Dealloying is a corrosion process in which one or more elements are selectively removed from an alloy leading to a 3-dimensional porous structure of the more noble element(s). These porous structures have been known to cause stress corrosion cracking in noble metal alloy systems but more recent interest in using the corrosion process to produce porous metals has developed. Applications for these structures range from high surface area electrodes for biomedical sensors to use as skeletal structures for fundamental studies (e.g. low temperature heat exchangers or sensitivity of surface diffusivity to chemical environment). In this work we will review our current understanding of alloy corrosion including our most recent results demonstrating a more accurate method for calculating alloy critical potential based on potential hold experiments. The critical potentials calculated through the potential hold method were â 0.030VMSE, 0.110VMSE, and 0.175VMSE for Cu80Pt20, Cu75Pt25 Cu71Pt29 respectively. We will present the use of porous metals for making surface diffusivity measurements in the Pt systems as a function of chemical environment. A review of the use of small angle neutron scattering to make accurate measurements of pore size is presented and the sensitivity of pore size to electrolyte, electrolyte composition, applied potential and temperature will be explained. The production of porous Pt with pore sizes ranging from 2-200nm is demonstrated. / Ph. D.

This study compared the effects of selective cutting (SC) and the first shelterwood (SW) cut in oak (Quercus)-dominated forests of western Virginia. The specific attributes compared were: (1) tree species composition; (2) seedling, sapling, and overstory tree density; (3) overstory tree quality and size; (4) sapling crown class; and (5) canopy closure. Seedlings, saplings, and overstory trees were sampled at 22 SC and 28 SW sites. Significant differences identified between the two harvest types included: biodiversity of overstory and seedling layers; species densities for seedlings, saplings, and overstory trees; species composition across forest layers; and average canopy closure. Regeneration was poorer on SC than on SW, especially among oak species where SC oak seedling density averaged 5,651 stems ha-1 and SW oak seedling density averaged 9,843 stems ha-1. Selective cutting and SW may both contribute to mesophication of oak-dominated forests in the southern Appalachian Mountains; however, SC resulted in a higher percentage of mesic species post-harvest, and the SW tended to have more oak regeneration. / Master of Science / Selective cutting in the form of high-grading (harvesting only the most valuable trees in a forest) and diameter-limit cutting (harvesting all merchantable trees in a forest above a designated diameter at breast height) is the predominant timber harvest practice in the southern Appalachian Mountains. It is contributing to a shift in forest composition away from oak species toward tree species of lower commercial and wildlife value. In this study, although there were fewer seedlings and saplings after selective cuts than after shelterwoods (a partial harvest of trees aimed at encouraging the regeneration of desirable tree species such as oaks in the future forest), there was higher tree species diversity among the seedlings and saplings at selective cutting sites than at shelterwoods. Oak regeneration remains a challenging goal to meet, but silvicultural systems such as shelterwoods that are designed to promote oak regeneration are likely to be more successful than selective cutting at maintaining oak dominance in this forested region.

This thesis presents work done investigating methods for constructing patterns on the nanometer scale. Various methods of nanolithography using atomic force microscopes (AFMs) are investigated. The use of AFMs beyond their imaging capabilities is demonstrated in various experiments involving nanografting and surface electrochemical modification. The use of an AFM to manipulate a monolayer of thiols deposited on a gold substrate via nanografting is shown in our work to enable chemical modification of the surface of the substrate by varying the composition of the monolayer deposited on it. This leads to the selective deposition of various polymers on the patterned areas. Conditions for enhancing the selective deposition of the self-assembled polymers are studied. Such conditions include the types of polymers used and the pH of the polyelectrolyte solutions used for polymer deposition. Another method of nanolithography is investigated which involves the electrochemical modification of a monolayer of silanes deposited on a silicon substrate. By applying a potential difference and maintaining the humidity of the ambient environment at a certain level we manage to change the chemical properties of select areas of the silane monolayer and thus manage to establish selective deposition of polymers and gold nanoparticles on the patterned areas. Parameters involved in the patterning process using surface electrochemical modification, such as humidity levels, are investigated. The techniques established are then used to construct circuit elements such as wires. / Ph. D.

