Master of Science / Department of Agronomy / David B. Mengel / Research has shown that nitrogen fertilizer is needed most years to optimize winter wheat yields in Kansas. Anhydrous ammonia (AA) has long been a favorite N fertilizer of producers as it has proven to be a reliable and economical source of N. Anhydrous application methods and equipment have changed little over the past 70 years. Recently John Deere has developed their 2510 HSLD (2510H) anhydrous ammonia applicator designed to improve efficiency and performance in no-till systems. The 2510H is designed to be run at high speed with low soil disturbance and low draft. This is achieved by using a rolling coulter type injection unit, designed much like modern single disk opener grain drill units, to apply AA at relatively shallow depths. With this low soil disturbance design, topdress AA applications may also be possible. Due to the environmental risks associated with wheat production, many Kansas producers prefer an N management system that consists of a “starter” application at planting with the majority of the N fertilizer applied in the spring. This approach makes certain that the crop survives the winter before the investment in N is made and eliminates the potential for fertilizer N being lost over the winter months. It has not been feasible to use AA for topdressing in the past due to the damage to the growing crop from application with traditional knife style applicators. The first part of this research revisits traditional preplant AA application methods by evaluating proper unit spacing and the use of nitrification inhibitors as well as comparing these AA treatments to common topdress applications of N. Over three site years, few consistently significant advantages between unit spacing, use of nitrification inhibitor or N management method were found. Unit spacing did show a notable trend favoring 50 cm spacing. The second part of this research was a two-year experiment conducted with the objective of assessing the feasibility of topdressing with AA using the 2510H as compared with topdressing with granular urea. A number of factors such as application direction in relation to crop row, speed of application and timing as a function of crop development were examined to minimize crop injury and maximize crop yield. The initial 2010 study was promising, showing no significant yield loss topdressing with AA compared to topdressing with urea. The experiment was repeated at two locations in 2011. Results were mixed, indicated that soil conditions and the plants ability to recover from the AA application injury were important for the success of topdressing with AA. Lastly, an economic evaluation of the production economics of preplant and topdress AA was compared to the traditional practice of topdressing winter wheat with urea. Through evaluation of the agronomic and economic factors affecting the feasibility of uses of AA and the 2510H, three main conclusions can be made: 1. Preplant application of AA has no agronomic advantage and only a small economic advantage over topdressing with urea when yields are the same. 2. Topdressing with AA is agronomically feasible but is at an economic disadvantage when compared to topdressing with urea, due to the yield reduction associated with the AA method. 3. Further research focused on reducing yield loss with topdress AA applications is needed before this N management strategy can be promoted on a large scale.

Master of Science / Department of Agronomy / David B. Mengel / Anhydrous ammonia (AA) is one of the most commonly used nitrogen (N) fertilizer sources for corn (Zea mays L.) in the US. Traditional knife applicators are slow, have high power requirements and create substantial soil disturbance. Thus, there is considerable interest in high speed, shallow placement, and low draft AA applicators like the newly introduced JD 2510 series, particularly for no-till production systems. The objective of this project was to compare a prototype high speed, low draft applicator (JD) with a traditional knife type AA applicator (TRAD) for irrigated and dryland corn production in the Kansas River Valley. Field studies were conducted from 2007 through 2009. Six N rates ranging from 0 – 224 kilograms N per hectare, in 45 kilogram increments, were applied at 3 application timings, Fall (FALL), Preplant (PRE), and Sidedress (SD) with both type applicators. Gaseous AA emissions were collected over a seven to nine day period after each application for both the TRAD and JD applicators for all application timings. The impact of applicator, timing and N rate was also measured on plant stand, earleaf N content, total N uptake, nitrogen use efficiency and grain yield. Statistically higher post application losses of ammonia at high N application rates were seen at all application timings with the JD applicator. However, these N losses were not of agronomic significance, and did not affect grain yield in 2007 or 2008. In 2009, there did appear to be a significant difference between applicators in grain yield, however this was primarily due to a significant yield decrease at the JD SD 224 kilograms N per hectare treatment from high application loss and resulting plant tissue damage. A significant response to N application was seen every year. Optimum N rate varied between years. FALL and PRE treatments had significantly higher grain yield than SD applications in 2008. However, in 2009 there was no significant difference in N application timing.

