr70, is evaluated with gravimetric and electrochemical methods. The impact of wood chip weathering on process corrosion was also evaluated. Results were used to identify black liquor components, depending on the wood species, which play a significant role in the activation and inhibition of corrosion for carbon steel A516-Gr70 process equipment. Further, the effect of black liquor oxidation on liquor corrosivity was evaluated. Corrosion and stress corrosion cracking performance of selected materials provided information on classes of materials that may be reliably used in aggressive pulping environments.

Apesar de toda a atenção dada à eletro-oxidação do íon boroidreto, pela possibilidade de seu uso em células a combustível, pouco se tem discutido a respeito das instabilidades cinéticas associadas a esse processo. A maioria das pesquisas tem como foco o estudo da cinética dos processos na região de baixos sobrepotenciais, numa região relativamente próxima ao estado de equilíbrio termodinâmico. Em uma região afastada do equilíbrio, diferentes mecanismos regem o sistema e desta forma diferentes informações podem ser obtidas. O objetivo da presente dissertação consiste na investigação sistemática da cinética complexa associada aos processos de adsorção, oxidação e interação do íon boroidreto em superfícies policristalinas de platina. As investigações foram realizadas em condições afastadas do equilíbrio utilizando-se técnicas eletroquímicas convencionais, incluindo: voltametria cíclica, cronoamperometria, experimentos quase estacionários sob controle potenciostático utilizando diferentes valores de resistência total e transientes de circuito aberto. Dentre os resultados obtidos pode-se destacar: a alta velocidade na redução dos óxidos de platina em transientes de circuito aberto (i.e. 0,5 s), sendo esta mais alta do que para álcoois ou hidrogênio; dois processos auto-catalíticos no perfil de potencial de circuito aberto, que podem ser relacionadas com uma biestabilidade do sistema; as oscilações de corrente obtidas em experimentos quase estacionários utilizando diferentes valores de resistência externa; e as oscilações de baixa frequência obtidas na ausência de resistência externa presentes em uma ampla faixa de potencial. Estes resultados apresentam aspectos tecnológicos, como a relação direta entre o baixo tempo de redução de óxido e a perda de desempenho de células a combustível por conta de difusão de combustível, e fundamentais, como a emergência de oscilações e a caracterização do sistema como N-NDR, que podem contribuir para um maior entendimento sobre o uso deste combustível. Esses são resultados ainda não explorados na literatura e o presente trabalho propõe o preenchimento desta lacuna. / Despite all attention given to the electro-oxidation of the ion borohydride, for its applicability in fuel cells, few discussions have been made on the kinetical instabilities possibly present on this process. Most researches focuses on the kinetical study of these processes at a low overpotential range, relatively close to the thermodynamic equilibrium. Under far from thermodynamic condition, different mechanisms rule the system and different information can be obtained. The present dissertation aims at a systematic investigation of the complex kinetic associated to the adsorption, oxidation and interaction processes of the borohydride ion over polycrystalline platinum surface. The investigations were realized under far from thermodynamic equilibrium conditions using conventional electrochemical techniques, including: cyclic voltammetry, chronoamperometry, quasi-steady experiments under potentiostac control using different values of external resistance and open circuit transients. Among the results it is possible to highlight: the fast reduction of platinum oxides in open circuit transients (i.e. 0.5s), which is faster than when alcohol or hydrogen is used; two auto-catalytic processes in the open-circuit profile, which can be related to a bistability of the system; current oscillations in quasi-steady experiments using different values of external resistances; and the low frequency oscillations obtained without external resistance under a large potential range. These results show technological aspects, such as the direct relationship of the short time for oxide reduction and the performance loss of a fuel cell by crossover, and fundamental, such as the emergency of oscillations and the characterization of the system as a N-NDR, which can contribute to a better understanding of this fuel. These are yet not explored results in literature and the present research propose filling the gap.

Recently, conductive polymer/carbon nanomaterials have drawn attention for use in corrosion inhibition, sensors, energy storage devices, and coatings for electromagnetic shielding applications due to their good mechanical properties and electronic conductivity. Therefore, efforts have been made to find fast and facile methods for the synthesis and development of these hybrids that allow control over key parameters, such as the thickness of the conductive polymer coating. In this study, such hybrids were prepared using polyaniline (PANI) as the conductive polymer and vapor-grown carbon nanofibers (VGCNFs) as the carbon nanomaterial or filler by a semi-dilute in situ polymerization method to be evaluated for their effectiveness as corrosion inhibitory additives to alkyd paints. Spectroscopic, colorimetric, and electric properties of PANI-coated VGCNFs were investigated. The thickness of the PANI coating, along with other parameters, impacts the behavior and mechanisms by which the nanomaterial performs its role in a given application, particularly in the corrosion inhibition processes. Thus, different synthesis conditions, including pretreatment of the nanofibers, the presence of sodium dodecyl sulfate (SDS) surfactant, PreT-VGCNF/ANI ratios (w/w), and polymerization times were tested and their effects on the PANI thickness were microscopically and statistically evaluated. It was found that only different PreT-VGCNF/ANI ratios allowed definite control of the PANI thickness. No clear effect on the thickness was observed after three hours of polymerization. The presence of SDS and pretreatment of VGCNFs displayed a synergistic effect on the appearance and thickness of the PANI film. PANI-coated VGCNF additives, with PANI in the leucoemeraldine base (LEB) and emeraldine base (EB) forms, were synthesized using a PreT-VGCNF/ANI ratio of 0.4 in the presence of SDS. Cold-rolled steel coupons were coated with 20-30 ìm thick alkyd paint coatings, and their electrochemical behavior was investigated by open circuit potential (OCP) and electrochemical impedance (EIS) measurements. The results indicate that, overall, EB/VGCNF additive performed better as a corrosion inhibitor, followed by PreT-VGCNF and LEB/VGCNF additives.

