Thermal behavior and molecular packing of a series of £\-helical poly(L-glutamates), with n-alkyl side chain of various lengths (m(number of carbons in the alkyl group) = 1, 2, 6, 12,18), were studied by means of differential scanning calorimetry, polarizing light microscopy and X-ray diffraction. For polymers of m = 1 and 2, There is a pseudohexagonal structure below ca. 130 oC and above this temperature the stable phase is the hexagonal columnar phase. There exists a layered structure in the polymer of m = 6, as well as a solvent induced hexagonal columnar structure which formed during solution casting process. In the polymer of m = 12, a layered structure was formed in the temperature range between 20 to 255 oC. However, for longer side chain, m = 18, tendency of crystallization of alkyl long side chain forced the backbone to pack into layer structure. There are two distinct melting temperature at ca. 60 oC, and the enthalpy are ca. 53 and 19 J/g, which corresponding to the melting of hexagonal and monoclinic side chain crystallines. The polymers with longer side chain (m = 6, 12 and 18) tend to be lyotropic liquid crystalline phase within lamellar inter-rod distance of 1.25 nm in solution state, and the structure will remain after drying. However, the inter-rod distance will collapse at the temperature above ca. 200 ¢J and will not recover after cooling.

ABSTRACT Structural evolution and its effect on optical absorption/emission behavior of derivative of PPVs upon isothermal heat treatment at elevated temperatures were studied by means of a combination of polarized light microscopy, x-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, and photoluminescence spectroscopy. The main physical picture drawn from results of this study over a series of PPVs with flexible side-chains may be summarized as the following: (1) They are generally liquid-crystalline in nature, typically biaxially nematic in optical texture but morphologically characterized as of lamellar or hexagonal columnar structure. This is consistent with the nematogenic nature one would expect from the rigid backbone as well as the smectogenic nature one would expect from the aliphatic side-chains. (2) The aggregates formed in solutions and the supramolecular assemblies formed in the bulk state are structurally similar (in terms of the similar level of conjugation), and hence possibly of the same thermodynamic origin. This surfactant-like self-ordering behavior is consistent with the tendency towards segregation between the aromatic, rigid backbone and the aliphatic, flexible side-chains. (3) The collapse of these conjugated polymers with flexible side-chains into aggregates appears to be a general phenomenon upon slow to moderate solvent removal and not limited to the present case of poor solvency power. This is consistent with the strong tendency toward phase separation in rigid rod solutions delineated by Flory some 30 years ago. (4) All the above observations may be explained in terms of lyotropic or thermotropic self-assembly of hairy-rod chains into coiled helical conformation with ellipsoidal cross section for the conjugated backbone as shown schematically in Figure 4-42 and 4-43. The flexible side-chains generally tend to fill the space within the ellipsoidal cylindrical structure. As the side-chain length is increased, the increased Van der Waals attraction among side-chains results in more extended period of helical twist or more straighten backbone conformation, rendering preference of lamellar structure over hexagonal helical structure. (5) As a consequence, supramolecular aggregation is basically enhanced by increased side-chain length or backbone rigidity. This in turn results in more extended conjugation length or more fully developed

The field of organic electronics has received much attention over the last few years, and engineering of organic crystals to grow with pi-electron systems arranged in a face-to-face motif has been shown to be beneficial in electronic devices. The effects of combining aromatic and perfluorinated aromatic derivatives have shown that the intramolecular stacking pattern can be changed from an edge-to-face arrangement to that of a face-to-face motif. Before the work described herein, there were no reported studies of the supramolecular behavior of fused polycyclic aromatic compounds with partial peripheral fluorination, inducing the desired face-to-face behavior. This is the main focus of the thesis. Furthermore, by exploiting the interactions between the fluorinated and non-fluorinated faces of the molecule, columnar liquid crystalline behavior can be achieved through variations of the alkyl substituents on the molecule.

