Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1981. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Bibliography: leaves 43-44. / by Miral Eonhah Kim-E. / M.S.

The industrial use of recycled aluminium is greatly limited by the degraded mechanical properties due to the increased impurities. Fe, one of the common impurity content in Al alloys, is difficult to eliminate once introduced into aluminium during primary production or recycling processes. Due to the low solid solubility of Fe in Al, the formation of Fe-rich intermetallic compounds (Fe-IMCs) is inevitable, which is one of the main causes for the deterioration of mechanical properties in various cast Al alloys. In order to obtain desirable mechanical properties of recycled Al alloys, modification and refinement of the Fe-IMCs are urgently required as the compact and refined morphologies of such intermetallics are generally non detrimental to Al alloy's performance. However, manipulating the solidification behaviour of the Fe-IMCs phases, including nucleation and growth, is very challenging because of the inherently more difficult heterogeneous nucleation of the Fe-IMCs compared with that of a pure metal or a solid solution; and the strong growth anisotropy. Limited understanding on mechanisms of nucleation and growth of the multicomponent Fe-IMCs is available in the literature. The aim of this study is to gain a deeper understanding on the heterogeneous nucleation and growth behaviour of Fe-IMCs in various Al alloys. The nucleation and growth of both primary and eutectic Fe-IMCs have been investigated during various solidification conditions including a number of different cooling rates and casting temperatures. Based on the experimental results of the solidification of several ternary and quaternary alloys, effect of Mg on the solidification behaviour of Fe-IMCs was investigated. Further the surface modified TiB2 particles were used to enhance the heterogeneous nucleation of Fe-IMCs in order to refine the Fe-IMCs particles. The dominant Fe-IMC in Al-5Mg-2Si-1.2Fe-0.7Mn alloy is identified, using transmission electron microscopy (TEM), as α-AlFeMnSi with a body centred cubic (BCC) lattice structure and lattice parameter of 1.256nm. In the current alloy system, the nucleation of primary α-AlFeMnSi occur at lower cooling rate (≤0.8K/s) when required nucleation undercooling is reached, as the slower cooling rate allows longer diffusion time for the solute to form a stable nucleation embryo. When casting with 20K superheat, the size of primary α-AlFeMnSi increases gradually from 24.5±3.1μm (870K/s) to 251.3±75.3μm (0.02K/s) and the size of α-AlFeMnSi eutectic increased gradually from 102.0μm (870K/s) to 623.3μm (0.02K/s). The Fe and Mn concentration in α-AlFeMnSi appears to reduce with the increased cooling rate due to the relatively insufficient solute supply when solute concentration is low (1.2wt.% Fe and 0.7wt.% Mn). Microstructure observation reveals that the {011} plane, especially on <111> orientation, is the preferred growth orientation of BCC primary α-AlFeMnSi, resulting in rhombic dodecahedral in 3D. The eutectic α-AlFeMnSi, prefers to initiate on the primary α-AlFeMnSi. In addition to the substantial nucleation undercooling, the research revealed that the nucleation of primary α-AlFeMnSi also rely on the local solute concentration and the solute diffusion. Compared with α-Al, the growth of α-AlFeMnSi is less sensitive to the cooling rate changes due to the complexities in multi-components interaction and different diffusion efficiency of different elements. The addition of Mg to Al-1.2Fe-0.7Mn and Al-2Si-1.2Fe-0.7Mn alloys was found to lead to a morphology change of Fe-IMCs. Al6(Fe,Mn), the predominant Fe-IMC in the Al-1.2Fe-0.7Mn-xMg alloy, changed from needle morphology to interconnected lamellar morphology when Mg composition increased from 0.004wt.% to 6.04wt%. A Mg-rich layer at about 5-20nm in thickness was commonly observed on the Fe-IMC/α-Al interface in the alloys with Mg content. The eutectic lamellar spacing for Al6(Fe,Mn) increases from 1.8±0.3μm to 4.5±0.8μm when Mg content increased from 0.004wt.% to 6.04wt.%. In the case of α-Al12(Fe,Mn)3Si, the predominant Fe-IMC in Al-2Si-1.2Fe-0.7Mn-yMg alloys, its lamellar spacing of the eutectic increased from 1.4±0.3μm to 3.25±0.8μm when Mg increased from 0.04wt.% to 5.41wt.