Summary Serpentinites from the northern Vermont were examined for the distribution and abundance of As. XRD and electron microprobe showed the samples are composed of antigorite, chromite, magnetite, and carbonate minerals (magnesite, dolomite, calcite). The concentration in As when the samples were dissolved in H3PO4 was 10% of the concentration in As when the samples were dissolved in concentrated HF/HNO3, suggesting that As is mainly incorporated in the structure of antigorite. X-ray absorption near-edge structure spectra showed that the As is As(III) in the samples. Extended X-ray absorption fine structure spectra suggested that the As has a tetrahedral coordination and is located in the Si-site in serpentine.

We have performed fluorescence extended X-ray absorption fine structure (EXAFS) measurements on the Cd K-edge of partial electrolyte (PE) treated Cu(In[subscript 0.7]Ga[subscript 0.3])Se��� (CIGS) thin film samples using synchrotron X-ray radiation. This data was compared to the EXAFS spectra of CdSe and CdO standards. Cd local structure models were constructed and used for the least square analysis of the spectra. The first model employed implantation of a cadmium atom and a single oxygen atom into the CIGS lattice. Specifically, an oxygen atom was introduced in the tetrahedral bonded Cd-Se local structure. Employing FEFF8 with WinXAS software package, experimental data was theoretically fitted to the first shell single-scattering paths of the Cd atom in the (PE) treated Cu(In[subscript 0.7]Ga[subscript 0.3])Se��� thin film samples. The main peak observed in the data represents the Cd-Se bonds and the shoulder corresponds to the Cd-O bond. However, the number of total nearest neighbors is not consistent with this model. A two-phase model that includes both Cd-Se tetrahedron and Cd-O octahedron were then reconstructed. Again, a least-agrees very well with the experimental data, and the total first nearest neighbor number is consistent with the two phase model at NN=4.2. This study indicates the surface of Cd partial electrolyte treated Cu(In[subscript 0.7]Ga[subscript 0.3])Se��� thin films contains both CdSe and CdO. / Graduation date: 2004

La diffraction des neutrons avec substitution isotopique du fer combinée avec des simulations structurales (Empirical Potential Structure Refinement, EPSR) a permis de sonder les sites de Fe2+ et de Fe3+ dans un verre NaFeSi2O6 oxydé. Cette étude met en évidence la présence de deux sites pour Fe3+. 70% du Fe3+ est en site tétraédrique (dFe3+-O=1.866±0.001 Å), le reste de Fe3+ et tout Fe2+ (~12% de Fetot) est en coordinence 5. Fe3+ en coordinence 4 jouerait un rôle de formateur de réseau, alors que le fer en coordinence 5 a tendance à ségréger et jouerait le rôle de modificateur. La présence de cette espèce, bien que minoritaire, permettrait d'expliquer les variations de certaines propriétés physiques des verres contenant du fer. Le remplacement progressif de Fe par Al a été étudié le long du joint NaFeSi2O6- NaAlSi2O6 en utilisant la diffraction des neutrons combinée avec des simulations EPSR. Quelle que soit la teneur en fer (et en aluminium), les rôles structuraux de Fe, Al3+ et Si4+ ne sont pas modifiés. Quelle que soit la teneur en aluminium, Al (en coordinence 4) est réparti de façon aléatoire dans le réseau, ce qui est en accord avec un rôle de formateur. Il en est de même pour le fer : les deux populations mises en évidence dans le pôle NaFeSi2O6 ainsi que les rôles structuraux qu'on leur a assignés sont conservés jusqu'au pôle NaAlSi2O6. Pour la première fois, la spectroscopie d'absorption des rayons X (XANES) aux seuils L2,3 de l'aluminium a été utilisée pour suivre l'évolution de l'environnement de l'aluminium dans ces verres. Enfin, la spectroscopie Mössbauer a permis de déterminer le rapport redox du fer le long du joint.