Ingeniero Civil de Minas / La flotación de minerales es un proceso industrial ampliamente utilizado en minería, para separar selectivamente material valioso desde una roca original, utilizando propiedades superficiales relacionadas con la hidrofobicidad/hidrofilicidad que todos los minerales poseen. El proceso utiliza burbujas de gas, que atraviesan una fase pulpa (agua y partículas suspendidas de la roca inicial), para colectar material previamente hidrofobizado. En términos netos, las burbujas, principalmente gobernadas por fuerzas de empuje, se mueven verticalmente hacia arriba mientras que el líquido (pulpa) se mueve verticalmente hacia abajo. Estudios indican que la distribución y el movimiento de las burbujas en columnas no es homogéneo. Consecuentemente, se puede hipotetizar que el movimiento de las burbujas en celdas de flotación de tipo columnar está asociado a patrones de flujo que impactan el transporte de líquido, y con esto, la transferencia de reactivos. El objetivo de este trabajo es estudiar cómo dicho movimiento conjunto de líquido y gas afecta el transporte de reactivo superficialmente y no superficialmente activo a través de un flujo de burbujas. Simultáneamente se presentan variantes en la metodología de medición de la velocidad superficial de gas para obtener un parámetro de caracterización de gas en celdas de flotación columnar más robusto y de mayor significado físico. La metodología experimental de trabajo involucra el estudio del transporte radial de reactivo en un sistema de laboratorio 2-D mientras que la dispersión de gas y el transporte axial de reactivo se evalúa en una columna piloto de flotación. Estudios de laboratorio en el sistema 2-D indicaron que la resistividad aparente al transporte de los reactivos utilizados (Espumante Aerofroth 70 Plus y Sulfato pentahidratado de cobre) fue menor en el uso del reactivo no superficialmente activo (Sulfato de cobre) y que esta disminuyó en presencia de un flujo de burbujas. De lo anterior se concluye que la metodología y el punto de incorporación de reactivos son clave para el correcto funcionamiento de una operación de flotación. En el sistema 3-D se confirma que el diámetro del tubo muestreador es relevante para obtener resultados representativos de la velocidad superficial de gas en una celda columnar. Un modelo matemático del tipo exponencial para estimar este valor a partir de un tubo muestreador de diámetro arbitrario fue obtenido. Finalmente los resultados del transporte de reactivo axial indican que es posible dispersar un reactivo con una tendencia cercana a la homogeneización a lo largo de todo el eje axial, comportamiento que es esperable en una columna de flotación a escala industrial. / 10/10/2022

The present work represents a systematical study of the growth of columnar, metallic thin films deposited under highly oblique vapor incidence on planar substrates. Oblique angle deposition is a physical vapor deposition technique that is based on the self-shadowing effect. This enables the fabrication of highly porous thin films that are composed of three-dimensionally separated, micro-, and nano-sized columns. For this study, metals that cover a wide range of melting points and crystal structures have been chosen, and the observed growth characteristics are compared with each other to gain information about the growth of obliquely deposited metallic thin films in general. Among the various parameters that have an influence on the growth of columnar thin films, in the focus of this work are the angle of the incoming particle flux, substrate rotation frequency, and substrate temperature as well as the influence of the residual gas atmosphere. The first part deals with a morphological analysis of the columnar, metallic thin films by scanning electron microscopy (SEM). The columnar shape, the columnar tilt angle, and the thin film porosity are investigated depending on the incidence flux direction as well as substrate temperature and rotation. It is examined how a reduction of the substrate temperature down to 77 K - realized by a liquid nitrogen cooled sample holder - influences the growth of the columnar thin films. Further, it is analyzed how substrate rotation influences the local deposition geometry and accordingly the growth behavior of tilted columns, spirals, screws, and upright columns. Based on geometrical considerations, a theoretical model is proposed and compared with the made observations. The second part focusses on the high-resolution local structure analysis of individual columns via (scanning) transmission electron microscopy (TEM). On the one hand, the columnar structure is analyzed depending on the substrate temperature and substrate rotation via high resolution TEM. On the other hand, the crystallinity of individual columns is studied along the entire column by nanobeam electron diffraction. This technique is also applied to gain information about the orientation of the crystallites at the substrates surface and to investigate the selection processes of crystalline orientations during the growth. Moreover, the presented studies reveal under which conditions single crystalline columns are forming. In the final part, the texture of the columnar, metallic thin films is analyzed depending on the film thickness, the angle of the incoming particle flux as well as on the substrate temperature. X-ray diffraction (XRD) measurements, such as pole figures, are applied to determine the