%. Owing to the strong anisotropy of the Fe-IMC crystals, the segregation of solute Mg on preferred growth orientation is higher, causing greater growth restriction on this orientation. Consequently, the growth velocity on other orientations becomes relatively more significant. To optimise the morphology of Fe-IMCs in Al alloys, a novel Αl-Ti-B(Fe) grain refiner for Fe-IMCs has been developed to enhance the heterogeneous nucleation of Fe-IMCs. The addition of the novel grain refiner to an Al-5Mg-2Si-1.2Fe-0.7Mn alloy under controlled solidification condition results in a considerable refinement of the primary Fe-IMCs from 251.3±75.3μm to 110.9±45.5μm and from 127.3±36.2μm to 76.5±18.2μm at cooling rates of 0.02K/s and 0.15K/s, respectively. TEM investigations on the refiner reveal a Fe-rich adsorption monolayer in a zigzag fashion on the prismatic planes on the boride particles. This surface modification is beneficial for the heterogeneous nucleation of the Fe-IMCs. Further investigation of the Al alloy with this grain refiner addition revealed that there existed specific orientation relationships (ORs) between TiB2 and Fe-IMCs: (001)[020]Al13Fe4 // (11-20)[10-10]TiB2, and (001)[120]Al13Fe4 ∠6.05˚ (11-20)[10-11]TiB2; (0-11)[100]α-AlFeMnSi // (0001)[-2110]TiB2, and (0-11)[111]α-AlFeMnSi ∠4.5˚ (0001)[10-10]TiB2. The Fe adsorption on substrate particle, the observed ORs between TiB2 and Fe-IMCs, and the refinement of primary α-AlFeMnSi with the addition of modified TiB2 provide evidence of structure templating and composition templating required by heterogeneous nucleation of Fe-IMCs. This research has delivered contribution to the understanding and new approach for optimizing the morphology of Fe-IMCs in the Fe-containing Al alloys. Using the slow cooling rates (≤0.15K/s), the formation compact primary α-AlFeMnSi can be considerably encouraged. With a lower casting temperature, the size and volume fraction of large Chinese-script α-AlFeMnSi can be significantly reduced. With addition of reasonable Mg content the morphology of Fe-IMC can be modified. Particularly, with the addition of the Al-Ti-B(Fe) grain refiner in well-controlled condition, the primary α-AlFeMnSi can be significantly refined. Thus, by implementing these approaches, the optimized Fe-IMC morphology in the microstructure of Fe-containing Al alloy is able to offer promising mechanical performance.

The microtubule [MT] cytoskeleton of S. pombe is a highly dynamic network of filaments that facilitates intracellular transport, determines cell polarity and plays an essential role in chromosome separation during mitosis. In fission yeast, MTs are nucleated in a temporally and spatially regulated manner from sites called Microtubule Organising Centres [MTOCs], through the activity of both the g-tubulin complex [g-TuC] and the Mto1/2 complex. The Mto1/2 complex determines the localisation of the g-TuC at MTOCs, which change throughout the cell cycle. As cells enter mitosis the cytoplasmic array of MT bundles depolymerise. They are replaced by the intranuclear mitotic spindle and cytoplasmic spindle pole bodyderived astral MTs that in turn give way to the formation of the post-anaphase array. Although much is known about the properties of each type of MT array, the mechanism by which the timing of MT nucleation at different MTOCs is regulated over the cell cycle remains unclear. In the Mto1/2 complex, Mto1 is thought to provide the primary interaction with the g-TuC, and Mto2 functions by reinforcing this interaction. Due to the lack of structural information for the Mto1/2 complex, the molecular mechanism of Mto1/2- mediated assembly of the g-TuC at MTOCs is unknown. The aim of my study is to investigate the possibility that the Mto1/2 complex is able to promote g-TuC assembly by forming a direct template. In addition, I will attempt to determine the molecular role of Mto2 within the Mto1/2 complex and examine ways in which regulation of Mto2 may influence the function the Mto1/2 complex at specific MTOCs. As part of the investigation into the mechanism of Mto2 function, an in vitro analysis of recombinant protein demonstrated that in the absence of Mto1, purified Mto2 is able to self-interact as a tetramer. I have confirmed this interaction in vivo and have also shown that Mto2 forms a dimer as cells enter mitosis. However, in the context of an Mto1/2 complex the significance of the change in Mto2 oligomeric state remains unknown. Hydrodynamic analysis of a truncated form of the Mto1/2 complex suggests that it may form a heterotetramer, a hypothesis which is consistent with the equimolar levels of Mto2 and Mto1 protein within the cell. This information provides some structural insight as to how the Mto1/2 complex may interact with the g-TuC at MTOCs. Further analysis of the Mto1/2 complex revealed that in vivo, the Mto1-Mto2 interaction is disrupted during mitosis. This was found to correlate with the hyperphosphorylation of Mto2, which occurs as cells enter mitosis. Subsequently, an in vitro kinase assay demonstrated that phosphorylation of the Mto1/2 complex reduces the stability of the complex. Mass spectrometry techniques and sequence conservation were used to identify several phosphorylated residues within Mto2 and the ability of these mutants to bind to Mto1 was analysed in vivo and in vitro. In summary, in this study I have uncovered a mechanism which allows fission yeast cells to regulate the nucleation of cytoplasmic MT nucleation in a cell-cycle dependent manner, through a phosphorylation-dependent remodelling of the Mto1/2 complex.

