Typescript (photocopy). / Digitized by Kansas Correctional Industries

Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2007. / Martha A. Gallivan, Committee Member ; Andrei G. Fedorov, Committee Member ; Christopher Summers, Committee Member ; Thomas H. Sanders, Jr., Committee Member ; Mo Li, Committee Chair.

The hemlock woolly adelgid (HWA), Adelges tsugae Annand (Hemiptera: Adelgidae), is an invasive pest from Japan that is causing significant hemlock mortality in the eastern U.S. The most promising control method is biological control. Beetles in the genus Laricobius are adelgid specialists. In 2005, Laricobius osakensis, was discovered in Japan and in 2010 was approved for release in the eastern United States and there have now been more than 60 releases. In 2014, the polar vortex resulted in significant HWA mortality in the eastern U.S., depleting the food source for L. osakensis, which resulted in low field recoveries of them. In the 2015-2016 field season, there were 14 larvae recovered from the field, and the 2016-2017 field season yielded 90 larvae. A significant correlation was found between Laricobius beetles recovered and HWA density, between HWA density and plant hardiness zone, and a negative correlation between Laricobius beetles recovered and average tree health. Understanding more about the supercooling point of L. osakensis gave insight to its ability to survive subfreezing temperatures as occurred in 2014. Comparison of the supercooling point between the northern and southern populations of L. osakensis, and to the other released HWA predator, L. nigrinus, will allow us to determine which biological control agent is best suited for release in the coldest regions. The overall mean supercooling points of northern L. osakensis was -13.52 oC, southern L. osakensis was -13.42 oC, and L. nigrinus was -13.57 oC. There were no significant differences between species or populations. / Master of Science in Life Sciences

Le travail de recherche mené au cours de cette thèse a été effectué dans le cadre d’une collaboration industrielle et a porté sur la technologie de prilling et le développement de microparticules lipidiques par cette technique originale. La première partie de ce travail a consisté à sélectionner des excipients lipidiques puis à étudier leurs comportements lors des deux grandes étapes du procédé : la formation de la goutte par rupture vibrante et la cristallisation par refroidissement brutal dans la tour de prilling. Ces études ont permis de mettre en évidence des paramètres clés pour la réussite du procédé et donc pour la qualité du produit fini : la viscosité et les propriétés thermiques et structurales des lipides. Ces paramètres devront donc faire l’objet d’une étude systématique avant d’envisager leur application à la technologie de prilling. La seconde partie de ce travail concerne la formulation de trois molécules actives par prilling : le Kétoprofène, la Dronédarone et la Fexofénadine. Ces trois exemples ont permis d’illustrer différents modes d’incorporation du principe actif dans le procédé et leurs problématiques associées : la fusion, la solubilisation ou la mise en suspension d’un principe actif dans les excipients fondus. / This work was conducted within the framework of an industrial collaboration and focused on the prilling technology and the development of lipid microparticles by this original technique.The first part of this work was to select lipid excipients and to study their behavior in the two main steps of the process: the droplet’s formation by vibrating nozzle and the droplet’s crystallization by quenching in the prilling tower. These studies highlight the critical key parameters involves in the success of the process and therefore the quality of the final product: viscosity and thermal and structural properties of lipids. These parameters should be therefore systematically studied before considering their application to technology prilling.The second part of this work concerns the formulation of three active molecules by prilling: Ketoprofen, Dronedarone and Fexofenadine. These three examples were used to illustrate different ways of incorporating the active ingredient in the process and their associated problems: the melting, the solubilisation and the suspension of active molecules in melted lipids.

