Incorporation of water molecules in the crystal structure of an organic compound has strong effects on its physical and chemical properties. Therefore, the study on stability of water-incorporated pharmaceutical compounds and mechanisms of hydration and dehydration is very important for the pharmaceutical industries. The main goals of the present research project were quantitative description of the crystallization and solid-state transformations of pseudopolymorphs of sodium naproxen in order to provide fundamental information concerning stability of the pseudopolymorphic forms. Furthermore, macroscopic phenomena of size reduction and anisotropic water-removal by dehydration were rationalized by microscopic aspects of crystal lattice structures. The heats of solution for each pseudopolymorph were estimated by fitting the solubility data with the vant Hoff equation, and their use was extended by the thermodynamic cycle developed in the present study. According to the thermodynamic cycle, for an enantiotropic system, a form with a lower degree of hydration always has the lower heat of solution than a form with a higher degree of hydration, implying that a form with a lower degree of hydration is more stable. The relative stabilities of the dihydrated, the monohydrated, and the anhydrous sodium naproxen at 0% relative humidity were investigated by dehydration of the dihydrated form and powder X-ray diffraction. The monohydrate is more stable than the dihydrate and the result was supported by isothermal TGA experiments. This research explained why powder-like crystals of the anhydrous sodium naproxen were produced by dehydration of hydrated forms. The surfaces of the dehydrated crystals displayed cracks aligned along the b-axis of the monohydrate. These cracks made the anhydrous crystals, which were produced from the monohydrated species, very brittle and, eventually, such crystals were disrupted into much smaller entities. In addition, the existence of water channels in the unit cells of the monohydrate facilitates the dehydration in a direction more rapidly, especially, along the b-axis of the monohydrate. Rapid removal of water in a specific direction caused anisotropic dehydration.

The expansion of prison privatisation presents distinctive traits. One of them is its peculiar temporal expansion in a comparative point of view. This research focuses on the intrastate temporal expansion and more specifically in the case of England and Wales. What is researched is the reason behind the delay in the emergence of prison privatisation, in other words the asynchrony between the introduction of general and prison privatisation policies. This Thesis rejects explanatory frameworks based on historical analogies, pragmatic concerns or economic arguments and puts the explanation in a discourse of political interaction. In this framework, previous approaches related to the concept of globalisation, commodification of citizenry and political culture do not provide either suitable analytical tools in explaining the asynchrony in question. This research, instead, aims to bring forward the class struggle as catalytic agent in criminal justice system developments using a Structural Marxist concept of the State and its transformations. In the Capitalist Mode of Production the State acquires a unifying role among the contradicting classes by promoting the supposed general interest of the society, in order to allow the continuation of class domination and labour exploitation. This is feasible through the constantly unfolding hegemonic strategy which organizes the cohesion of the power bloc and disorganizes the dominated classes. Hegemonic strategy substantiates in the State Apparatuses which is not just a tool for policy making but rather a point where contradicting class powers condense; policy formation as such reflects the vector of class power in the apparatuses. Hegemonic strategy is set in motion by the State Personnel which is relatively independent knot in the transmission of domination between the power bloc and the dominated classes. State transformations are indications of this strategy since they inscribe in the structure of the State the vector of the class struggle. Hegemonic strategy took interesting contours after the mid-‘60s. The capital over-accumulation crisis on the one hand and on the other Authoritarian Statism promoted extensive State transformations as in the case of privatisations. Massive reactions, however, caused by the labour movement, required their containment and consequently a smoothly operating criminal justice system. The entrenchment of prison officers, therefore, from the wider changes in the labour status became crucial and a state transformation in itself, although by absence. This explains the delay of prison privatisation which appears indeed at the end of a long socially unstable period.

This thesis addresses the problem of developing a quantum counter-part of the well established classical theory of control. We dwell on the fundamental fact that quantum states are generally not perfectly distinguishable, and quantum measurements typically introduce noise in the system being measured. Because of these, it is generally not clear whether the central concept of the classical control theory --- that of observing the system and then applying feedback --- is always useful in the quantum setting. We center our investigations around the problem of transforming the state of a quantum system into a given target state, when the system can be prepared in different ways, and the target state depends on the choice of preparation. We call this the "quantum tracking problem" and show how it can be formulated as an optimization problem that can be approached both numerically and analytically. This problem provides a simple route to the characterization of the quantum trade-off between information gain and disturbance, and is seen to have several applications in quantum information. In order to characterize the optimality of our tracking procedures, some figure-of-merit has to be specified. Naturally, distance measures for quantum states are the ideal candidates for this purpose. We investigated several possibilities, and found that there is usually a compromise between physically motivated and mathematically tractable measures. We also introduce an alternative to the Uhlmann-Jozsa fidelity for mixed quantum states, which besides reproducing a number of properties of the standard fidelity, is especially attractive because it is simpler to compute. We employ some ideas of convex analysis to construct optimal control schemes analytically. In particular, we obtain analytic forms of optimal controllers for stabilizing and tracking any pair of states of a single-qubit. In the case of stabilization, we find that feedback control is always useful, but because of the trade-off between information gain and disturbance, somewhat different from the type of feedback performed in classical systems. In the case of tracking, we find that feedback is not always useful, meaning that depending on the choice of states one wants to achieve, it may be better not to introduce any noise by the application of quantum measurements. We also demonstrate that our optimal controllers are immediately applicable in several quantum information applications such as state-dependent cloning, purification, stabilization, and discrimination. In all of these cases, we were able to recover and extend previously known optimal strategies and performances. Finally we show how optimal single-step control schemes can be concatenated to provide multi-step strategies that usually over-perform optimal control protocols based on a single interaction between the controller and the system.