In fission yeast, microtubule (MT) nucleation is regulated in space and time. In interphase, MTs are nucleated in the cytoplasm to regulate cell polarity, whereas in mitosis, nucleation takes place inside the nucleus to form a mitotic spindle. We hypothesize that several non-exclusive mechanisms may be responsible for this differential regulation of MT nucleation. Two fission yeast proteins, Mto1 and Pcp1, are involved in MT nucleation in interphase and mitosis, respectively. These proteins share a sequence motif, called CM1 that is responsible for interaction with the γ-tubulin complex (γ-TuC). In the first part of my project, I tested whether sequence differences between Mto1 and Pcp1 CM1 regions contribute to the differential regulation of MT nucleation in interphase vs. mitosis. I showed that the two CM1 regions are interchangeable and play no role in differential regulation of Mto1 and Pcp1. By generating Pcp1-9A1 mutant, where conserved residues within the Pcp1 CM1 region was replaced with alanines, I showed that Pcp1 CM1 region is required for its function. Moreover, using CM1 regions from two human proteins that are implicated in schizophrenia and microcephaly development, MMGL and CDK5RAP2, I showed that human CM1 domains could rescue yeast protein function, demonstrating that the CM1 region is conserved across evolution. In the second part of my project, I focused on regulation of cytoplasmic MT nucleation. In fission yeast, cytoplasmic MT nucleation occurs from several distinct sites in the cell and is promoted by the Mto1/2 complex. The Mto1/2 complex is composed of multiple copies of Mto1 and Mto2 and interacts with the γ-TuC. Disruption of the interaction of Mto1/2 with the γ-TuC, or of the Mto1-Mto2 interaction, results in a complete loss of interphase cytoplasmic nucleation. As cells enter mitosis, Mto2 is hyperphosphorylated, and the Mto1-Mto2 interaction is disrupted, leading to abolishment of cytoplasmic nucleation. This led to a hypothesis that Mto2 phosphorylation regulated the Mto1/2 complex mitotic disassembly. I showed that Mto2 phosphorylation is used to control levels of cytoplasmic nucleation in both interphase and mitosis. During interphase, I found that Mto2 is phosphorylated in order to reduce levels of MT nucleation. When Mto2 phosphorylation is prevented by mutation of phosphorylatable residues to alanines, Mto1/2 mutant complexes show a more robust interaction with the γ-TuC, and more MTs are nucleated in the cytoplasm. During mitosis, hyperphosphorylation of Mto2 plays a role in the disassembly of Mto1/2 complexes. In particular, while the interaction of wild-type Mto2 with Mto1 is disrupted during mitosis, Mto2-alanine mutants, in which phosphorylation was nearly abolished, are still able to interact with Mto1 in mitosis. Interestingly, Mto1/2 complexes containing Mto2-alanine mutants are still disassembled in mitosis by disruption of Mto2 self-interaction. I used SILAC phosphoproteomics to show that Mto2-alanine is still phosphorylated in mitosis, suggesting the Mto2 self-interaction might also be controlled by phosphorylation. While doing so, I developed a novel SILAC quantification method that is particularly useful for quantification of multiply phosphorylated proteins and peptides. Using data obtained by SILAC, I generated additional Mto2 alanine mutants with more phosphorylation sites mutated. Preliminary analysis showed that these mutants are similar to the alanine mutants analysed previously; however, more analysis is required to generate more definitive conclusions. In summary, in this study I have uncovered the functional conservation of the CM1 region from yeast to human. I also showed that Mto2 phosphorylation regulates cytoplasmic MT nucleation in both interphase and mitosis, by regulating the Mto2-Mto1 interaction and the Mto2-Mto2 self-interaction and therefore remodelling the Mto1/2 complex.