Additive manufacturing introduces a new design paradigm that allows the fabrication of geometrically complex parts that cannot be produced by traditional manufacturing and assembly methods. Using a cellular heat exchanger as a motivational example, this thesis investigates the creation of a hybrid manufacturing approach that combines selective laser sintering with an electroforming process to produce complex, hollow, metal geometries. The developed process uses electroless nickel plating on laser sintered parts that then undergo a flash burnout procedure to remove the polymer, leaving a complex, hollow, metal part. The resulting geometries cannot be produced directly with other additive manufacturing systems. Copper electroplating and electroless nickel plating are investigated as metal coating methods. Several parametric parts are tested while developing a manufacturing process. Copper electroplating is determined to be too dependent on the geometry of the part, with large changes in plate thickness between the exterior and interior of the tested parts. Even in relatively basic cellular structures, electroplating does not plate the interior of the part. Two phases of electroless nickel plating combined with a flash burnout procedure produce the desired geometry. The tested part has a density of 3.16g/cm3 and withstands pressures up to 25MPa. The cellular part produced has a nickel plate thickness of 800µm and consists of 35% nickel and 65% air (empty space). Detailed procedures are included for the electroplating and electroless plating processes developed. / Master of Science

A computer-based parametric study of the effect of reinforcement architectures on fracture response of aluminum compact-tension (CT) specimens was performed using the finite element code ABAQUS. A three-dimensional crack propagation procedure based on the crack tip opening angle (CTOA) was developed using Python. Eleven different reinforcement architectures consisting of rectangular and triangular cross-section reinforcements were evaluated. Reinforced specimens produced between 13 and 28 percent higher fracture load than achieved with the non-reinforced case. Reinforcements with blunt leading edges (rectangular reinforcements) exhibited superior performance relative to the triangular reinforcements with sharp leading edges. Relative to the rectangular reinforcements, the most important architectural feature was reinforcement thickness. At failure, the reinforcements carried between 58 and 85 percent of the load applied to the specimen, suggesting that there is considerable load transfer between the base material and the reinforcement. The amount of load transfer is linked to strains experienced by the reinforcement ahead of the crack tip. / Master of Science

No / A laboratory-based experiment was carried out to examine the dissolution characteristics of testate amoebae (Protozoa: Rhizopoda) under acidic conditions. The results suggest a large degree of variability in the dissolution susceptibility of taxa and no straightforward distinction between the relative robustness of xenosomic and idiosomic test types. Individuals from the genus Euglypha have tests composed of thin-walled siliceous plates, which are prone to severe dissolution. Certain other taxa are relatively unaffected by low pH conditions, including Assulina muscorum, Amphitrema flavum and Trigonopyxis arcula type. Differential preservation of subfossil testate amoebae must be acknowledged as a particular problem for peat-based palaeoclimate studies.

This diploma thesis deals with the design of a universal muzzle device for the assault rifle. The device is designed to produce Selective Laser Melting. The main objective is the elimination negative effects of gunshot. The paper explores possibilities of using porous structures for this type of equipment. The influence of individual types of porous structures on the flow of gases is monitored. The universal muzzle device itself is optimized using CFD analyzes. The device was made using SLM technology and experimentally verified. His impact on the impact, gun lift, noise and flame elimination was investigated.

V současnosti musí velké energetické podniky k dodržení emisních předpisů, zejména pak vyžadovaných limitů NOx, uplatňovat denitrifikační metody. Tématem předkládané diplomové práce jsou moderních denitrifikační metody a jejich praktické uplatnění v lokálních poměrech uhelného kotle s parním výkonem 640 t.h-1 v elektrárně Počerady. Práce obsahuje rešerši moderních denitrifikačních metod používaných velkými uhelnými kotli se zaměřením zejména na sekundární denitrifikační metody. Jsou uvažovány dvě možné varianty denitrifikace – varianta 1 využívá selektivní katalytickou redukci (SCR) a varianta 2 selektivní nekatalytickou redukci (SNCR) společně s nízkoemisními hořáky a stupňovaným přívodem spalovacího vzduchu. Pro výběr vhodné denitrifikační metody jsou studovány investiční náklady jednotlivých variant – nižší investiční náklady (o 19.4%) slibuje varianta 2. Při srovnávání SCR se SNCR vyšlo najevo, že investiční náklady metody SNCR jsou 5krát nižší než metody SCR. V souladu s investičními náklady, s dispozicí kotle a se složitostí jeho instalace je pro navazující studium problematiky využita varianta 2. Stěžejní část práce se zabývá stanovením optimálního tzv. teplotního okna pro konkrétní metodu SNCR. Těžištěm práce je tepelný výpočet ohniště a části deskového přehříváku pro stanovený rozsah paliv a výkon kotle v rozmezí 60-100%. S uvažováním výsledků z výpočtu jsou navrženy dvě vstřikovací roviny, které mají zaručit vysokou efektivitu denitrifikačního procesu při uvažovaných provozních podmínkách kotle. Diplomová práce rovněž diskutuje obecnou vhodnost instalace SNCR a SCR ve stávajících uhelných kotlích.