På senare år har efterfrågan på stålmaterial av låg vikt ökat, speciellt inom transportsektorn. Genom att addera Al till stål sänks densiteten vilket gör att FeAl-legeringar är ett lovande material för fordonskonstruktion. Vätskekorrosionsegenskaper undersöktes av 3D – printade FeAl prover som innehöll 0 – 10 vikt% Al och 0,1 vikt% Zr för att bestämma hur korrosionsegenskaperna förändrades med avseende på Al – innehållet. Korrosionsresistansen var i stor utsträckning beroende av huruvida en passiv film av Al2O3 bildades på ytan eller ej. Korrosionshastigheten bestämdes genom EIS – och PDP – analyser utförda i 3,5 vikt% NaCl-lösning samt genom viktförlusttester i 1 M HCl respektive 0,5 M H2SO4. Vidare karaktäriserades proverna genom XRF, XRD, EDS, SEM och optisk mikroskopi vilket bland annat visade på att samtliga prover var enfassystem samt att den kemiska sammansättningen var enligt förväntan. Vidare indikerade optisk mikroskopi och SEM att ett högre Al – innehåll resulterar i att proverna blir mer porösa. Elektrokemiska tester antyder att ett Al – innehåll om 10 vikt% förbättrade korrosionsresistansen. Detta antyder möjligen, men kan inte definitivt fastslås från de utförda experimenten, att det krävs 10 vikt% Al för att en passiv film som täcker hela materialytan ska bildas. Korrosionshastigheten var 7 – 10 gånger högre vid viktförlusttest jämfört med elektrokemiska test. Detta förklaras genom att den skyddande passiva filmen bröts ned under de sura förhållanden som viktförlusttesten utfördes i medan den passiva Al2O3 filmen kunde bestå i de pH – neutrala förhållanden som elektrokemiska test utfördes vid. Detta speglar att bildandet och stabiliteten av Al2O3-filmen är vitalt för att sänka korrosionshastigheten. / In recent years the demand for lightweight ferritic steels has increased, particularly for transport applications. The addition of Al lowers the density, hence making FeAl alloys promising materials for such constructions. Aqueous corrosion properties of 3D – printed FeAl samples ranging from 0 – 10 wt% Al and containing 0.1 wt% Zr were investigated to determine how the Al content affects the corrosion resistance. The corrosion rate was found to greatly depend on the formation and stability of a protective passive film of Al2O3 forming on the material surface. A corrosion rate was obtained via EIS and PDP in 3.5 wt% NaCl as well as via weight loss testing in 1 M HCl and 0.5 M H2SO4. Additionally, XRF, XRD, EDS, SEM and optical microscopy tests were carried out to characterize the samples. XRF and EDS confirmed that the elemental composition of the samples was as expected and XRD indicated that all samples were single phase systems. Furthermore, optical microscopy and SEM indicated that higher Al content makes the samples more porous. Electrochemical testing indicated that addition of 10 wt% Al greatly improves the corrosion properties suggesting that it may require 10 wt% Al to form a passive film that covers the whole surface, although this cannot be said for certain from these experiments. Moreover, the corrosion rate was 7 – 70 times lower during electrochemical testing compared to weight loss testing, in which the passive film breaks down due to the acidic conditions. This emphasizes that the stability of the Al2O3 film is vital for slowing down the corrosion rate of FeAl alloys.

Organic coatings are extensively used as protective coatings in several industries including the automotive and aircraft industries. The last few years have witnessed an increased interest in improving not only the mechanical properties but also the corrosion protection properties of organic coatings. Among the currently investigated methods of improving the performance of organic coatings is the incorporation of additives in the organic paint matrix. Vapor grown carbon nanofibers (VGCNFs) are a class of carbon fibers that are produced by catalytic dehydrogenation of a hydrocarbon at high temperatures. Depending on the method of synthesis and the post-treatment processes, the diameter of the VGCNFs is normally in the 10-300 nm range. The small size, light weight, high aspect ratio, and unique physical, thermal, mechanical, and electrical properties of VGCNF make it an ideal reinforcing filler in polymer matrix nanocomposites to enhance the mechanical properties of the pure polymeric material in high performance applications in several industries such as the automotive, aircraft, battery, sensors, catalysis, electronics, and sports industries. The main objective of the current investigation was to study the corrosion protection offered by the incorporation of VGCNFs into a commercial alkyd paint matrix applied to the surface of mild steel coupons. The corrosion protection was investigated by immersing samples in air saturated 3% NaCl solution (artificial seawater). The samples were studied by electrochemical impedance spectroscopy (EIS) along with other measurements, including electrochemical (open circuit potential, cyclic voltammetry), chemical (salt spray test), electrical conductivity, and surface analysis (SEM, AFM, optical profilometry, and nanoindentation). The study involved the investigation of the effect of the weight percent (wt %) of the VGCNF as well as the coating film thickness on the corrosion protection performance of the coated steel samples when exposed to the corrosive electrolyte. By way of contrast, the EIS behavior of steel coupons coated with a paint coating incorporating different weight percents of powdered silicon carbide (SiC) particles was also studied. The EIS spectra were used to calculated and graph several corrosion parameters for the investigated systems. At the end, the studied coatings were ranked in order of their anticorrosive properties.