La fabrication de nano-cristaux métalliques suscite un effort de recherche en constante augmentation depuis plusieurs années. Cet immense intérêt est motivé par les propriétés uniques et fascinantes qui apparaissent à l’échelle des tailles nanométriques. En effet, le confinement des électrons au sein d’un nanocristal est un moyen puissant de moduler les propriétés électroniques, optiques et magnétiques d’un matériau. Les synthèses par voies chimiques sont des stratégies très rependues pour fabriquer des nanoparticules métalliques avec des morphologies originales en exploitant la versatilité des milieux réactionnels liquides pour contrôler les mécanismes de formation. Cependant, si la chimie employée lors de ces synthèses n’est pas très compliquée, la compréhension des processus de nucléation/croissance en milieu liquide complexe et l’influence de chaque espèce chimique est un tout autre challenge. Pour y répondre, nous avons utilisé la microscopie électronique en transmission en milieu liquide pour visualiser des phénomènes de croissance à l’échelle nanométrique. Cette récente technique de microscopie in situ nous a permis d’étudier en temps réel la dynamique de croissance de nanoparticules d’or et d’or-cuivre dans des milieux réactionnels de composition contrôlée. Le premier objectif de cette thèse était de distinguer les effets cinétiques (liés aux flux de matière) et les effets thermodynamiques (liés à l’équilibre des nanostructures en fonction de leur environnement) qui dictent tous les deux la forme finale des nanoparticules. De plus, des études systématiques nous ont permis de séparer les inévitables effets du faisceau d’électron, des effets de paramètres spécifiques de la synthèse, comme la forme des germes ou la fonctionnalisation organique, qui sont de toute première importance en chimie des colloïdes. Enfin, des phénomènes induits par le faisceau ont aussi été exploité pour comprendre l’influence de l’irradiation sur la chimie du milieu réactionnel, qui peut induire des réactions d’oxydo-réductions réversibles et contrôlables dans les nano-systèmes bimétalliques. / Recent years have seen a remarkable increase in research activities related to the synthesis of metallic nanocrystals. This intense interest is fueled by the unique and fascinating properties delivered at such size domains. Indeed, electrons confinement by nanocrystals is a powerful means to modulate electronic, optical and magnetic properties of a material. Most current strategies employ chemical synthesis to formulate unique nanoparticle morphologies by exploiting the versatility of liquid reaction media to control the formation mechanisms. Although the chemistry of metal nanocrystal synthesis is not complicated, understanding the nucleation and growth processes in complex liquid media and the influence of each chemical species is altogether a different challenge. It is in this regard, that we have utilized liquid cell transmission electron microscopy to visualize relevant growth phenomenon at the nanoscale. This recent in situ technique allowed us to study in real time the dynamics of growth of Au and Au-Cu nanoparticles in reaction media of controlled composition. The primary goal of this thesis was to distinguish the kinetics effects (related to the flow of matter) and the thermodynamics effects (related to the environment-dependent equilibrium of nanostructures) on final nanoparticle shapes. In addition to this, systematic studies were performed to separate the inevitable beam effects from the influence of specific synthesis parameters such as the seed crystal morphology and the organic functionalization that are of primary importance for colloidal chemists. Beam induced phenomena were also utilized to understand the solution chemistry of the exposed solvent which is in turn responsible for driving reversible redox reactions in bimetallic nano-systems.

Nucleation is the first step in the formation of a new phase in a thermodynamic system. The Classical Nucleation Theory (CNT) is the traditional theory used to describe this phenomenon. The object of this thesis is to investigate nucleation beyond one of the most significant limitations of the CNT: the assumption that the surface tension of a nucleating cluster of the new phase is independent of the cluster’s size and has the same value that it would have in the bulk of the new phase. In order to accomplish this, we consider a microscopic, two-dimensional Lattice Gas Automata (LGA) model of precipitate nucleation in a supersaturated system, with model input parameters Ess (solid particle-to-solid particle bonding energy), Esw (solid particle-to-water particle bonding energy), η (next-to-nearest neighbour bonding coeffiicent in solid phase), and Cin (initial solute concentration). The LGA method was chosen for its advantages of easy implementation, low memory requirements, and fast computation speed. Analytical results for the system’s concentration and the crystal radius as functions of time are derived and the former is fit to the simulation data in order to determine the system’s equilibrium concentration. A mean first-passage time (MFPT) technique is used to obtain the nucleation rate and critical nucleus size from the simulation data. The nucleation rate and supersaturation are evaluated using a modification to the CNT that incorporates a two-dimensional, radius-dependent surface tension term. The Tolman parameter, δ, which controls the radius-dependence of the surface tension, decreases (increases) as a function of the magnitude of Ess (Esw), at fixed values of η and Esw (Ess). On the other hand, δ increases as η increases while Ess and Esw are held constant. The constant surface tension term of the CNT, Σ0, increases (decreases) with increasing magnitudes of Ess (Esw) fixed values of Esw (Ess), and increases as η is increased. Together, these results indicate an increase in the radius-dependent surface tension, Σ, with respect to increasing magnitude of Ess relative to the magnitude of Esw. Σ0 increases linearly as a function of the change in energy during an attachment or detachment reaction, |ΔE|, however with a slope less than that predicted for a crystal that is uniformly packed at maximum density.