Das Laserschneiden ist ein in der Industrie fest etabliertes Trennverfahren für Metalle und eine Vielzahl weiterer Materialien. Trotz der weitgehenden Beherrschung des Schneidprozesses durch empirische Untersuchungen und praktisches Erfahrungswissen sind die zugrundeliegenden physikalischen Mechanismen bisher nicht vollständig verstanden. Besonders für die qualitätsbestimmende Schnittkantenrauheit und die Gratbildung ist mit den bisherigen Verbesserungsansätzen nur eine begrenzte Beeinflussung möglich. Auch wenn die fundamentale Bedeutung der Gasströmung für die Bewegung der Schmelze allgemein akzeptiert ist, existieren für den konkreten Impuls- und Wärmeaustausch zwischen Gasströmung und Schmelze bisher nur unzureichende theoretische oder numerische Ergebnisse. Weiterhin können die in experimentellen Untersuchungen dokumentierten charakteristischen Schmelzströmungen nicht mit den bereits existierenden einfachen Modellen zur Gas-Schmelze-Interaktion abgebildet oder erklärt werden. Die vorliegende Dissertation thematisiert erstmals die lokale Wechselwirkung zwischen Schneidgasströmung und der Oberfläche des Schnittspaltes bzw. der Schmelzfilmoberfläche und untersucht insbesondere die Eigenschaften der Gasgrenzschicht. Die Arbeit verfolgt einen kombinierten Ansatz aus experimentellen, theoretischen und numerischen Untersuchungen. Die Analyse typischer Schnittkanten betrachtet detailliert die charakteristische Oberflächenstruktur der Kanten und resultiert in einer für das Schneiden mit Festkörperlasern angepassten Einteilung in horizontale Strukturzonen. Der festgestellte Zusammenhang zwischen den Prozessparametern, der Spaltgeometrie und den Zonen der Schnittkante dokumentiert ebenso wie die lokalen Ansammlungen von erstarrten Schmelzresten mit spiralförmiger Oberflächenstruktur den fundamentalen Einfluss der Gasströmung auf die globale und lokale Schmelzbewegung. Die Abschätzung der Grenzschichteigenschaften anhand semi-empirischer Kennzahlgleichungen unter den spezifischen Randbedingungen des Laserschneidens zeigt erstmalig, dass weder von einer laminaren noch von einer turbulenten Grenzschichtströmung ausgegangen werden kann, sondern dass ein transitioneller Grenzschichtcharakter vorliegt. Die Übertragung grundlegender Erkenntnisse der Grenzschichttheorie, insbesondere zum Einfluss von Strömungsablösungen und Stoß-Grenzschicht-Interaktionen auf die Stabilität der Grenzschicht, ermöglicht eine Eingrenzung der beim Laserschneiden relevanten Instabilitätsmechanismen auf räumlich-periodische und quasi-stationäre Moden und resultiert in einem Ansatz zur Interpretation experimenteller Schnittkanten im Rahmen der Grenzschichtentwicklung des Schneidgases. Das hierzu entwickelte numerische Modell der Schneidgasströmung bestätigt die theoretischen Ergebnisse zur Grenzschichtentwicklung und ist fähig, die relevanten Instabilitätsmoden wiederzugeben und die resultierenden lokalen Verteilungen des Impuls- und Wärmeübergangs zwischen Gas und Schmelze zur quantifizieren. Der Vergleich zu realen Schnittkanten und die Untersuchung grundlegender Einflussgrößen liefert eine sehr gute Übereinstimmung zu experimentellen Befunden. Die vorliegende Dissertation leistet damit einen grundlegenden Beitrag zur Bedeutung der Schneidgasströmung und ihrer Grenzschicht für das Verständnis des Laserschneidens und eröffnet neue Möglichkeiten für eine Prozessbeeinflussung und Optimierung. / Laser cutting is a firmly established cutting process in industry for metals and a variety of other materials. Despite the fact that the cutting process has been largely mastered by empirical studies and practical experience, the underlying physical mechanisms are not yet fully understood. Particularly for the quality-determining cut edge roughness and burr formation, only a limited influence is possible with the previous improvement approaches. Even if the fundamental influence of the gas flow on the movement of the melt is generally accepted, only insufficient theoretical or numerical results exist so far for the specific momentum and heat transfer between gas flow and melt. Furthermore, the characteristic melt flows documented in experimental investigations cannot be represented or explained with the already existing simple models for gas-melt interaction. The present dissertation addresses the local interaction between cutting gas flow and the surface of the kerf respectively the melt film surface, and considers in particular the properties of the gas boundary layer. The work follows a combined approach of experimental, theoretical and numerical investigations. The