Master of Science / Department of Agronomy / David B. Mengel / World population, together with the cost of crop production inputs, is increasing rapidly. The current seven billion people on earth are expected to reach nine billion by 2050 with resulting demands on world food production. In addition, the quality of our environment is being impacted by human activities, including agricultural production and crop fertilization. Nitrogen (N) management is the process of applying N fertilizers in a way to maximize use of N by crops, while minimizing loss to the environment. It is becoming imperative, as a means of increasing crop yields and food supplies, while reducing input usage, and minimizing the impact of N fertilization on the quality of our environment, that improved N application practices be identified and utilized. The objectives for this study were to compare the timing of anhydrous ammonia (AA) fertilizer N applications, fall and spring, with and without two different nitrification inhibitors (NI) as possible tools to enhance yield and Nitrogen Use Efficiency (NUE) in corn (Zea mays) and winter wheat (Triticum aestivum L.) in Kansas. Two different nitrification inhibitors were tested as alternatives, N-Serve (nitrapyrin) produced and marketed by Dow AgroSciences, and an experimental product under development by Koch Agronomic Services LLC. Three differing rates of the experimental product were used to assist in determining the optimal rate for this product. The study was conducted over two growing seasons, 2012 and 2013, which differed significantly in rainfall, rainfall distribution, and resulting NUE. Experiments were established at three sites for both crops in both years, on sites/soils selected for differing potentials for N loss, and mechanisms of N loss. One site was established at the Kansas State University Agronomy North Farm (N Farm), where yield potential was high, and N loss potential was low. A second site was established under irrigation at the Kansas River Valley Experiment Field near Topeka, KS (KRV), on a coarse silt loam soil with high potential for N loss through leaching. The third site was established at the East Central Kansas Experiment Field near Ottawa KS (ECK), on a clay pan soil with a high potential for denitrification loss. Weather conditions together with soil characteristics played a major role in the performance of N timing applications and impacted the response to the use of the inhibitors. In low N loss environments such as the N Farm, fall applications of AA to increase spring time-availability for producers showed minimal negative effects on yield or NUE. When combined with a nitrification inhibitor in the fall, performance was similar to spring application for both corn and wheat. At the KRV site leaching loss or potential loss from fall application was high for corn and wheat in both years, however little impact on NUE with NI use was observed. At the high ECK denitrification site, there was only one N loss potential event leading to inhibitor performance at Ottawa in corn in 2013.

A study of the reactions between molybdenum and tungsten disilicide (MoSi2 and WSi2) with anhydrous hydrogen fluoride and fluorine was carried out to investigate the chemical behaviour of the materials. These two compounds were used as alternatives that resemble the chemical behaviour of uranium silicide (U3Si2). An extensive literature survey of U3Si2 processing techniques is included, which guided the process selection for this work. The thermogravimetric results of a study into the dry fluorination of molybdenum and tungsten disicilides using both anhydrous hydrogen fluoride and dilute fluorine gas as fluorinating agents are reported. For both solids the observed reactions with fluorine follow the thermodynamically predicted routes, in which the formation of the volatile metal hexafluorides, along with gaseous silicon tetrafluoride was observed. The disilicides get fully converted at roughly 300 to 400 °C respectively. The expected products for the reactions of both solids with hydrogen fluoride are solid tungsten metal, solid molybdenum metal, hydrogen gas, and gaseous silicon tetrafluoride. The metal fluorides (WF4 and MoF3) were not obtained because they form at low temperatures only. Therefore the metals of molybdenum and tungsten were obtained as final products respectively from both reactions; and were verified with the aid of XRF and XRD analyses. Mass-transfer phenomena are shown to play a role in the reactions between hydrogen fluoride and both disilicides, preventing unrestrained complete fluorination of the two solids. Kinetic parameters are reported and the rate limiting mechanisms identified. Copyright / Dissertation (MSc)--University of Pretoria, 2012. / Chemical Engineering / unrestricted

