The Materials Genome Initiative was announced by the White House in June of 2011, and is a multi-agency initiative which calls the materials community to find ways to discover, develop, manufacture, and deploy advanced materials systems faster and more cost-efficiently. Currently, the amount of time it takes to discover and develop a new material system, optimize its properties, integrate it in to a system, certify that system, and develop the manufacturing capability so that it can be deployed in a commercial component takes at least 20 years. Since this trend holds regardless of the material system in question, the implication is that it is the process by which we as a community move through these seven steps, which causes the lengthy timeline. Historically, the discovery, development, and property optimization of a material system relies heavily on deep scientific knowledge, intuition and trial-and-error physical experimentation. Therefore much of the design and testing of materials in these early stages is currently performed through time-consuming and repetitive experimental and characterization feedback loops. Some of these feedback loops could be eliminated in the property optimization step with improved powerful and accurate computational modeling tools. However, while the ability of computational models to be used in this way is not new, models that have been developed in this space have consistently underperformed. Oftentimes, these models fail because they fail to accurately account for the various physical and chemical mechanisms that are driving the system, or because they fail to account for all of the variables which must be included. Here we propose a standard method of communication for these relationships in the form a process-structure-property-performance map, which leverages the known knowledge database of the material system to clearly and visually communicate the relevant variables and their various relationships in a defined materials design space. Such a map is developed here for high-strength Al-Zn-Mg-Cu alloys, which offer a good example of a material system which could benefit from such a standard. This class of alloys, which are typically utilized in aircraft components, have been incorporated in commercial components for nearly 75 years, and due to its long history is a well characterized and well developed system that is highly suited to this kind of examination. In Part I of this work, we develop this standard by first examining the known knowledge database in this system to deduce what the important process, microstructure, and mechanical property variables are that are of interest. Once these variables and the relationships between them are identified, they are organized into a PSPP map according to a proposed set of steps, and can act as a visual standard that can clearly communicate critical information about the mechanisms of the system. For example, if a model developed within this system does not include a variable or a mechanism depicted within the map, it can be used to communicate the ways in which the model will be constrained. Similarly, when experimental data is collected within this space the map can be used to clearly communicate which variables in the space were held constant, which variables were tracked and accurately measured, and if any variables were unaccounted for. This information can help to communicate what situations the data can be used in, and how the space that the experimental data can be used in is constrained. In Part II of this work, we vary multiple parameters within the high-strength Al-Zn-Mg-Cu system defined in Part I, and attempted to track and measure as many of the variables within the space as possible using commonly available testing and characterization methods. In tackling such a large project in the complicated materials system of high-strength wrought Al-Zn-Mg-Cu alloys, we are able to understand which current testing and characterization methods are well suited to tracking these variables when the number of test specimens becomes quite large and when variability among those specimens is involved. We are also able to identify opportunities for future work in this area, which could be focused on improving our ability to implement projects of the scope that is required here. In addition to evaluating the feasibility of the various measurement and characterization methods, the raw data and the analyzed results for this work are cataloged in an associated data repository and have been made available for use in future work in this and other areas.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23023号 / 理博第4700号 / 新制||理||1674(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 島川 祐一, 教授 寺西 利治, 教授 長谷川 健 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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This study examined several features of flexible polyurethane foams from a structure-property perspective. A major part of this dissertation addresses the issue of connectivity of the urea phase and its influence on mechanical and viscoelastic properties of flexible polyurethane foams and their plaque counterparts. Lithium salts (LiCl and LiBr) were used as additives to systematically alter the phase separation behavior, and hence the connectivity of the urea phase at different scale lengths. Macro connectivity, or the association of the large scale urea rich aggregates typically observed in flexible polyurethane foams was assessed using SAXS, TEM, and AFM. These techniques showed that including a lithium salt in the foam formulation suppressed the formation of the urea aggregates and thus led to a loss in the macro level connectivity of the urea phase. WAXS and FTIR were used to demonstrate that addition of LiCl or LiBr systematically disrupted the local ordering of the hard segments within the microdomains, i.e., it led to a reduction of micro level connectivity or the regularity in segmental packing of the urea phase. Based on these observations, the interaction of the lithium salt was thought to predominantly occur with the urea hard segments, and this hypothesis was confirmed using quantum mechanical calculations. Another feature of this research investigated model trisegmented polyurethanes based on monofunctional polyols, or "monols", with water-extended toluene diisocyanate (TDI) based hard segments. The formulations of the monol materials were maintained similar to those of flexible polyurethane foams with the exceptions that the conventional polyol was substituted by an oligomeric monofunctional polyether of ca. 1000 g/mol molecular weight. Plaques formed from these model systems were shown to be solid materials even at their relatively low molecular weights of 3000 g/mol and less. AFM phase images, for the first time, revealed the ability of the hard segments to self-assemble and form lath-like percolated structures, resulting in solid plaques, even though the overall volume of the system was known to be dominated by the two terminal liquid-like polyether segments. In another aspect of this research, foams were investigated in which the ratios of the 2,4 and 2,6 TDI isomers were varied. The three commercially available TDI mixtures, i.e., 65:35 2,4/2,6 TDI, 80:20 2,4/2,6 TDI, and 100:0 2,4/2,6 TDI were used. These foams were shown to display marked differences in their cellular structure (SEM), urea aggregation behavior (TEM), and in the hydrogen bonding characteristics of the hard segments (FTIR). Finally, the nanoscale morphology of a series of 'model' segmented polyurethane elastomers, based on 1,4-butanediol extended piperazine based hard segments and poly(tetramethylene oxide) soft segments, was also investigated using AFM. The monodisperse hard segments of these 'model' polyurethanes contained precisely either one, two, three, or four repeating units. Not only did AFM image the microphase separated morphology of these polyurethanes, but it also revealed that the hard domains preferentially oriented with their long axis along the radial direction of the spherulites which they formed. / Ph. D.