analysis of typical cut edges considers in detail the characteristic surface structure of the edges and results in a subdivision into horizontal structural zones adapted for cutting with solid-state lasers. The observed correlation between the process parameters, the gap geometry and the zones of the cut edge documents the fundamental influence of the gas flow on the global and local melt movement, as do the local accumulations of solidified melt residues with a spiral surface structure. The estimation of the boundary layer properties based on semi-empirical parameter equations under the specific boundary conditions of laser cutting shows for the first time that neither a laminar nor a turbulent boundary layer flow can be assumed, but that a transitional boundary layer character is present. The transfer of fundamental findings of boundary layer theory, in particular on the influence of flow separation and shock-boundary layer interactions on the stability of the boundary layer, allows a confinement of the instability mechanisms relevant in laser cutting to spatially-periodic and quasi-stationary modes. Additionally, an approach for the interpretation of experimental cut edges in the context of the boundary layer development of the cutting gas is derived. Furthermore, the developed numerical model of the cutting gas flow confirms the theoretical results on boundary layer development. It is capable of reproducing the relevant instability modes and for quantifying the resulting local distributions of momentum and heat transfer between gas and melt. The comparison to real cut edges and the investigation of fundamental parameters yields a good agreement to experimental findings. This thesis thus provides a fundamental contribution to the importance of the cutting gas flow and its boundary layer for the understanding of laser cutting and opens up new possibilities for process control and optimization.

Poultry litter ash (PLA) is a co-product from manure-to-energy systems that originated in response to increased poultry litter (PL) volumes generated in concentrated poultry production regions. Investigating PLA as a crop fertilizer is an alternative solution to balancing poultry and crop regional nutrient cycling in the Commonwealth of Virginia. As the expanding world population places pressure on the poultry industry to meet consumption demands, increased PL production presents an obstacle to identify alternative uses for increased volumes. Currently, Virginia produces 44 million broilers with PL produced predominately in the Shenandoah Valley and Eastern Shore. Likewise, a growing world population places pressure on crop production areas and subsequently finite natural resources used for crop fertilization. Poultry litter ash is an alternative phosphorus (P) and potassium (K) source enhancing transportation logistics, repurposing PL nutrients, and offers dual purpose as a fertilizer and an energy source when compared to PL. Three PLA products [(fluidized bed bulk (FB Bulk), fluidized bed fly (FB Fly), and combustion Mix (CMix)], two manufactured co-products [(granulated poultry litter ash (GPLA), and ash coated urea (ACU)] were evaluated as P, K, and N sources for corn (Zea Mays L.) production in comparison to industry fertilizers [(PL, triple superphosphate (TSP), muriate of potash (KCL), and urea). A comprehensive examination of elemental composition, P speciation, P and K solubility, improved functionality into granulized forms, and field testing were conducted to discern PLA potential as an alternative fertilizer source. Poultry litter ash products were evaluated by total elemental analysis, backscatter-electron dispersive (BSED) microscopy, and X-ray absorption near edge structure (XANES) spectroscopy. Poultry litter ash elemental concentrations were highly variable ranging from 50.6 to 102.0 g P kg -1 and 62.6 to 120.0 g K kg -1 and were comparatively higher than PL concentrations. Phosphorus structures that provided and controlled P solubility were Ca and Ca-Mg-phosphate compounds. Spectroscopy confirmed Ca structures as predominately monetite (dicalcium phosphate anhydrous; CaHPO4; log K ̊ 0.30) and brushite (dicalcium phosphate dihydrate; CaHPO4.2H20; 0.63 log K ̊ ) species that were supported by BSED and elemental stoichiometric ratios (Ca:P; 1.12 to 1.71:1). Additionally, GPLA acidified from FB Fly had higher brushite and monetite percentages described by spectra models, translating into a more soluble Ca-phosphate species when compared to FB Fly original P species. Granulated poultry litter acidulation trials successfully