This thesis addresses the problem of developing a quantum counter-part of the well established classical theory of control. We dwell on the fundamental fact that quantum states are generally not perfectly distinguishable, and quantum measurements typically introduce noise in the system being measured. Because of these, it is generally not clear whether the central concept of the classical control theory --- that of observing the system and then applying feedback --- is always useful in the quantum setting. We center our investigations around the problem of transforming the state of a quantum system into a given target state, when the system can be prepared in different ways, and the target state depends on the choice of preparation. We call this the "quantum tracking problem" and show how it can be formulated as an optimization problem that can be approached both numerically and analytically. This problem provides a simple route to the characterization of the quantum trade-off between information gain and disturbance, and is seen to have several applications in quantum information. In order to characterize the optimality of our tracking procedures, some figure-of-merit has to be specified. Naturally, distance measures for quantum states are the ideal candidates for this purpose. We investigated several possibilities, and found that there is usually a compromise between physically motivated and mathematically tractable measures. We also introduce an alternative to the Uhlmann-Jozsa fidelity for mixed quantum states, which besides reproducing a number of properties of the standard fidelity, is especially attractive because it is simpler to compute. We employ some ideas of convex analysis to construct optimal control schemes analytically. In particular, we obtain analytic forms of optimal controllers for stabilizing and tracking any pair of states of a single-qubit. In the case of stabilization, we find that feedback control is always useful, but because of the trade-off between information gain and disturbance, somewhat different from the type of feedback performed in classical systems. In the case of tracking, we find that feedback is not always useful, meaning that depending on the choice of states one wants to achieve, it may be better not to introduce any noise by the application of quantum measurements. We also demonstrate that our optimal controllers are immediately applicable in several quantum information applications such as state-dependent cloning, purification, stabilization, and discrimination. In all of these cases, we were able to recover and extend previously known optimal strategies and performances. Finally we show how optimal single-step control schemes can be concatenated to provide multi-step strategies that usually over-perform optimal control protocols based on a single interaction between the controller and the system.

This thesis addresses the problem of developing a quantum counter-part of the well established classical theory of control. We dwell on the fundamental fact that quantum states are generally not perfectly distinguishable, and quantum measurements typically introduce noise in the system being measured. Because of these, it is generally not clear whether the central concept of the classical control theory --- that of observing the system and then applying feedback --- is always useful in the quantum setting. We center our investigations around the problem of transforming the state of a quantum system into a given target state, when the system can be prepared in different ways, and the target state depends on the choice of preparation. We call this the "quantum tracking problem" and show how it can be formulated as an optimization problem that can be approached both numerically and analytically. This problem provides a simple route to the characterization of the quantum trade-off between information gain and disturbance, and is seen to have several applications in quantum information. In order to characterize the optimality of our tracking procedures, some figure-of-merit has to be specified. Naturally, distance measures for quantum states are the ideal candidates for this purpose. We investigated several possibilities, and found that there is usually a compromise between physically motivated and mathematically tractable measures. We also introduce an alternative to the Uhlmann-Jozsa fidelity for mixed quantum states, which besides reproducing a number of properties of the standard fidelity, is especially attractive because it is simpler to compute. We employ some ideas of convex analysis to construct optimal control schemes analytically. In particular, we obtain analytic forms of optimal controllers for stabilizing and tracking any pair of states of a single-qubit. In the case of stabilization, we find that feedback control is always useful, but because of the trade-off between information gain and disturbance, somewhat different from the type of feedback performed in classical systems. In the case of tracking, we find that feedback is not always useful, meaning that depending on the choice of states one wants to achieve, it may be better not to introduce any noise by the application of quantum measurements. We also demonstrate that our optimal controllers are immediately applicable in several quantum information applications such as state-dependent cloning, purification, stabilization, and discrimination. In all of these cases, we were able to recover and extend previously known optimal strategies and performances. Finally we show how optimal single-step control schemes can be concatenated to provide multi-step strategies that usually over-perform optimal control protocols based on a single interaction between the controller and the system.