Blendas poliméricas são largamente utilizadas nas indústrias de pneus por causa de seu baixo custo e das melhores propriedades que podem ser obtidas. Quando os componentes da blenda não são miscíveis entre si, métodos de compatibilização química (utilizando agentes compatibilizantes) ou mecânica (aumentando o tempo de mistura dos elastômeros) são necessários para melhorar a compatibilidade dos componentes da mistura. Neste trabalho, o Trans-Polioctenileno (TOR) foi usado como agente compatibilizante da blenda de NR/SBR. A viscosidade Mooney, a Carga e o Alongamento na Ruptura de diversas blendas foram avaliados, utilizando um planejamento fatorial. Os resultados obtidos mostraram que o TOR tem maior influência na alteração da viscosidade Mooney, seguido pelo tempo de premix e de repasse. No caso das propriedades dinamométricas, a carga e o alongamento na ruptura são mais sensíveis às alterações do tempo de processamento dos polímeros. O TOR leva a uma ligeira diminuição destas propriedades. Baseado nos resultados estatísticos, equações de regressão para avaliar as propriedades estudadas em função da concentração de TOR e do tempo de processamento foram propostos e posteriormente verificados, utilizando blendas que não estavam incluídas no planejamento original. Os resultados foram bastante satisfatórios, tanto na determinação dos efeitos das variáveis quanto na determinação das equações. Concluiu-se que a viscosidade Mooney é mais sensível às alterações da concentração de TOR do que às alterações do tempo de mistura dos elastômeros e que as propriedades dinamométricas são mais afetadas pelo tempo de processamento. / Polymer blends are used in tyre industries because of their low cost and better properties. When the blend components are not miscible, chemical methods (using compatibilizing agents) or mechanical methods (increasing the mixture time of elastomers) of compatibilization are necessary to improve the compatibility of the components of the blend. In this work, Trans-Polyoctenylene Rubber (TOR) was used as a compatibilizing agent of the NR/SBR rubber blend. The Mooney viscosity, stress and elongation at break of different blends were evaluated, using a Factorial Design. The experimental results obtained showed that the Mooney viscosity is greatly affected by the addition of TOR whereas the dynamometric properties, the stress and elongation at break are more sensitive to the changes of processing time of polymers. Based on statistical results, regression equations to evaluate the properties studied as a function of TOR concentration and processing time were obtained and verified using blends which were not on the original design. The results were very satisfactory, either on the effects determination or on the regression equation determination. It was concluded that the Mooney viscosity is more sensitive to the alterations of TOR concentration than the changes in the processing time of the elastomers and the dynamometric properties are more affected by the processing time.

Aim of this thesis is to explain the role of property relations in the production of urban form. It is assumed that urban form is produced not only as a physical setting but also as a concrete and relatively fixed manifestation of property relations. In this respect, urban form should be considered in a relational conception of space. The study departs from the proposition that property relations are the main determinants of the formation of urban space, and private property constitutes the generator of the dynamics and contradictions of urban formation, through a continuous process of fragmentation. For this reason, in the control of urban formation, property rights are the basic element that city planners have to face. Therefore, this study presents a comprehensive framework that integrates the categories of urban morphology with a structural analysis of urban formation process. As the essential unit of capitalist city, &ldquo / production of the parcel as a commodity&rdquo / is elaborated as the core of urban formation process. In this framework, morphogenesis of Yenisehir&ndash / Ankara is analyzed in order to understand its historical transformation with reference to the context of property relations. Its morphological layers are depicted as a product of the contradictory relation between urban planning and property relations. It is seen that the morphogenesis of Yenisehir includes three distinct layers of formation, which are characterized by the gradual domination of commodity production in the formation process of urban space.

