The crystallization kinetics and the melting behavior of a random copolyester with equal amounts of ethylene- and trimethylene- terephthalate units were studied by using a modulated differential scanning calorimeter in both conventional mode (DSC) and modulated mode (TMDSC). Polarizing light microscope (PLM) was used to study the spherulite growth rates and spherulite patterns. Isothermal crystallization was performed at temperatures (TC) between 115 and 142¢J. The Avrami exponents, n1, were found to increase from 3.00 to 3.22 with an increasing TC. At the highest TC, it should be a sporadic nucleation with spherical growth, i.e. n1 = 4. The value of n1 less than 4 and the slow rate of crystallization indicate that both primary and secondary crystallization occurs in parallel rather than in series. Triple- and double- melting peaks were observed for the melting behavior of DSC at 10¢J/min and of TMDSC at 2¢J/min. The results of WAXD, DSC and TMDSC indicate the coexistence of two melting mechanisms, i.e., dual morphologies and the recrystallization process. The Hoffman-Weeks plot gave an equilibrium melting temperature of 176.6¢J from the reversing curves of TMDSC. In this study, the regime II¡÷III transition temperature can be estimated from the inverse of the half-time of crystallization as overall growth rate and the growth rate. Meanwhile, a clear change in morphology from negative regular to banded spherulites was also observed around 132¢J by using PLM. The heat of fusion of polymer is customarily evaluated through the melting point depression measurements with the thermodynamic melting points. Application of the Flory equation to the PET/PTT random copolyesters diluted with di-n-butyl phthalate gave the values of the heat of fusion to be 4.48, 3.43 and 3.07 kcal/mole, respectively, for the random copolyesters containing 28, 38 and 50 mole % of ethylene terephthalate unit. The corresponded values of the interaction energy of mixing at infinite dilution were 3.90, 2.85 and 2.75 cal/cc.

This study examines the process of state gender policy reform. It seeks to explain legal changes in gender issues in Venezuela across time. The study entails observations of state policy changes in gender issues during specific periods of the Punto Fijo era (1958-1998) characterized as those of democratic consolidation and deconsolidation, and during the transition towards a new type of democracy, the Chávez era (1999-2007). The policies considered are the ones addressing women’s equality at home and at work, reproductive rights, women’s economic rights and political participation. The analysis shows that gender policy reform by the state depends on the degree of opening of the institutions and on the combination of certain configurations of state institutions and elite interests. In addition, women’s groups’ capacity to influence state gender policy change depends on their organizational capacity as well as the institutional opportunities provided by changes in state structures, elite interests, and allies of the movement.

Nested by linear cointegration first provided in Granger (1981), the definition of nonlinear cointegration is presented in this paper. Sequentially, a nonlinear cointegrated economic system is introduced. What we mainly study is testing no nonlinear cointegration against nonlinear cointegration by residual-based test, which is ready for detecting stochastic trend in nonlinear autoregression models. We construct cointegrating regression along with smooth transition components from smooth transition autoregression model. Some properties are analyzed and discussed during the estimation procedure for cointegrating regression, including description of transition variable. Autoregression of order one is considered as the model of estimated residuals for residual-based test, from which the teststatistic is obtained. Critical values and asymptotic distribution of the test statistic that we request for different cointegrating regressions with different sample sizes are derived based on Monte Carlo simulation. The proposed theoretical methods and models are illustrated by an empirical example, comparing the results with linear cointegration application in Hamilton (1994). It is concluded that there exists nonlinear cointegration in our system in the final results.