The freezing kinetics of binary nitric acid/water aerosols is of fundamental importance to the modelling of polar stratospheric clouds and the role they in ozone depletion over the Arctic/Antarctic regions. Cirrus clouds are also often composed of nitric acid solutions, hence an understanding of freezing process in these aerosols also aids in modelling the earth's radiation budget and global warming. This thesis explores the kinetic phase diagram of nitric acid/water aerosols with sizes ranging between 0. 2 and 1. 5 mm in radius and concentrations ranging between pure water and 0. 45 mole fraction HNO3. Although the kinetic phase diagram has now been studied between 0. 46 mole fraction HNO3 and pure water, more data is needed in the region between 0. 18 and 0. 25 mole fraction HNO3 to confirm the results reported. The project described in this thesis are a continuation of a project begun by Allan Bertram. The measurements involving aerosols with compositions greater than 0. 25 mole fraction HNO3 were carried out as part of Allan Bertram's Ph. D. thesis (see ref. 20) These data were later examined using a more comprehensive data analysis method (as presented in this thesis) in an effort to obtain a more complete understanding of this system.

Understanding the mechanism of zeolite nucleation and crystallization will enable the zeolite science community to tune zeolite properties during synthesis in order to accommodate the purposes of various applications. Thus there has been considerable research effort in "deciphering" the mechanism by studying the growth course of tetrapropylammonium (TPA)-mediated silicalite-1 using several techniques, such as dynamic light scattering (DLS), small-angle X-ray/neutron scattering (SAXS/SANS), and nuclear magnetic resonance (NMR). While these studies have generated a more comprehensive picture on the silicalite-1 growth mechanism, the general application of the mechanism and how it could be applied to other zeolite systems have not been addressed. This work initially tried to apply the insights developed from the TPAsilicalite- 1 clear solution synthesis by investigating the nanoparticles formation and zeolite growth in several tetraethyl orthosilicate (TEOS)-organocation-water solutions heated at 368 K using SAXS. The results are in contrast to TEOS-TPAOH-water mixtures that rapidly form silicalite-1 at 368 K. These results imply that the developed TPA-silicalite-1 nucleation and crystallization mechanism is not universally applicable to other zeolite systems and TPA-silicalite-1 itself could be a special case. With this in mind, the next goal of this work uses in situ SAXS to revisit silicalite-1 growth kinetics prepared by using several TPA-mimic organocations and some asymmetric geometry organocations. The results clearly show the TPA cation is an extraordinarily efficient structure-directing agent (SDA) due to its moderate hydrophobicity and perfect symmetric geometry. Any perturbation of the hydrophobicity and symmetry of SDA leads to a deterioration of zeolite growth. This work further investigates the influences of alcohol identity and content on silicalite-1 growth from clear solutions at 368 K using in situ SAXS. Several tetraalkyl orthosilicates (Si(OR)4, R = Me, Pr, and Bu) are used as the alternative silica sources to TEOS in synthesizing silicalite-1. Increasing the alcohol identity hydrophobicity or lowering the alcohol content enhances silicalite-1 growth kinetics. This implies that the alcohol identity and content do affect the strength of 1) hydrophobic hydration of the SDA and 2) the water-alcohol interaction, through changing the efficiency of the interchanges between clathrated water molecules and solvated silicate species.

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Thesis (Ph. D.)--University of California, Riverside, 2009. / Includes abstract. Available via ProQuest Digital Dissertations. Title from first page of PDF file (viewed March 20, 2010). Includes bibliographical references. Also issued in print.