identified a desired granulation point of 29% (14.5 g acid to 50 g PLA) phosphoric acid (75% H3PO4) acidulation. Acidulation dose response relationships created simple linear regression (SLR) equations that sufficiently (R2 > 0.80) described changes in total measurable P and water soluble P, pH, and exothermic reaction temperatures to increasing H3PO4 acidulation. Solubility tests included: sequential extraction, particle size effect on solubility, carbon effect on water soluble P, and Mehlich-1 extraction of PLA sources that confirmed decreased P solubility. A majority PLA P was found in bound plant unavailable fractions (87.7 to 97.7% P of total P). Granulated poultry litter ash had improved P plant available P of 36.0% P of total P. Carbon (C) effects on PLA P were examined by ashing PLA samples in a muffle furnace at 550 ̊C. Differences in total carbon content negatively impacted FB Bulk and CMix total P (1.30 and 4.56 g P kg -1); however, muffle furnace temperatures increased FB Fly total P by 6.74 g P kg -1. All fertilizer products were investigated under field conditions in separate P, K and N corn studies across Virginia coastal plain soils to determine fertilizer effects on corn plant parameters [(most mature leaf (V6), corn ear leaf (R1), and grain (R6)]. Poultry litter P treatments, averaged over rate, recorded highest yield in both years. At eight of nine field sites, FB Bulk resulted in numerically or significantly higher Mehlich-1 concentrations than other P sources post-harvest. Although Mehlich-1 P increased, yield and plant parameters did not; which leads to the conclusion that PLA sources increased soil residual P that did not translate into immediate plant availability recorded within a growing season. Across plant efficacy parameters examined, PLA K is a comparable nutrient source and improved plant parameters when compared to control. Eighteen out of twenty-one plant parameters examined found similar ACU and urea effects on N concentrations. Therefore, ACU is a comparable N source to urea. When compared to industry fertilizer sources, we concluded that PLA is a slowly available P source, decreased P availability negatively affected early plant growth, K is a comparable nutrient source and improved plant parameters compared to control, and ACU effectively provided N to maintain sufficient corn growth. In conclusion, PLA co-products serve as a densified nutrient source that may provide plant available nutrients if processed to aid in nutrient distribution to grain producing areas. / Doctor of Philosophy / Poultry litter ash (PLA) is a co-product from manure-to-energy systems that originated in response to increased poultry litter (PL) volumes generated in concentrated poultry production regions. Investigating PLA as an alternative crop fertilizer is essential to balancing poultry and crop regional nutrient cycling in the Commonwealth of Virginia. As the expanding world population places pressure on the poultry industry to meet consumption demands, heightened PL production presents an obstacle to identify alternative uses for increased volumes. Currently, Virginia produces 44,683,904 broilers with PL produced predominately in the Shenandoah Valley and Eastern Shore. Likewise, a growing world population places pressure on crop production areas and subsequently finite natural resources used for fertilization vital to maintaining crop yields. Poultry litter ash, a co-product from manure-to-energy systems, is an alternative phosphorus (P) and potassium (K) source enhancing transportation logistics, repurposing PL nutrients, and offers dual purpose as a fertilizer and an energy source when compared to PL. In this dissertation, three PLA products [(fluidized bed bulk (FB Bulk), fluidized bed fly (FB Fly), and combustion Mix (CMix)], two manufactured co-products [(granulated poultry litter ash (GPLA), and ash coated urea (ACU)] were evaluated as P, K, and N source for corn (Zea Mays L.) production in comparison to industry fertilizers (PL, triple superphosphate (TSP), muriate of potash (KCL), and urea). Each of the following chapters provides a comprehensive examination of the following topics: elemental composition, P speciation, P and K solubility, improved functionality into granulized forms, and field testing designed to provide parameters to conclude PLA potential as an alternative P, K and N source. In the second chapter, PLA products were evaluated by total elemental analysis, backscatter-electron dispersive (BSED) microscopy, and X-ray absorption near edge structure (XANES) spectroscopy. Poultry litter