orientation of the lattice planes in the columns depending on the incident flux direction and on the substrate temperature. The observations are backed by reflection high-energy electron diffraction (RHEED) investigations. A model is developed that enables to explain why the tilt of the lattice directions in the columns is not equal to the tilt angle of the columns. A further theoretical model is introduced that enables to roughly estimate the tilt angle of the lattice direction that ensures the fastest vertical columnar growth.:1 MOTIVATION 7 2 BASICS OF OBLIQUE ANGLE DEPOSITION 9 2.1 Thin film growth by oblique deposition 9 2.1.1 Physical vapor deposition 9 2.1.2 Nucleation 10 2.1.3 Shadowing 11 2.1.4 Structure of individual columns 12 2.2 Sculpturing thin films on the nanometer scale 13 2.2.1 Angle of the incoming particle flux 13 2.2.2 Substrate rotation 16 2.2.3 Substrate temperature 17 2.3 Application areas for metallic nanostructured thin films 20 3 EXPERIMENTAL DETAILS 23 3.1 Sample fabrication 23 3.1.1 General deposition system setup and evaporation process 23 3.1.2 Crucibles, substrates, and sample holders 25 3.1.3 Controlling substrate movement and temperature 26 3.1.4 Controlling film thickness and deposition rate 29 3.2 Sample characterization 30 3.2.1 Scanning electron microscope (SEM) 30 3.2.2 Transmission electron microscopy (TEM) 31 3.2.3 X-Ray Diffraction (XRD) and In-Plane Pole Figure measurements (IPPF) 33 3.2.4 Reflection high-energy electron diffraction (RHEED) 36 3.2.5 Raman scattering spectroscopy 36 4 MORPHOLOGICAL ANALYSIS OF COLUMNAR THIN FILMS 39 4.1 Oblique angle deposition 40 4.1.1 Deposition at room temperature 40 4.1.2 Deposition at different temperatures 43 4.2 Glancing angle deposition 61 4.2.1 Continuous substrate rotation 61 4.2.2 Discrete substrate rotation 66 4.3 Summary of results 69 5 STRUCTURAL ANALYSIS OF INDIVIDUAL COLUMNS 71 5.1 Oblique angle deposition 71 5.1.1 Tilted columns grown at room temperature 71 5.1.2 Tilted columns grown at different substrate temperatures 78 5.2 Glancing angle deposition 82 5.2.1 Vertical columns grown by continuous substrate rotation 82 5.2.2 Zigzag columns grown by discrete substrate rotation 85 5.3 Discussion 87 5.4 Summary of results 89 6 TEXTURE ANALYSIS OF COLUMNAR THIN FILMS 91 6.1 Influence of the film thickness 91 6.2 Influence of the incoming flux direction 99 6.3 Influence of the substrate temperature 110 6.4 Summary of results 116 7 SUMMARY AND CONCLUSIONS 119 8 LIST OF LITERATURE 123 9 LIST OF ABBREVIATIONS 134 10 LIST OF VARIABLES AND CONSTANTS 136 11 ACKNOWLEDGEMENTS 139 PUBLICATION LIST 140 SELBSTSTÄNDIGKEITSERKLÄRUNG 143

Ferritic stainless steel is typically used in the automotive industry to fabricate welded tube that is plastically deformed for flanging, bending and necking. The effect of welding parameters during autogenous gastungsten arc welding (GTAW) of thin sheet on the weld metal structure and tensile properties were determined. Two grades of ferritic stainless steels, a titanium-containing Grade 441 and a titanium-free molybdenum-containing Grade 436, were used as base metal. Statistical analysis was used to determine the influence of welding parameters on the microstructure of autogenous GTAW welds. The results of Grade 441 indicated that the welding speed and peak welding current had a statistically significant influence on the amount of equiaxed grains that formed. For Grade 436, the same welding parameters (welding speed and peak welding current) had a statistically significant influence on the grain size of the weld metal grains. The ductility of a tensile test coupon machined parallel to the weld direction, for both base metal grades, was unaffected by the welding parameters or the weld metal microstructure. The elongation was determined by the amount of weld metal in the gauge area of a tensile coupon. The titanium content of the base material seems to have the most significant effect on the formation of equiaxed grains. / Dissertation (MEng)--University of Pretoria, 2019. / Materials Science and Metallurgical Engineering / MEng / Unrestricted

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L'objectif de ce travail de thèse, est de développer un matériau d'apport et un mode opératoire de soudage associé permettant d'assembler des tôles d'acier K44X pour la fabrication de collecteurs d'échappement automobiles. Les propriétés de l'acier K44X ayant été optimisées pour répondre au mieux aux contraintes de l'application, les conditions de soudage recherchées devront, dans la mesure du possible, éviter de dégrader les caractéristiques de l'acier, en particulier en termes de tenue mécanique à haute température et de résistance à l'oxydation et à la fatigue thermique. Ce mémoire est divisé en quatre chapitres. Le premier chapitre est consacré à une présentation synthétique des évolutions dans le domaine de la fabrication des collecteurs d'échappement automobiles, et des connaissances actuelles dans les domaines des aciers inoxydables ferritiques et sa soudabilité, des procédés de soudage à l'arc. Le second chapitre présente les caractéristiques de l'acier K44X et la problématique de l'étude, puis décrit le travail d'élaboration des matériaux d'apport de différentes compositions. Ainsi que les résultats d'une caractérisation préliminaire des soudures obtenues avec les différents matériaux. Le chapitre 3 traite de la caractérisation de la tenue en service de l'assemblage