David Richard Walker’s Metrology of the Roman Silver Coinage analyzed the silver content of over 5000 Roman denarii, antoniniani, and drachmae using x-ray fluorescence (XRF) spectrometry. His results have been widely cited and used by scholars in the fields of Roman economic theory and numismatics. This thesis seeks to prove that Walker’s XRF results were not only inaccurate, but inconsistently so. Corrosion and surface enrichment on silver-copper coins have caused surface-level elemental examinations, like XRF, to produce incorrect results. The results from Walker’s XRF analysis have been compared against results from four individual wet chemical studies. The comparisons display striking, and significant, differences. I am forced to conclude that Walker’s data does not in any way align with the true silver content of the coins he analyzed. As a result, this thesis will re-examine several theories and hypotheses posed by scholars who used Walker’s data and propose new, more appropriate, uses for Walker and XRF analysis outside of the examination of corroded silver-copper coins.

Oxide nanowire arrays are playing an important role in energy sciences nowadays, including energy harvesting, energy storage, and power management. By utilizing a wet chemical growth method, we demonstrated the capabilities of synthesizing density controlled vertical ZnO nanowire arrays on a general substrate, optimizing the aspect ratio of the vertical ZnO nanowire arrays guided by a statistical method, epitaxially growing patterned vertical ZnO nanowire arrays on inorganic substrates, epitaxially growing patterned horizontal ZnO nanowire arrays on non-polar ZnO substrates, and the lift-off of the horizontal ZnO nanowire arrays onto general flexible substrates. In addition, single crystalline PbZrxTi1-xO3 (PZT) nanowire arrays were epitaxially grown on conductive and nonconductive substrates by hydrothermal decomposition. Beyond that, based on the as-synthesized ZnO nanowire arrays, we demonstrated multilayered three dimensionally integrated direct current and alternating current nanogenerators. By integrating a ZnO nanowire based nanogenerator with a ZnO nanowire based nanosensor, we demonstrated solely ZnO nanowire based self-powered nanosystems. Also, utilizing a commercial full-wave bridge rectifier, we rectified the alternating output charges of the nanogenerator based on PZT nanowire arrays, and the rectified charges were stored into capacitors, which were later discharged to light up a laser diode (LD). In addition, blue/near-ultraviolet (UV) light emitting diodes (LED) composed of ordered ZnO nanowire arrays on p-GaN wafers were presented.

Natural nanominerals are abundant in Earth's critical zone and important in innumerable environmental processes that affect water quality. The chemical behavior of many natural nanominerals is related to their extreme small size (<10 nm) and high surface area. Atomic structural and chemical heterogeneity are also important factors affecting nanoparticle reactivity, and are a consequence of the mechanisms and complex (natural) conditions by which they form. The relationships between these factors remain poorly understood and limit our ability to predict the formation, transformation, and chemical behavior of natural nanominerals in the environment. We are using a poorly crystalline ferric hydroxysulfate nanomineral, schwertmannite, as a model system to understand the effect of formation conditions, specifically solution chemistry, on its physico-chemical characteristics. Previous studies indicate schwertmannite has highly variable bulk sulfate (Fe/S molar from 3-15) and water contents (Caraballo et al., 2013). In addition, both natural and synthetic schwertmannites have recently been described as "polyphasic" (i.e., consisting of sulfate-poor, goethite-like ordered domains embedded in a sulfate-rich, amorphous material) from observations using transmission electron microscopy (French et al., 2012). We hypothesize that solution chemistry at the time of schwertmannite formation directly affect its composition and structure. Using a factorial experiment design, we investigated the effects of increasing solution sulfate concentration ([SO4]/[Fe] at 1, 2, 3 and 5) and pH (2.4-5.6) on the crystallinity and composition of the products. Ferric hydroxide and hydroxysulfate solids were precipitated in batches by the rapid oxidation of Fe(II) by hydrogen peroxide, similar to what is seen in natural environmental systems. Sulfate and hydroxide concentrations were varied by addition of NaSO4 and NaOH, respectively. Solids were characterized using synchrotron X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), inductively coupled plasma-mass spectrometry (ICP-MS), scanning electron microscopy (SEM), and high resolution- transmission electron microscopy (HR-TEM). Our results show that schwertmannite is the only precipitate formed at low pH and that goethite rapidly becomes dominant at pH > 3.5. High-resolution TEM showed our synthetic schwertmannite samples consist of poorly crystalline goethite-like nanodomains within an amorphous solid, similarly seen in previous results. ICP-MS results reveal a narrow Fe/S molar ratio of 4.5 ±0.1 for our synthetic schwertmannite, which suggests that schwertmannite chemical composition does not depend strongly on pH or initial solution sulfate concentration. Increasing pH from 2.4 to 3.2 also has little effect on the crystallinity, bulk Fe/S ratio and water contents of schwertmannite. Increasing solution [SO4]/[Fe] also has little to no impact on crystallinity, water content or the amount of sulfate incorporated in schwertmannite. Thus, schwertmannite crystallinity and composition is not affected by initial solution sulfate and concentration under our experimental conditions. Thermal analysis allows us to independently measure OH and SO4 content in synthetic schwertmannite. In doing so, we propose a more accurate chemical formula (Fe8Oz(OH)24-2z-2x(SO4)x). The average stoichiometry based on thermal analysis of schwertmannite precipitated at [SO4]/[Fe] = 1 and pH ranging from ~2.4 2.9 is Fe8O6.51(OH)8.4(SO4)1.28. Interestingly, the calculated number of moles of oxygen is less than 8, which suggests that the standard formula Fe8O8(OH)8-2x(SO4)x is incorrect. These results for synthetic samples provide important constraints for future studies aimed at better understanding the formation, compositional variability and chemical behavior of natural schwertmannite. / Master of Science