Drawing upon formal modeling, cross-national statistical analysis, and in-depth case studies, this dissertation explores the relationship between patterns of government revenue generation and political regime stability. Considering both tax and non-tax revenue (the latter of which includes foreign aid and revenue from state-owned natural resource enterprises), and building on recent redistributive theories of regime change, I use formal modeling to generate testable hypotheses about the impact of non-tax revenue on regime dynamics in both democratic and authoritarian regimes. <em>The central prediction is that rises (falls) in non-tax resources increase (decrease) the stability of authoritarian and democratic regimes, by reducing (increasing) redistributional conflicts in society.</em> I provide evidence supporting the implications of the theory for both redistribution and regime stability, drawing upon cross-national time-series statistical analysis as well as in-depth examination of three theoretically important cases: Bolivia, Mexico, and Kenya.The research has important implications for three bodies of literature. First, it advances the broad literature on the political economy of redistribution. The existing literature has generally assumed that government revenues are raised solely by taxation, the source of redistributional conflict. I demonstrate that this is not a plausible assumption---non-tax revenue makes up about a quarter of government revenue on average, and in some countries represents the large majority of government revenue---and that in fact non-tax revenue systematically decreases redistribution.Second, building on this insight, I advance the literature on democratization by developing a theory of how government revenues---both their size and their source---factor into regime change. This work builds on and extends recent influential works that have focused on formally modeling the distributional dynamics underlying regime transitions. Finally, the research sheds light on commonalities between literatures studying different areas of the world. In particular, it argues that there are similarities between insights developed in the literature on the <em>"rentier"</em> state---principally regarding how oil revenues affect regime dynamics---and those developed in the literature on foreign aid and political regimes. The reason is that oil revenues and aid are significant examples of a broader set of resources---non-tax revenues---whose importance has been underappreciated. / Dissertation

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Plusieurs régimes d’écoulement diphasiques adiabatiques eau/air horizontaux (écoulements dispersés àbulles et intermittents) et leur développement axial ont été étudiés dans l'expérience METERO,constituée d’une conduite circulaire horizontale de 100 mm de diamètre interne. Différentes techniques d’instrumentation ont été améliorées et utilisées pour mesurer les grandeurs caractéristiques de l’écoulement afin d’apporter une description locale et l'évolution axiale des écoulements. Les mécanismes physiques responsables des régimes d’écoulement et de leurs transitions, notamment la compétition entre forces turbulente et de flottabilité ont été explicités. Les différences entre les régimes à bulles et intermittent ont été mises en évidence et les processus physiques à l’origine de ces différences ont été expliqués. Deux nouvelles cartes de régime d’écoulement adimensionnelles ont été proposées: la première apporte une amélioration à la représentation de Taitel & Dukler (1976) et propose un nouveau critère de transition. La deuxième, novatrice, quantifie les effets des forces de turbulence et de flottabilité en fonction du taux de vide. / Several horizontal water-air two-phase adiabatic flows (dispersed bubbly flows and intermittent flows)and their axial evolutions have been studied in the METERO experiment which is consisted of ahorizontal circular test section with an internal diameter of 100 mm. Different measurement techniqueshave been improved and utilized to measure the flow characteristics in order to bring a localdescription and axial evolution of the flows. The responsible physical mechanisms of the flow regimesand their transitions, particularly the competition between turbulent force and buoyancy force havebeen explained. The differences between dispersed bubbly flows and intermittent flows have beenhighlighted and the physical process at the origin of these differences has been explained. Two newdimensionless flow regime maps have been proposed: the first one brings an improvement to therepresentation of Taitel & Dukler (1976) and proposes new transition criteria. The second novel maptakes into account the effects of turbulent and buoyancy forces and the void fraction.