Following a series of profound conflicts in the early 21st century, Bolivia became the world’s first pluri-national state in 2009. The idea of the pluri-national state goes beyond the (uni-)national state; imagining a state that allows peoples’ coexistence on an equal footing in a state that facilitates their autonomy (Garcés, 2011). However, recent research indicates that, in practice, the Bolivian state transformation is full of tensions. Based on a framework that brings together Open Marxism (Holloway and Picciotto, 1977; Clarke, 1991c; Bonefeld et al., 1992b, a; Bonefeld et al., 1995b) and the 'de-colonial option' (Quijano, 2006), I offer in-depth insights into contemporary Bolivia. In this, I understand the state as the political form of the social relations of capital, which is marked by modernity and its 'darker side' - coloniality (Mignolo, 2011). This thesis offers tools for studying how the state 'translates' indigenous- and non-indigenous struggles into policies, law and polity (Dinerstein, 2015) while also mediating external pressures. After embedding the pluri-national state in its historical context, covering the emergence and development of the Bolivian state form, I look in depth at the pluri-national state. In this, I unpack the multifaceted struggles for autonomy and find that when mediating autonomy into the pluri-national state, something essential to the definition of plurinationality is lost in translation. First, struggles for autonomy as peoples’ self-determination and deepened decentralisation became subordinated to, yet not annihilated by the government’s social-communitarian model that is advocated in the name of the pueblo’s self-determination and ensures the state’s material basis. Secondly, state-recognised autonomy comes at the cost of submission to a state which continuously operates pre-dominantly according to modern/colonial ideas of law, order and organisation. The contradictions found in the pluri-national autonomy regime and the state are inherent in it and hence, cannot be resolved through reform.

Compacted graphite iron (CGI) is rapidly becoming an attractive alternative material for engine components in the automotive industry, replacing lamellar graphite iron (LGI) in applications where high mechanical strength is desired. However, the gain in mechanical strength comes with a cost; thermal conductivity, process control and machining are three areas that are more challenging for CGI. This generates a need for research regarding various aspects concerning CGI. In this thesis the microstructure formation during solidification and solid state transformation will be the focus of interest. The phase transformations relevant for microstructure formation of importance to properties in CGI were studied. Experiments were performed in an industrial foundry giving this research direct relevance to regular production of CGI castings. Solidification of the grey (graphite/austenite) eutectic will be discussed, focusing on some relevant aspects influencing the graphite morphology of CGI. The formation of graphite nodules has been investigated by studying colour-etched microstructures. In a material containing mainly CGI cells it was found that nodules form either early during solidification as a consequence of high undercooling or late in the solidification sequence due to a combination of high undercooling and segregation of nodularising elements. Solidification of the white (cementite/austenite) eutectic was studied using chill wedges and the influence of some alloying elements on the amount of carbides was examined. To further enhance the understanding of carbide formation in CGI a commercial casting simulation software was used to correlate real castings to simulations. It was found that the alloying elements investigated influence the carbide formation in a similar way as in other graphitic cast irons and that high nodularity CGI is more prone to chill formation than low nodularity CGI. The solid state transformation was studied and a deterministic model was developed. The model divides a eutectic cell into layers, in order to take into account segregation of alloying elements, which was observed to be influential for the ferrite growth. Moreover, the effect of alloying elements on mechanical properties (tensile properties and hardness) was evaluated. Properties were correlated to microstructural features originating from both solidification and solid state transformations. The trends found generally confirmed previous results regarding properties in graphitic cast irons.

Orientador: Angelo Del Vecchio / Banca: José Antônio Segatto / Banca: Rogério Baptistini Mendes / Resumo: O presente trabalho estuda as transformações sofridas pelas elites econômicas e políticas paulistas durante o processo de reforma do Estado brasileiro ocorrido no período de 1990 a 2002. Busca-se entender a transformação sofrida pelo Estado Brasileiro desde 1980 até os dias atuais, a qual resultou na substituição do modelo desenvolvimentista para o liberalgerencial, as razões de sua crise e as conseqüências em relação aos atores sociais aqui estudados. Com base em um modelo que busca a intersecção entre os conceitos de classe dominante e elites, procura entender o comportamento dos dirigentes políticos no período e quais as razões que levaram às substituições ocorridas entre estas a partir de 1990, com a ascensão de um novo grupo político. Ainda, no que tange às elites econômicas, como a crise econômica dos anos 80 alterou a composição dessas elites, sendo os empresários ligados ao setor industrial substituídos por outros alinhados aos novos setores da economia que emergiram dos processos de reforma do Estado, entre os quais os de serviços, surgidos das privatizações e o financeiro. Apresenta ainda dados empíricos que apontam para a direção das hipóteses trabalhadas, auxiliando na visualização das transformações que se deseja demonstrar. Ao final, propõe a discussão acerca do modelo nacional-desenvolvimentista e de seu futuro enquanto ideologia na sociedade atual / Abstract: The present work studies the transformation occurred by the economic elite and São Paulo State politics during the process of the Brazilian state reformation occurred on 1990 to 2002. We look for to understand the transformation occurred by the Brazilian State since 1980 until now, which resulted on the substitution of the developmental model to the managementliberal model, the reasons of its crisis and the consequences toward the social actors studied here. With basis in a model that searches the meeting point between the concepts of dominant class and elites, looking for to understand the behavior of the politics chairperson on the period and what reasons took to the occurred substitution between them since 1990, with the rising of a new politic group. Still, about the economics elites, with de economics crisis in the 80's changed the composition of these elites, so the business men connected to the industrial housing substituted for others aligned to the new economy sectors that emerged from the process of the State reformation, between them there were the services, arise from the privatization, and the financial services. Still, this study presents empirical datum which point to the directions of the worked hypothesis, helping on the visualization of the transformation that is to be demonstrated. At last, it is proposed a discussion about the nationaldevelopmental model and its future as ideology in the present society / Mestre