No description available.

Optical resonators, which confine light by resonant recirculation, serve as the basis for a wide variety of optical components. Though they appear in many geometric forms, the most effective of optical resonators show axial symmetry in at least one dimension. A popular variation that finds broad application is the dielectric sphere. Acclaimed for their high quality (Q) factor and small modal volume, spheres owe credit of these attractive features to their support of whispering gallery mode (WGM) resonances. The sensitivity of a resonance's frequency and Q to strain, temperature, and other parameters of the surrounding medium can be the basis for ultracompact modulators and sensors. Physically, WGMs are special optical modes which can be understood as light rays that orbit the equator of the sphere guided by total internal reflection. Like a smooth stone can be skipped along the surface of a pond, light can be confined to the inside of a sphere by successive reflections. To best excite WGMs, the source light should initially trace a line tangent to the sphere's circumference. But incorporating a tiny sphere with such nanometric tolerances into a practical sensor structure has its challenges and the prospects for microsphere applications have suffered because of the plight of this problem. The work in this dissertation details the fabrication and function of three new "press fit" spherical resonators. These etched fiber micro-devices were developed to meet the demand for a robust, self-integrated means of coupling light between an optical fiber and WGMs in a microsphere resonator. The etching processes have been tuned to enable secure storage of a microsphere while also providing efficient excitation and interrogation of WGMs. Furthermore, the methods have been designed to be staightforward, quick, and repeatable. Using standard etchants on common polarization-maintaining fiber with readily purchased microspheres, the press fit resonators demonstrated here can be batch-fabricated and assembled. The press fit spherical resonator offers an alignment-free and conveniently pigtailed WGM coupler that has great potential for bio-science sensing applications and studies of resonant bispheres. / Ph. D.