abstract: The transport of hydrogen to the Earth’s deep interior remains uncertain. The upper mantle minerals have very low hydrogen solubilities (hundreds of ppm). The hydrogen storage capability in the transition zone minerals (2 wt%) is high compared to those of the upper mantle. The hydrogen storage in the lower mantle is not well known. The main minerals in the lower mantle bridgmanite and ferropericlase have very low hydrogen storage capacities (less than 20 ppm). In order to further understand the hydrogen storage in the lower mantle, a series of experiments had been conducted to simulate the environment similar to the Earth’s mantle. The experiments with hydrous Mg2SiO4 ringwoodite (Rw) show that it converts to crystalline dense hydrous silica, stishovite (Stv) or CaCl2-type SiO2(mStv), containing ∼1 wt% H2O together with bridgmanite (Brd) and MgO at the pressure-temperature conditions expected for lower mantle depths between approximately 660 to 1600 km. Brd would break down partially to dense hydrous silica (6–25 mol%) and(Mg,Fe)O in mid-mantle regions with 0.05–0.27 wt% H2O. The hydrous stishovite has a CaCl2 structure, which is common among hydrous minerals in the lower mantle. Based on this observation, I hypothesize the existence of hydrous phases in the lower mantle. The experiments found a new hexagonal iron hydroxide (η-Fe12O18+x/2Hx) between the stability fields of the epsilon and pyrite-type FeOOH at 60–80 GPa and high temperature. The new phase contains less H2O, limiting the H2O transport from the shallow to the deep mantle in the Fe–O–H system. Possible hydrogen storage in Ca-perovskite was studied. CaPv could contain 0.5–1 wt% water and the water in CaPv could distort the crystal structure of CaPv from cubic to tetragonal structure. In conclusion, hydrogen can be stored in hydrous stishovite in the shallower depth of the lower mantle. At greater depth, the new η phase and pyrite-type phase would take over the hydrogen storage. The role of CaPv in deep water storage needs to be considered in future studies. / Dissertation/Thesis / Doctoral Dissertation Natural Science 2019

<p> A number of new ternary borate compounds have been synthesized, and their crystal structures have been characterized via X-ray and neutron diffraction techniques. A series of new compounds with the composition PbMBO4 (M = Cr, Mn, Fe, Ga) has been prepared from solid-state reactions and from single crystal growths using PbO as a flux. They crystallize in the orthorhombic Pnma space group and represent a new structure-type for the family of anhydrous borates. The PbAlBO4 compound undergoes a phase transformation at high temperatures, which has been investigated by in-situ powder neutron diffraction experiments. The structure of β-PbAlBO4 has been solved from powder X-ray diffraction data and subsequently confirmed by a Rietveld refinement of powder neutron diffraction data. The investigation of the SrO - Ga2O3 - B2O3 system has led to the synthesis of a new structure-type, SrGaBO4, from solid-state reactions. Its crystal structure has been determined from powder X-ray diffraction data. It crystallizes in the orthorhombic Pbam space group, and is structurally related to the previously known alumino-borate compounds, SrAlBO4 and CaAlBO4. The "Ba2Ti2B2O9" compound has been re-formulated as Ba3Ti3B2O13, and its crystal structure has been determined by single crystal X-ray diffraction. This compound crystallizes in the non-centrosymmetric P6 2m space group. It is isostructural with K3Ta3B2O12 and the high temperature phase of K3Nb3B2O12.</p> / Thesis / Master of Science (MSc)

No description available.

The arid conditions found in the west allow for the production of high quality hay for export. However, hay production in this region is highly dependent upon irrigation. There is significant interest in developing a hay export market in the eastern U.S. Therefore, a greater understanding of the challenges and opportunities with containerizing hay in high humidity environments is needed. The objective of this study was to evaluate the impact of hay preservatives on the stability of containerized hay. Treatments included 1) propionic acid at baling, 2) propiopnic acid at baling + surface applied propionic acid at container loading, 3) propionic acid at baling + ammonization of the container after loading, and 4) no preservatives. Propionic acid was applied at a rate of 2.5 kg Mg-1 of hay at baling to all treatments except the control. Hay was then stored for 5 weeks before compressing to a density of 320.0 kg m-3. Immediately before containerizing hay, treatment 2 received a surface application of propionic acid at a rate of 3.4 g bale-1. After loading hay into containers, treatment 3 was ammoniated at a rate of 1.5 kg NH3 Mg-1 DM. Temperature and relative humidity in the containers were monitored for the 45-day storage period. Hay was sampled at compression and immediately after opening the containers. There were no treatment effects on nutritive value parameters after containerization (P > 0.05). Neither propionic acid at harvest, nor treatments at containerization had an effect on mold development in this study (P > 0.05). / Master of Science / Hay exports from the western U.S. have more than doubled since 2000. The arid conditions found in the west allow for the production of high quality hay for export. However, hay production in this region is highly dependent upon irrigation. There is significant interest in developing a hay export market in the humid east. The objective of this study was to evaluate the impact of two hay preservatives on the stability of containerized hay. Treatments included 1) propionic acid at baling, 2) propionic acid at baling + surface applied propionic acid at container loading, 3) propionic acid at baling + ammoniaization of the container after loading, and 4) no preservatives. Propionic acid was applied at a rate of 2.5 kg Mg⁻¹ of hay at baling to Treatments 1, 2, and 3. Hay was then stored for 5 weeks before double compressing. After compression, bales were placed into containers with treatment 2 receiving a surface application of propionic acid at a rate of 3.4 g bale⁻¹ . Treatment 3 was ammoniated in the container after loading at a rate of 1.5 kg NH₃ Mg⁻¹ DM. Temperature and relative humidity in the containers were monitored for the 45 day storage period. Hay was sampled prior to compression, at compression, and immediately after opening the containers. Samples were analyzed for neutral detergent fiber, acid detergent fiber, and crude protein. Subsamples were collected and sent for mold analysis. Results suggest that no treatments are needed in order to export quality alfalfa hay from the Mid-Atlantic.