retenu à l'issu du chapitre précédent. Les tests d'oxydation, de traction à chaud sur zone fondue des soudures ou sur assemblages complets, et de fatigue thermique, utilisés pour réaliser cette caractérisation sont décrits, et les résultats sont discutés. La fin de ce chapitre est consacrée à la caractérisation des précipités formés dans les zones fondues. Enfin, le dernier chapitre est consacré à la modélisation thermique du soudage et à la modélisation de la solidification, dans le but de tenter de prédire le type de microstructure de zone fondue formée lors d'une opération de soudage, en fonction des paramètres procédés. Cette modélisation, qui s'appuie sur les résultats d'un essai de soudage instrumenté, doit notamment permettre de prédire si les conditions de soudage, pour une composition d'acier donnée, permettent ou non de former une structure de grains équiaxe en zone fondue des soudures. / The objective of this work is to develop a filler metal and an associated welding procedure allowing to join sheets of steels K44X for the manufacturing of exhaust manifolds for automotive. The properties of the steel K44X having been optimized to answer at best the constraints of the application, the welding conditions will have to, as possible, avoid degrading the characteristics of the steel, in particular in terms of mechanical strength with high temperature, oxidation resistance and in thermal fatigue.This report is divided into four chapters.The first chapter is dedicated to a synthetic presentation of the evolutions in the field of the manufacturing of the automotive exhaust manifolds, and current knowledge in the domains of ferritic stainless steels and its weldability, and in arc welding processes.The second chapter presents the characteristics of the steel K44X and the problem of the study, then described the work of elaboration of the filler metals with various compositions. As well as the results of a preliminary characterization of the welds obtained with the various materials.The chapter 3 is about the characterization of the in-service behavior of the assembly stemming from the previous chapter. The tests of oxidation, hot traction on molten zone of the welds or on complete assemblies, and of thermal fatigue, used to realize this characterization are described, and the associated results are discussed. The end of this chapter is dedicated to the characterization of precipitates formed in the molten zones.Finally, the last chapter is dedicated to the thermal modelling of the welding and to the modelling of the solidification, with the aim of trying to predict the type of microstructure of molten zone formed during a welding operation, according to the process parameters. This modelling, based on the results of a instrumented experimental test of welding, has to allow in particular to predict if the welding conditions, for a given composition of steel, allow or not to form a structure of grains equiaxed in molten zone of the welds.

Magnésio e suas ligas têm adquirido importância cada vez mais significativa como material estrutural de peso leve despertando um singular interesse pela indústria uma vez que oferece a melhor relação peso/resistência entre os metais. Os campos mais conhecidos de sua aplicação consistem na construção de veículos, na aeronáutica, manipulação industrial (robôs, automatização) e tecnologia de comunicação. Em particular, a indústria automobilística tem crescentemente ampliado a utilização de ligas de magnésio na produção de peças que vão desde caixas de câmbio até aros de rodas. As principais razões para este desenvolvimento são: mudanças na legislação ambiental, as exigências de cliente, e objetivos corporativos que requerem veículos mais leves diminuindo o consumo de combustível. O uso do magnésio para aplicações estruturais em altas temperaturas é limitado devido a sua baixa resistência à fluência. Isso se deve ao enfraquecimento do contorno de grão a partir da precipitação descontínua da fase b-Mg17Al12 de baixo ponto de fusão. Dentre as ligas de magnésio desenvolvidas para resistência à fluência, as ligas do sistema Mg-Al-RE-Ca oferecem ótimo desempenho com resultados similares à liga de alumínio ADC12. Muitos trabalhos sobre o sistema de ligas Mg-Al-RE-Ca foram realizados visando compreender a relação entre microestruturas e propriedades mecânicas. Entretanto, poucos estudos relacionaram a influência das variáveis de solidificação na formação das microestruturas. O presente trabalho tem como objetivo realizar um estudo em uma liga Mg-4%Al-3%La-1%Ca analisando a influência das variáveis térmicas tais como taxas de resfriamento, velocidade da isoterma liquidus e gradientes de temperatura, na formação de estruturas, na transição colunarequiaxial e espaçamento dendrítico durante o processo de solidificação. A previsão das distintas estruturas, tais como zona colunar e equiaxial é de grande interesse para avaliação e projeção das propriedades mecânicas dos fundidos. Dessa forma, a liga estudada foi submetida à solidificação unidirecional vertical ascendente e análise térmica. Foram realizadas análises metalográficas nos lingotes solidificados. Os resultados colaboram para uma melhor compreensão do fenômeno de solidificação da liga e serve como ferramenta no desenvolvimento de modelos de previsões de formação de micro e macroestruturas que influenciam diretamente nas propriedades mecânicas. / Due to their superior weight/resistance relation, magnesium