A produção de fundidos com baixo nível de defeitos e com propriedades mecânicas adequadas é facilmente alcançada com a previsão do comportamento do metal durante a solidificação. A transferência de calor entre o metal-líquido e o molde, nos primeiros instantes de contato, compromete definitivamente as propriedades mecânicas e a qualidade do produto final. O comportamento da transferência de calor entre o metal e o molde foi explorado através da análise térmica experimental e confrontado com o Modelo de Schwarz Modificado (MSM). Para comprovar experimentalmente os fenômenos previstos no MSM tais como: superesfriamento aparente, posição das interfaces líquido-superaquecido/líquido- superesfriado e da sólido/líquido durante a solidificação foram realizados experimentos com alumínio puro, gálio puro e estanho. Para a análise térmica foram utilizados dois sistemas de solidificação vertical descendente (Griffiths et al., 1993; Jinho et al., 1996; Jamgotchian et al., 1987). O sistema A e o sistema B, sendo que o sistema B também permitia a solidificação vertical ascendente. Em ambos os casos, o fluxo de calor foi direcionado através de uma barra de alumínio (na temperatura ambiente) que foi inserida verticalmente no banho (técnica do “dedo frio”). A barra extrai calor do líquido em função da diferença de temperatura entre a massa líquida e a massa sólida e simula o choque térmico do metal líquido com as paredes de um molde. Os resultados experimentais e os obtidos pela simulação foram confrontados. Apresenta-se a relação experimental entre o superesfriamento e a taxa de solidificação. Discute-se o redimensionamento da Ti (temperatura de interface) na solução de Schwarz e a comprovação experimental da solução do MSM. / The production of casting with low level of defects and adjusted mechanical properties can be obtained with the previous knowledge of the metal solidification behavior. The transference of heat between the metal-liquid and the mold, in the first instants of the contact, compromises definitively the mechanical properties and the final product quality. The behavior of the transference of heat between the metal and the mold was carried out through the experimental thermal analysis and the results were compared with the Modified Schwarz Model (MSM). To experimentally prove, the cooled phenomena in the MSM such as: apparent supercooling, liquid superheated/liquid supercooled interfaces position and of the liquid/solid during the solidification experiments had been carried out with pure aluminum, pure gallium and tins. Two systems A and B, one of descending vertical solidification and another one of descending and ascending solidification, had been used for the thermal analysis. In both systems, the heat flow was directed through a bar of aluminum (in the ambient temperature) that was inserted vertically in the bath (“cold finger” technique). The bar extracts heat of the liquid, had the difference of temperature between the liquid mass and the solid mass, and simulates the thermal shock of the metal with the mold walls. The experimental results were compared with simulated data. In this work are presented experimental relation between the supercooling and the rate of solidification. The new dimension of the Ti (temperature of interface) in the Schwarz equation and the experimental evidence of MSM solution, are considered.

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In the work presented in this dissertation, extensive molecular dynamics (MD) simulations have been performed to investigate various physical problems related to the solid-liquid transitions over a wide range of supercooling and superheating temperatures in model Lennard-Jones systems. The major focus of this work is to investigate the thermodynamics, kinetics, and underlying mechanisms of these problems. There are five topics in this work: (1) The classical nucleation theory (CNT) was tested for both liquid supercooling and solid superheating via different solid-liquid coexistence models. It is found that the CNT is valid for liquid supercooling but invalid for solid superheating. The arising elastic energy plays a significant role in affecting the liquid nucleation in a superheated solid. A new nucleation theory was proposed for describing the internal liquid nucleation of solid superheating. (2) Based on CNT, a new and accurate method was developed for calculating the crystal-melt interfacial free energy and its anisotropy. Our result is very close to Turnbulls experimental results. (3) The face, temperature, and size dependences of the crystallization rate were investigated in this work. The results show that the crystallization rate decreases substantially with the increasing system size. Different from the conventional models, a new model is developed to describe these dependences. (4) Melting from internal nanovoids was investigated in this work. It is found that the mechanism of void melting is quite different from bulk melting and nanoparticle melting. There are four different stages and three local melting temperatures in void melting. The mechanism of the complex melting sequence is systematically explained. (5) The homogenous melting at the upper limit of superheating was investigated in this work. For the first time, the ring diffusion is found to take place in superheated crystals and causes the spontaneous melting. The prevailing instability theories are unsuitable to describe this type of melting. The mechanism of the diffusion-loop mediated melting is carefully discussed in this work.

The liquid-to-crystal nucleation temperature is measured for clathrate-forming mixtures of tetrahydrofuran and water using both an automatic lag time apparatus (ALTA) and a ball screening apparatus. Our results are conclusive evidence that no so-called “memory effect” exists. Either the solid form melts fully or it does not. If it does not, then no supercooling is possible on the next cooling down of that sample, and if it does then the second cooling run and freezing on a sample is just as likely to have a colder nucleation temperature as a hotter one.

According to optimal foraging theory, generalist predators, such as spiders, are thought to feed indiscriminately on prey according to its availability, especially when food is scarce. In contrast, generalists can display selective feeding decisions under regimes of high prey abundance, but few studies have tracked changes in prey choice on a seasonal basis under open field conditions. Additionally, adaptations to surviving winter have been largely ignored in the research of foraging behavior. To elucidate this, I monitored prey availability and collected common forest-dwelling wolf spiders for molecular gut-content analysis, in parallel for 18 months, to assess the temporal changes occurring in spider preferences of common leaf litter prey. In addition, to determine if any physiological improvements to resisting low temperature mortality were affecting spider foraging, I also collected spiders monthly to track changes in spider supercooling points. The results revealed that spiders do exhibit selective feeding throughout the year, and appear to do so in a way that diversifies their diets. Also, despite low litter temperatures putting them in severe freezing risk, cold tolerance in these spiders remained unchanged throughout the winter, which suggests opportunity for growth during this uncompetitive period is paramount to accumulating survivorship-increasing, but also mobility-decreasing, cryoprotectants.