The thesis begins with a brief introduction and relevant literature references. The novelty of synthesis, methodology and results of the work reported in the thesis and highlighted subsequently. The thesis consist of three parts, Part A of the thesis consist of five chapters describing new methods of synthesis of orthovanadates, mainly dealing with the structure and photocatalytic properties of synthesized materials. Part B of the thesis consist of two chapters dealing with an unique crystallization methodology for subliming and low melting organic compounds and the crystal structure determination via single crystal X-ray diffraction. Part C consists of one chapter presenting the ab-initio approach of structure determination via powder X-ray diffraction methods. Chapter 1 of the thesis presents the synthesis of three zircon type lanthanide orthovanadates, LnVO4 (Ln = Ce, Pr and Nd) via a new solution based approach at room temperature and photodegradation of a variety of water pollutants have been investigated. Chapter 2 describes the importance of microwave synthesis to produce nano particles of the zircon type lanthanide orthovanadates LnVO4. The importance of the surface area in photocatalysis is evaluated. Chapter 3 consist of the synthesis of a series of new compounds, Ln0.95φ0.05Mo0.15V0.85O4 (Ln = Ce, Pr and Nd) via solid state method. The photocatalytic activities of these compounds are investigated both under UV exposure and sunlight. Chapter 4 presents the synthesis of MxCe1-xVO4+ (M = Li, Ca and Fe) with x = 0.1, 0.25 and 0.05 respectively. Different kinds of dyes and organics are degraded under UV radiation and the specificity towards the same are evaluated. Chapter 5 describes a comparative photocatalytic conversion of cyclohexane and benzene to cyclohexanol, cyclohexanone and phenol respectively by LnVO4, LnMo0.15V0.85O4 and MxCe1-xVO4+ (Ln = Ce, Pr and Nd, M= Li, Ca and Fe with x = 0.1, 0.25 and 0.05 respectively). Kinetics of above photoconversions are established by proposing a mechanism and determining the rate constants. Chapter 6 describes the development of a novel apparatus for the crystallization of anhydrous adenine, whose structure has not been solved over the last few decades. The crystal structure is solved via single crystal X-ray diffraction. Chapter 7 presents a modified design for crystallization of low melting organic compounds and co-crystals. A new polymorph of anhydrous thymine has been grown with this apparatus and its structure has been analyzed and compared with the known form of thymine. Chapter 8 presents the ab-initio approach of structure determination via powder X-ray diffraction methods. The methodology of using the direct space approach for the determination of the crystal structure of N-(2-fluorophenyl) benzamide (a drug intermediate), which could not yield good quality single crystals, is outlined.

Um grande problema atual do mundo é o efeito estufa causado pela combustão de petróleo e seus derivados. Além disso, as reservas de petróleo não são ilimitadas, nem renováveis. Uma maneira de minimizar o problema é a utilização de combustíveis renováveis, tais como o etanol, derivado da cana de açúcar. É o caso dos motores de ignição por centelha que usam o etanol há décadas no Brasil. Este trabalho descreve as tecnologias existentes para utilização de etanol em motores de ignição por compressão. Apresenta resultados energéticos e de consumo de mistura de etanol anidro com diesel em diversas proporções. Mostra como substituir parcialmente o Diesel pelo etanol hidratado em determinadas proporções, sem realizar a mistura de combustíveis. Os combustíveis entram no motor por caminhos diferentes. Finaliza realizando estudos econômicos da utilização do etanol etílico em conjunto com o óleo diesel. / A major problem in the world nowadays is the \"green-house\" effect, caused by the combustion of petrol and its derivatives. Besides, oil reserves are not lirnitless, nor renewable. One way to rninirnize this problem is by using renewable combustibles, like ethanol, derived from sugar cane. This is the case of ignition spark engines, that have been using ethanol for decades, in Brazil. This thesis describes the existing technologies for ethanol utilization in ignition compression engines. It also presents energy and consumption results for the rnixture of anhydrous ethanol and diesel, in different proportions. It shows how to partially replace the diesel by hydrated ethanol in certain proportions, without fuel\'s blend. The fuels enter into the motor by different routes. It finally describes econornic studies for the utilization of ethylic alcohol m association to diesel.