This study, by focusing on the economic reform attempts in the USSR and the privatization process in the Russian Federation, will question the scope of political change in Russia during the capitalist transformation process until the end of the Yeltsin period. It will be argued that the determination of the political processes on property relations during the time of the USSR persisted in the Yeltsin period since after the collapse of the USSR, main political actors of the Soviet system such as the Party and ministry officials and the enterprise managers maintained their dominant positions within the property relations. As will be shown in the thesis, this was ensured through their successful interventions in the privatization processes. Hence, people who had important positions in the former Soviet Union, became whether the new owners of state assets, or had the authority to determine the new owners.

Blendas poliméricas são largamente utilizadas nas indústrias de pneus por causa de seu baixo custo e das melhores propriedades que podem ser obtidas. Quando os componentes da blenda não são miscíveis entre si, métodos de compatibilização química (utilizando agentes compatibilizantes) ou mecânica (aumentando o tempo de mistura dos elastômeros) são necessários para melhorar a compatibilidade dos componentes da mistura. Neste trabalho, o Trans-Polioctenileno (TOR) foi usado como agente compatibilizante da blenda de NR/SBR. A viscosidade Mooney, a Carga e o Alongamento na Ruptura de diversas blendas foram avaliados, utilizando um planejamento fatorial. Os resultados obtidos mostraram que o TOR tem maior influência na alteração da viscosidade Mooney, seguido pelo tempo de premix e de repasse. No caso das propriedades dinamométricas, a carga e o alongamento na ruptura são mais sensíveis às alterações do tempo de processamento dos polímeros. O TOR leva a uma ligeira diminuição destas propriedades. Baseado nos resultados estatísticos, equações de regressão para avaliar as propriedades estudadas em função da concentração de TOR e do tempo de processamento foram propostos e posteriormente verificados, utilizando blendas que não estavam incluídas no planejamento original. Os resultados foram bastante satisfatórios, tanto na determinação dos efeitos das variáveis quanto na determinação das equações. Concluiu-se que a viscosidade Mooney é mais sensível às alterações da concentração de TOR do que às alterações do tempo de mistura dos elastômeros e que as propriedades dinamométricas são mais afetadas pelo tempo de processamento. / Polymer blends are used in tyre industries because of their low cost and better properties. When the blend components are not miscible, chemical methods (using compatibilizing agents) or mechanical methods (increasing the mixture time of elastomers) of compatibilization are necessary to improve the compatibility of the components of the blend. In this work, Trans-Polyoctenylene Rubber (TOR) was used as a compatibilizing agent of the NR/SBR rubber blend. The Mooney viscosity, stress and elongation at break of different blends were evaluated, using a Factorial Design. The experimental results obtained showed that the Mooney viscosity is greatly affected by the addition of TOR whereas the dynamometric properties, the stress and elongation at break are more sensitive to the changes of processing time of polymers. Based on statistical results, regression equations to evaluate the properties studied as a function of TOR concentration and processing time were obtained and verified using blends which were not on the original design. The results were very satisfactory, either on the effects determination or on the regression equation determination. It was concluded that the Mooney viscosity is more sensitive to the alterations of TOR concentration than the changes in the processing time of the elastomers and the dynamometric properties are more affected by the processing time.

Property relations of spouses in the period of the Emperors Augustus and Justinian I. Abstract The topic of this thesis is the property relations of the spouses in Roman law during the reign of Emperors Augustus and Justinian I. Marriage is generally an important legal institute, which can be viewed from different points of view. Legal regulation of marriage was included also in Roman law. Since the Roman marriage was very specific, it was relatively often undergoing major or minor reforms. The aim of this thesis is to analyze the property situation of spouses during the reign of Emperors Augustus and Justinian I. Emperor Augustus came to power in 27 BC, in the time, when the institute of marriage and family was declining in importance and the whole Roman society was in a crisis. On the other hand, the religious-minded Justinian came to power in 527 AD. At this time the state religion was Christianity. The thesis is divided into six main chapters. The first chapter gives a general view of the institute of marriage. The second part of the first chapter focuses on Roman marriage. The second chapter explains the basic legal institutes of matrimonial property law. The third chapter deals with the historical development of the Roman Empire. Coming to power of Emperor Augustus is discussed at the end of this...