ash elemental concentrations are highly variable and are comparatively higher than PL concentrations. Phosphorus structure and species identified Ca as the primary element controlling P structure and subsequent solubility. The third component of this dissertation is granulation trials investigating phosphoric acid effects on granulizing and increasing total and water soluble P. Our results identified 29% (14.5 g acid to 50 g PLA) phosphoric acid acidulation for desired granule size. The third dissertation component examines PLA solubility. The results demonstrated PLA decreased P water solubility when compared to industry fertilizer sources. Granulated poultry litter ash demonstrated improved P plant availability due to the granulation process. The final and fourth dissertation components investigated PLA sources under field conditions in separate P, K and N corn studies across Virginia coastal plain soils to determine fertilizer effects on corn plant parameters. Minority of plant parameters tested revealed P control yielded numerically higher P concentrations than PLA P sources tested. Poultry litter P treatments, averaged over rate, recorded highest yield in both years. At eight of nine field sites, FB Bulk resulted in numerically or significantly higher Mehlich-1 concentrations than other P sources post-harvest. Although Mehlich-1 P concentrations increased, yield and plant parameters did not; which leads to the conclusion that PLA sources increased soil residual P that did not translate into immediate plant availability recorded within a growing season. Across plant efficacy parameters examined, PLA K is a comparable nutrient source and improved plant parameters when compared to controls. The majority of plant parameters examined found similar ACU and urea effects on N concentrations. Therefore, ACU is a comparable N source to urea. When compared to industry fertilizer sources, field results concluded that PLA is a slowly available P source, decreased P availability negatively affected early plant growth, K is a comparable nutrient source and improve plant parameters compared to control, ACU effectively provides N to maintain sufficient corn growth. In conclusion, PLA co-products serve as a densified nutrient source that may provide plant available nutrients if processed to aid in nutrient distribution to grain producing areas.

Master of Science / Department of Agronomy / Ganga M. Hettiarachchi / Phosphorus (P) management in reduced tillage systems has been a great concern for farmers. Conclusive results for benefits of deep banding of P fertilizers for plant yield in reduced tillage system are still lacking. Knowledge of the dominant solid P species present in soil following application of P fertilizers and linking that to potential P availability would help us to design better P management practices. The objectives of this research were to understand the influence of placement (broadcast- vs. deep band-P or deep placed-P), fertilizer source (granular- versus liquid-P), and time on reaction products of P. Greenhouse and field based experiments were conducted to study P behavior in soils. Soil pH, resin extractable P, total P, and speciation of P were determined at different distances from the point of fertilizer application at 5 weeks (greenhouse and field) and 6 months (field) after P application (at rate 75 kg/ha) to a soil system that was under long-term reduced tillage. X-ray absorption near edge structure spectroscopy technique was used to speciate reaction products of fertilizer P in the soil. The reaction products of P formed upon addition of P fertilizers to soils were found to be influenced by soil pH, P placement methods, and P sources. Acidic pH (below~5.8) tended to favor formation of Fe-P and Al-P like forms whereas slightly acidic near neutral pH soils favored formation of Ca-P like forms. Scanning electron microscope with energy dispersive X-ray analysis of applied fertilizer granules at 5-wk showed enrichment of Al, Fe and Ca in granule- indicating these elements begin to react with applied P even before granules dissolve completely. The availability of an applied P fertilizer was found to be enhanced as a result of the deep banding as compared to the surface broadcasting or deep placed methods. Deep banded liquid MAP was found to be in more adsorbed P like forms and resulted greater resin extractable P both at 5 wk and 6 month after application. Deep banding of liquid MAP would most likely result both agronomically and environmentally efficient solution for no-till farmers.

No description available.