The goal of this thesis is the development of scalable, low cost synthesis of metal oxide nanostructures based electrodes and to correlate the chemical modifications with their energy conversion performance. Methods in energy conversion in this thesis have focused on two aspects; a potentiometric chemical sensor was used to determine the analytical concentration of some components of the analyte solution such as dopamine, glucose and glutamate molecules. The second aspect is to fabricate a photo-electrochemical (PEC) cell. The biocompatibility, excellent electro-catalytic activities and fast electron transfer kinetics accompanied with a high surface area to volume ratio; are properties of some metal oxide nanostructures that of a potential for their use in energy conversion. Furthermore, metal oxide nanostructures based electrode can effectively be improved by the physical or a chemical modification of electrode surface. Among these metal oxide nanostructures are cobalt oxide (Co3O4), zinc oxide (ZnO), and bismuth-zincvanadate (BiZn2VO6) have all been studied in this thesis. Metal oxide nanostructures based electrodes are fabricated on gold-coated glass substrate by low temperature (&lt; 100 0C) wet chemicalapproach. X-ray diffraction, x-ray photoelectron spectroscopy and scanning electron microscopy were used to characterize the electrodes while ultraviolet-visible absorption and photoluminescence were used to investigate the optical properties of the nanostructures. The resultant modified electrodes were tested for their performance as chemical sensors and for their efficiency in PEC activities. Efficient chemically modified electrodes were demonstrated through doping with organic additives like anionic, nonionic or cationic surfactants. The organic additives are showing a crucial role in the growth process of metal oxide nanocrystals and hence can beused to control the morphology. These organic additives act also as impurities that would significantly change the conductivity of the electrodes. However, no organic compounds dependence was observed to modify the crystallographic structure. The findings in this thesis indicate the importance of the use of controlled nanostructures morphology for developing efficient functional materials.

Denna studie har utförts på Calamo AB som arbetar med elektropolering och betning av rostfritt stål. Efter ytbehandlingssteget krävs sköljning av godset för att avlägsna kemikalierester vilket medför att stora mängder surt sköljvatten uppstår. Idag används våtkemisk fällningsanläggning för att rena sköljvattnet. Det befintliga reningsverket kräver flertalet tillsatser samtidigt som mängden slam som går till deponi är stor. Företaget vill utreda miljönyttan med att installera en vakuumindunstare för att ersätta det befintliga reningsverket som reningsmetod samt se över möjligheten att minska sin vattenförbrukning i samband med sköljning av gods för att bland annat kunna reducera storleken på indunstaren, minska belastningen på reningsstegen samt reducera mängden avfall. Studiens mål var att kartlägga uppkomsten av förorenat sköljvatten, identifiera potentiella vattenbesparande åtgärder och hur dessa åtgärder påverkar effektiviteten hos reningsanläggningarna. Samt visa hur installation av en vakuumindunstare förändrar företagets miljöpåverkan och utreda om det finns möjligheter att återanvända eller återvinna kemikalier och metaller från processen. Kartläggning och flödesmätningar av sköljvattenbehovet utfördes med hjälp av information av personal på Calamo samt en ultraljudsmätare. Vattenbesparande åtgärder, påverkan på reningsanläggning samt möjligheter till återvinning av kemikalier undersöktes genom litteraturstudie samt modellering i Excel. Utredningen av miljönyttan genom att ersätta befintligt reningsverk med vakuumindunstare utfördes med hjälp av LCA-värden hämtade från databasen SimaPro 8.0.4. Flera olika förslag på vattenbesparande åtgärder studerades och dessa gav en total vattenreduktion till reningsverket på mellan 5 - 81 % beroende på hur många samt vilka åtgärder som vidtogs. Enligt miljöberäkningarna genererar vakuumindunstaren 3 gånger högre utsläpp av koldioxidekvivalenter och 7 gånger större behov av icke förnyelsebar energi jämfört med det befintliga reningsverket. Genom att installera sprutskölj med motströmsteknik i stycke, sammankoppla befintliga sköljkar i avdelningarna betning, AVFKA samt automaten och installera sparsköljstank i alla avdelningar uppnås en reduktion av förorenat vatten till reningsstegen på 81%, vilket ytterligare kan optimeras genom installation av jonbytare, återanvändning av varmt vatten från renrum. Dessutom ökar föroreningshalten med 61% då dessa åtgärder vidtas vilket gynnar reningseffektiviteten i reningsanläggningarna och därav rekommenderas detta alternativ. Även kemikalieanvändningen och förluster av metalljoner reduceras avsevärt i processen genom användningen av sparskölj. Att installera vakuumindunstare rekommenderas inte på grund av dess stora energianvändning, dock kan andra resultat uppstå då andra LCA-värden används samt genom andra antaganden och hänsyn till kemikalie- och metallåtervinning istället för deponi. / This study has been carried out at Calamo AB, which works with electropolishing and pickling of stainless steel. After the surface treatment step, rinsing of the material is required to remove chemical residues, which results in large amounts of acid rinse water. Today, wet chemical precipitation plant is used to clean the rinse water. The existing treatment plant requires most additives, while the amount of sludge that goes to landfill is large. The company wants to investigate the environmental benefits of installing a vacuum evaporator to replace the existing sewage treatment plant as a purification method and to review the possibility of reducing its water consumption in connection with rinsing of goods in order to reduce the size of the evaporator, reduce the load on the purification steps and reduce the amount of waste. The aim of the study was to map the emergence of polluted rinse water, identify potential water-saving measures and how these measures affect the efficiency of the treatment plants. And show how the installation of a vacuum evaporator changes the company's environmental impact and investigate whether there are opportunities to reuse or recycle chemicals and metals from the process. Mapping and flow measurements of the rinse water requirement were performed using information from staff at Calamo and an ultrasonic meter. Water-saving measures, impact on treatment plant and opportunities for recycling of chemicals were investigated through literature study and modeling in Excel. The study of the environmental benefits by replacing existing treatment plants with vacuum evaporators was carried out using LCA values obtained from the database SimaPro 8.0.4. Several different proposals for water-saving measures were studied and these gave a total water reduction to the treatment plant of between 5 - 81% depending on how many and what measures were taken. According to the environmental calculations, the vacuum evaporator generates 3 times higher emissions of carbon dioxide equivalents and 7 times the need for non-renewable energy compared to the existing treatment plant. By installing spray rinse with countercurrent technology in one piece, interconnecting existing rinses in the cuttings departments, AVFKA as well as the dispenser and installing sparse rinse tank in all departments, a reduction of contaminated water to the purification steps of 81% is achieved, which can be further optimized by installation of ion exchangers, reuse of hot water from clean room. In addition, the pollutant content increases by 61% as these measures are taken, which favors the purification efficiency of the treatment plants and hence this option is recommended. The use of chemicals and losses of metal ions are also considerably reduced in the process through the use of savings rinses. Installing vacuum evaporators is not recommended due to its large energy use, however, other results may arise when other LCA values are used, as well as through other assumptions and considerations for chemical and metal recycling instead of landfill.