No / Martensitic transformations are of considerable technological importance, a particularly promising application being the possibility of using martensitic materials, possibly proteins, as tiny machines. For organic crystals, however, a molecular level understanding of such transformations is lacking. We have studied a martensitic-type transformation in crystals of the amino acid DL-norleucine using molecular dynamics simulation. The crystal structures of DL-norleucine comprise stacks of bilayers (formed as a result of strong hydrogen bonding) that translate relative to each other on transformation. The simulations reveal that the transformation occurs by concerted molecular displacements involving entire bilayers rather than on a molecule-by-molecule basis. These observations can be rationalized on the basis that at sufficiently high excess temperatures, the free energy barriers to concerted molecular displacements can be overcome by the available thermal energy. Furthermore, in displacive transformations, the molecular displacements can occur by the propagation of a displacement wave (akin to a kink in a carpet), which requires the molecules to overcome only a local barrier. Concerted molecular displacements are therefore considered to be a significant feature of all displacive transformations. This finding is expected to be of value toward developing strategies for controlling or modulating martensitic-type transformations.

Made available in DSpace on 2014-06-11T19:28:01Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-05-21Bitstream added on 2014-06-13T20:36:49Z : No. of bitstreams: 1 freitasjunior_m_me_arafcl.pdf: 405016 bytes, checksum: b54c45043be9c3c5a37eace89b2110cc (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho estuda as transformações sofridas pelas elites econômicas e políticas paulistas durante o processo de reforma do Estado brasileiro ocorrido no período de 1990 a 2002. Busca-se entender a transformação sofrida pelo Estado Brasileiro desde 1980 até os dias atuais, a qual resultou na substituição do modelo desenvolvimentista para o liberalgerencial, as razões de sua crise e as conseqüências em relação aos atores sociais aqui estudados. Com base em um modelo que busca a intersecção entre os conceitos de classe dominante e elites, procura entender o comportamento dos dirigentes políticos no período e quais as razões que levaram às substituições ocorridas entre estas a partir de 1990, com a ascensão de um novo grupo político. Ainda, no que tange às elites econômicas, como a crise econômica dos anos 80 alterou a composição dessas elites, sendo os empresários ligados ao setor industrial substituídos por outros alinhados aos novos setores da economia que emergiram dos processos de reforma do Estado, entre os quais os de serviços, surgidos das privatizações e o financeiro. Apresenta ainda dados empíricos que apontam para a direção das hipóteses trabalhadas, auxiliando na visualização das transformações que se deseja demonstrar. Ao final, propõe a discussão acerca do modelo nacional-desenvolvimentista e de seu futuro enquanto ideologia na sociedade atual / The present work studies the transformation occurred by the economic elite and São Paulo State politics during the process of the Brazilian state reformation occurred on 1990 to 2002. We look for to understand the transformation occurred by the Brazilian State since 1980 until now, which resulted on the substitution of the developmental model to the managementliberal model, the reasons of its crisis and the consequences toward the social actors studied here. With basis in a model that searches the meeting point between the concepts of dominant class and elites, looking for to understand the behavior of the politics chairperson on the period and what reasons took to the occurred substitution between them since 1990, with the rising of a new politic group. Still, about the economics elites, with de economics crisis in the 80’s changed the composition of these elites, so the business men connected to the industrial housing substituted for others aligned to the new economy sectors that emerged from the process of the State reformation, between them there were the services, arise from the privatization, and the financial services. Still, this study presents empirical datum which point to the directions of the worked hypothesis, helping on the visualization of the transformation that is to be demonstrated. At last, it is proposed a discussion about the nationaldevelopmental model and its future as ideology in the present society