and its alloys have been acquiring a great deal of importance in the modern industry, specially as lightweight structural materials in the fields of vehicle construction, aeronautics, industrial robotics, automation, and communication technologies. In particular, the automotive industry has been increasingly expanding the use of magnesium alloys in the production of auto-parts, ranging from gearbox housings to steering wheels. The main reasons for this developments are changes in environmental legislations, new customer requirements, and corporate policies regarding fuel consumption and weight/power relations. The use of magnesium alloys for structural applications at high temperatures is limited due to the precipitation of the discontinuous phase b-Mg17Al12, which in fact, weakens the grain boundary during service resulting in a low creep resistance. Among the magnesium alloys developed for creep resistance, the alloys of the system Al-Mg-RE-Ca offer optimum performance with results similar to the ADC12 aluminum alloy. Many studies on the Al-Mg-RE-Ca system alloys were aimed to understand the relationship between microstructure and mechanical properties. However, few studies undertake the influence of the solidification variables in the microstructure formation. This work aims to study the influence of some thermal variables such as temperature gradients, solidification and growth tip rate on the formation of microstructures, the columnar/equiaxial transition and dendrite arm spacing, during the solidification process of a Mg-4%Al-3%La- 1%Ca alloy. The prediction of the different structures, such as the columnar and the equiaxial regions is of great interest for the assessment and projection of the mechanical properties of the casts. Therefore, the alloy studied in this work were submitted to thermal analysis during an unidirectional vertical ascending solidification, as well as optical and scanning electron microscopy characterization. The results contribute to a better understanding of the solidification phenomena of the magnesium alloys, as well as a tool in the development of numerical models for the prediction of structures which directly influence the mechanical properties of the parts.

Microstructure refinement was observed in the fusion zone of AZ31 magnesium (Mg) alloy resistance spot welds when an inoculant was added, either Ti, Al8Mn5, or Mn. The dependence of inoculant potency on the lattice disregistry between inoculants and matrix, and on the liquid cooling rate was studied. Microstructural characterization was performed via optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Thin foils containing the interface of the inoculant particles and Mg matrix were prepared using a focused ion beam (FIB) technique. Columnar dendritic structures in the vicinity of the fusion boundary and equiaxed dendritic structures in the central area were observed in the fusion zone of welds in the SA and SB AZ31Mg alloys from different suppliers. However, the columnar dendritic zone (CDZ) was well restricted, and the width of the CDZ and the diameters of equiaxed dendrites were much smaller in the SA alloy than those in the SB alloy due to the earlier columnar-equiaxed-transition (CET) in the SA alloy. The refined microstructure in the fusion zone of the SA alloy welds is attributed to the pre-existence of the larger Al8Mn5 particles of 4-10 microns in length in the SA alloy which act as an inoculant for alpha-Mg heterogeneous nucleation. Fatigue life and dislocation substructure were compared between the SA and SB welds. The SA welds with the refined microstructure displayed an enhanced fatigue resistance compared to the SB welds, when the interfacial failure took place across the fusion zone. The increased number and dispersion of slip systems in the fine-grained SA welds contributed to the improvement of fatigue life. The well-developed columnar dendritic grains were successfully restricted and the coarse equiaxed dendritic grains were efficiently refined by intentionally adding Ti or Mn inoculant particles into the as-received SB alloy welds. The Ti and Mn particles of about 8μm diameter were observed to promote the nucleation of alpha-Mg grains during welding. TEM examinations showed the existence of local orientation relationships between the respective inoculants Ti, Mn, and Al8Mn5 with the Mg matrix. The further lattice matching was observed between the Al8Mn5 particles and Mg. The diameter of the added inoculant should be larger than 1.8 microns to make it a potent inoculant based on the thermodynamic calculation. Microstructural examinations of samples with different inoculant additions and under different cooling rates showed that the inoculant potency was high for the Ti inoculant, medium for the Al8Mn5, but low for the Mn, when the cooling rate was low. This order in the decrease of grain refinement efficiency is inversely proportional with the order of crystallographic lattice disregistry between inoculants and matrix, which is calculated based on a crystallographic matching model. This implies that the lattice disregistry determines the potency of inoculants at the low cooling rates. In comparison, the lattice disregistry did not influence the heterogeneous nucleation, when the cooling rate was high. It could be inferred that an extremely high cooling rate produces a large supercooling, and provides a sufficient driving force for heterogeneous nucleation.