No description available.

Often synthetic graphene requires transfer onto an arbitrary substrate prior to use because the substrate it was originally synthesized on is inappropriate for either electrical measurement or characterization. While a variety of routes have been developed they are substrate dependant and often involve the use of harsh treatments. Here we present a facile and cheap route that can be applied to graphene over any substrate. This universal transfer route is based on a wet chemical reaction producing gaseous species which can intercalate between the substrate and the graphene and thus gently delaminate the two.

Der Siliciumauflöseprozess in HF-HNO3-H2SO4/H2O-Lösungen unterscheidet sich vom Ätzprozess in HF-HNO3-H2O-Standardmischungen in Bezug auf die Reaktivität gegenüber Silicium, erzielte Oberflächenmorpholgien sowie die beim Ätzen entstehenden gelösten und gasförmigen Produkte. Durch die Behandlung in H2SO4-reichen HF-HNO3-H2SO4/H2O-Lösungen werden auf Siliciumwafern Texturen mit hoher Rauigkeit und geringer Reflexion erzeugt. mc-Si-Solarzellen texturiert durch eine H2SO4-reiche Ätzlösung weisen vergleichend zu Solarzellen mit Standardtexturen höhere Wirkungsgrade auf. In HF-HNO3-H2SO4/H2O-Lösungen mit hohen Schwefelsäurekonzentrationen (c(H2SO4) > c(H2O)) wirkt sowohl das Salpetersäuremolekül HNO3 als auch das Nitrylion NO2+ als Oxidationsmittel. Trifluorsilan HSiF3 und Hexafluordisiloxan F3SiOSiF3 wurden erstmalig als gasförmige Produkte des sauren nasschemischen Ätzens identifiziert. Anhand von Modellreaktionen zur Reaktivität von Nitrylionen wurde deren Reduktionssequenz im Siliciumätzprozess aufgeklärt.