Highly selective and sensitive phosphate sensors have been fabricated by constructing a solid membrane disk consisting of variable mixtures of aluminium powder (Al), aluminium phosphate (AlPO4) and powdered copper (Cu). Both binary and ternary electrode systems are produced depending on their composition. The ternary membranes exhibit greater selectivity over a wide range of concentrations. The ternary electrode with the composition 25% AlPO4, 25% Cu and 50% Al was selected as our preferred electrode. The newly fabricated ternary membrane phosphate selective electrodes exhibited linear potential response in the concentration range of 1.0 × 10−6 to 1.0 × 10−1 mol L−1. The electrodes also exhibit a fast response time of <60 s. Their detection limit is 1.0 × 10−6 mol L−1. The unique feature of the described electrodes is their ability to maintain a steady and reproducible response in the absence of an ionic strength control. The electrodes have a long lifetime and can be stored in air when not in use. The selectivity of the new phosphate selective electrodes with respect to other common ions is excellent. The results obtained provide further insight into the working principles of the newly fabricated phosphate selective electrodes. Dephosphorylation and phosphorylation reactions were monitored using the preferred phosphate selective electrode. The following reactions were studied and inferences drawn; (a) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[OH(PO2O)]2- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[OH(PO2O)]2- ratios.(b) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[O2NC6H4PO2(O)(OH)]- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[O2NC6H4PO2(O)(OH)]- ratios. (c) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)2O]2- for 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)2O]2- ratios, and (d) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)3O2]3- for the 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)3O2]3- ratios. Further insight into dephosphorylation and phosphorylation reactions is unravelled by the novel phosphate selective electrode monitoring. *For clarity of the complexes utilized, see chapter 4, table 4.1. KEY WORDS; Dephosphorylation, phosphorylation, ion selective electrodes, phosphate ion selective electrode, decontamination, electromotive force, potential difference, activity, concentration, selectivity coefficient, calibration, ionic strength, hydrolysis, inorganic phosphates, nitrophenylphosphate, pyrophosphate, tripolyphosphate, organophosphate esters. / Chemistry / D.Phil (Chemistry)

Highly selective and sensitive phosphate sensors have been fabricated by constructing a solid membrane disk consisting of variable mixtures of aluminium powder (Al), aluminium phosphate (AlPO4) and powdered copper (Cu). Both binary and ternary electrode systems are produced depending on their composition. The ternary membranes exhibit greater selectivity over a wide range of concentrations. The ternary electrode with the composition 25% AlPO4, 25% Cu and 50% Al was selected as our preferred electrode. The newly fabricated ternary membrane phosphate selective electrodes exhibited linear potential response in the concentration range of 1.0 × 10−6 to 1.0 × 10−1 mol L−1. The electrodes also exhibit a fast response time of <60 s. Their detection limit is 1.0 × 10−6 mol L−1. The unique feature of the described electrodes is their ability to maintain a steady and reproducible response in the absence of an ionic strength control. The electrodes have a long lifetime and can be stored in air when not in use. The selectivity of the new phosphate selective electrodes with respect to other common ions is excellent. The results obtained provide further insight into the working principles of the newly fabricated phosphate selective electrodes. Dephosphorylation and phosphorylation reactions were monitored using the preferred phosphate selective electrode. The following reactions were studied and inferences drawn; (a) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[OH(PO2O)]2- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[OH(PO2O)]2- ratios.(b) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[O2NC6H4PO2(O)(OH)]- for 1:1, 2:1 and 3:1 *[{CoN4(OH)(OH2)}]2+ to *[O2NC6H4PO2(O)(OH)]- ratios. (c) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)2O]2- for 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)2O]2- ratios, and (d) the reactions between *[{CoN4(OH)(OH2)}]2+ and *[(OH)2(PO2)3O2]3- for the 1:1, 2:1 and 3:1 [{CoN4(OH)(OH2)}]2+ to *[(OH)2(PO2)3O2]3- ratios. Further insight into dephosphorylation and phosphorylation reactions is unravelled by the novel phosphate selective electrode monitoring. *For clarity of the complexes utilized, see chapter 4, table 4.1. KEY WORDS; Dephosphorylation, phosphorylation, ion selective electrodes, phosphate ion selective electrode, decontamination, electromotive force, potential difference, activity, concentration, selectivity coefficient, calibration, ionic strength, hydrolysis, inorganic phosphates, nitrophenylphosphate, pyrophosphate, tripolyphosphate, organophosphate esters. / Chemistry / D. Phil (Chemistry)