<div>The accelerating expansion of agricultural and urban areas fragments and degrades forests</div><div>and their capacity to provide essential ecosystem services while increasing physiological stress</div><div>and mortality rates of trees growing near forest edges. Previous studies have documented that</div><div>edges are hotter and drier than forest interiors and trees nearer the edge grow slower. However,</div><div>the physical structure of a forest’s canopy may serve to mitigate to these effects. This study</div><div>quantifies forest fragmentation across the Central Hardwoods Region (CHR; containing Missouri,</div><div>Illinois, and Indiana) and characterizes structural differences between the canopies of forest edges</div><div>and forest interiors. Importantly, we distinguish between edges that neighbor developed land and</div><div>agricultural lands since these landcover types may impose distinct effects on forest structure. We</div><div>characterized forest canopy structure in a subset of the CHR region using the 2016-2020 Indiana</div><div>3DEP Lidar Program data. Our findings indicate edge forest (forests within 30m of an edge) makes</div><div>up 29.8% of the total forest in our study extent, with urban and agricultural edges accounting for</div><div>17.8% and 72.8% of the edge edges in the region, respectively. Analysis of 15 separate structural</div><div>metrics derived from aerial laser scanning (ALS) showed no significant structural differences</div><div>between developed and agricultural edge canopies but did find differences between structure of</div><div>canopies in forest cores and those in forest edges of any kind. As developed and agricultural lands</div><div>increase so too will forest fragmentation and the creation of new forest edges. If there are no</div><div>significant differences between forest edge types, then we could begin to treat edges without</div><div>distinction. This could lead to simplified management practices for foresters and urban foresters</div><div>alike to protect and preserve forest fragments.</div>

Despite increasing attention for the recently found ferro- and antiferroelectric properties, the polymorphism in hafnia- and zirconia-based thin films is still not sufficiently understood. In the present work, we show that it is important to have a good quality X-ray absorption spectrum to go beyond an analysis of the only the first coordination shell. Equally important is to analyze both EXAFS and XANES spectra in combination with theoretical modelling to distinguish the relevant phases even in bulk materials and to separate structural from chemical effects. As a first step toward the analysis of thin films, we start with the analysis of bulk references. After that, we successfully demonstrate an approach that allows us to extract high-quality spectra also for 20 nm thin films. Our analysis extends to the second coordination shell and includes effects created by chemical substitution of Hf with Zr to unambiguously discriminate the different polymorphs. The trends derived from X-ray absorption spectroscopy agree well with X-ray diffraction measurements. In this work we clearly identify a gradual transformation from monoclinic to tetragonal phase as the Zr content of the films increases. We separated structural effects from effects created by chemical disorder when ration of Hf:Zr is varied and found differences for the incorporation of the substitute atoms between powders and thin films, which we attribute to the different fabrication routes. This work opens the door for further in-depth structural studies to shine light into the chemistry and physics of these novel ferroelectric thin films that show high application relevance.

<p>Silicon nanostructures formed in silicon-rich silicon nitride (SRSN) and cerium and terbium doped silicon oxide thin films grown using different types of plasma-enhanced chemical vapour deposition have been studied through photoluminescence (PL) and synchrotron-based X-ray absorption spectroscopies to determine the effects of deposition and processing parameters on the luminescent and structural properties of these materials. The SRSN films exhibited bright PL attributed to quantum confinement effects in the silicon nanoclusters (Si-ncs) as well as radiative defects in the silicon nitride host matrix. The peak emission energy could be tuned from the near-infrared across the entire visible spectrum by controlling the film composition and the post-deposition annealing temperature and time to change the size of the Si-ncs. Preliminary experiments on cerium doped SRSN samples indicated that although the cerium ions coordinate in the optically active trivalent oxidation state, they were not effectively sensitized by Si-ncs in the films tested, most likely due to the nanoclusters having bandgap energies that were unsuitable for this purpose. In cerium and terbium co-doped silicon oxide films, cerium disilicate (Ce₂Si₂O₇) nanocrystallites were formed by annealing at temperatures of 900°C and higher. The A-Ce₂Si₂O₇, G-Ce₂Si₂O₇, and Ce₆[Si₄O₁₃][SiO₄]₂ phases of cerium disilicate were observed to form under different deposition and annealing conditions. All three phases exhibited extremely bright violet-blue PL and were found to efficiently sensitize green emission from co-dopant Tb³⁺ ions in the films. The Tb³⁺ luminescence predominantly corresponded to the ⁵D₄→⁷F_3–6 emission lines, although weak ⁵D₃→⁷F_2–6 emission lines were also observed in films containing relatively high concentrations of terbium indicating that the sensitization of Tb³⁺ ions occurred through the ⁵D₃, ⁵L₁₀, or ⁵D₂ energy levels.</p> / Doctor of Philosophy (PhD)