Pour répondre aux défis environnementaux actuels, des solutions en rupture par rapport aux turbomachines existantes sont actuellement encours de développement. Elles s’appuient sur des cycles thermodynamiques plus efficients.L’objectif de ces travaux de thèse est d’étudier expérimentalement les mécanismes de transition de régime de combustion pour ce type d'applications en utilisant un surrogate de kérosène, le n-décane. Pour cela, une déflagration est initiée dans une enceinte fermée et comprime les gaz frais. La pression et la température de ces derniers augmentent jusqu’à atteindre les conditions propices à l’apparition de l’autoinflammation.3 régimes de combustion successifs sont caractérisés dans la chambre de combustion au moyen de diagnostics optiques rapides. Un premier dégagement de chaleur associé à la flamme froide pré-oxyde les gaz frais, il est suivi du dégagement de chaleur principal (Main Heat Release,MHR). Pour les températures initiales de mélange les plus élevées, une détonation est observée à la fin du processus. Deux chemins de transition différents sont mis en évidence : la transition Déflagration-Auto-inflammation (DAIT) et la transition Déflagration-Auto-inflammation-Détonation (DAIDT). La sensibilité des transitions de régime aux conditions initiales de pression, de température et de richesse a été caractérisée au moyen de plusieurs études paramétriques. Dans ce but, les conditions de température, de pression et de composition du mélange sont calculées aux instants d’apparition des différents fronts réactifs (flamme froide, MHR et détonation). Il a notamment été observé que les dégagements de chaleur successifs de l’auto-inflammation se déroulaient aux mêmes températures (740 K pour la flamme froide et 1050 K pour le MHR)quelles que soient les conditions initiales. L’étude s’est concentrée ensuite sur l’analyse d’un point de fonctionnement particulier. L’étude de ce point de fonctionnement, différents vitesses de front d’auto-inflammation ont été observées, mettant en évidence le mécanisme de SWACER lors de la transition.Un critère de transition de régime depuis l’auto-inflammation proposé de Zander et al., dans le cadre d’études numériques, a été testé dans notre configuration expérimentale. Un critère modifié a été développé en lui adjoignant la notion d’effets de compressibilité dans l’écoulement réactif. L’application de ce critère à l’ensemble des essais permet de prédire l’apparition de la détonation dans les conditions où 0 et 100 % de DAIDT sont observés. Les différents domaines de transition de régime ont également été positionnés sur le diagramme de Bradley (ξ, ϵ). Les modes de combustion prédits par le diagramme sont consistants avec ceux qui sont atteints dans la chambre.L’influence de la distribution initiale de température sur les modes de combustion atteignables dans la chambre a été étudiée. Trois topologies d’auto-inflammation ont été mises en évidence pour trois distributions de température dans la chambre. Ces topologies sont séparées en deux catégories, celles privilégiant une direction particulière lors de l’auto-inflammation séquentielle et celle présentant un comportement tridimensionnel.Les essais ayant un comportement tridimensionnel présentent une très forte propension à la DAIDT mais une propagation lente des fronts d’auto-inflammation. Dans ce cas, un autre mécanisme de transition vers la détonation est mis en évidence : l’auto-inflammation d’une poche homogène de gaz génère des ondes de choc et déclenchent des auto-inflammations successives pendant leur propagation. Le couplage choc/front réactif entraine la formation de la détonation.Différents mécanismes de transition vers la détonation ont été observés et étudiés sur une large plage de conditions de pression, température,richesse et gradient thermique. Les résultats obtenus permettront d’appuyer les études numériques réalisées sur le sujet, manquant jusque-là de données expérimentales en conditions académiques. / To meet the current environmental challenges, breakthrough solutions compared to existing turbomachines are currently under development.They rely on the use of more efficient thermodynamic cycles.The objective of this thesis is to study experimentally the mechanisms of transition of combustion regime using a kerosene surrogate, n-decane.For this purpose, a deflagration is initiated in a closed chamber and compresses the fresh gases. The pressure and the temperature of the endgas increase until reaching the conditions favorable to the appearance of the autoignition in the chamber.3 successive combustion regimes are characterized in the combustion chamber by means of fast optical diagnostics. A first heat release,associated with the cool flame phenomenon, pre-oxidizes the fresh gases, it is followed by the Main Heat Release (MHR). For the highest initial temperatures, a detonation is observed at the end of the process. Two different transition paths are highlighted: the Deflagration-Autoignition Transition (DAIT) and the Deflagration-Autoignition-Detonation Transition (DAIDT).The sensitivity of regime transitions to the initial conditions of pressure, temperature and mixture composition was characterized by means of several parametric studies. For this purpose, the conditions of temperature, pressure and composition of the mixture are calculated at the onset of the different reactive fronts (cool flame, MHR and detonation). In particular, it has been observed that the successive heat releases of theauto-ignition start at the same temperatures (740 K for the cool flame and 1050 K for the MHR) whatever the initial conditions. The study, then, focused on the analysis of a particular operating point. During the study of this operating point different self-ignition front velocities were observed, highlighting the mechanism of SWACER during the transition.A regime transition criterion proposed by Zander et al. based on numerical studies has been tested in our experimental setup. A modified criterion has been developed to take into account compressibility effects in the reactive flow. The application of this criterion to all the dataset makes possible to predict the appearance of the detonation under the conditions where 0 and 100% of DAIDT are observed. The different regime transition domains have also been positioned on the Bradley diagram (ξ, ε). The modes of combustion predicted by the diagram are consistent with those reached in the chamber.The influence of the initial temperature distribution on the combustion modes achievable in the chamber has been studied. Three topologies of autoignition have been demonstrated for three initial temperature distributions in the chamber. These topologies are separated into two categories, those favoring a particular direction during sequential self-ignition and that exhibiting a three-dimensional behavior.Three-dimensional tests show a very high propensity for DAIDT but a slow spread of autoignition fronts. In this case, another mechanism of transition to detonation is evidenced: the self-ignition of an homogeneous gas pocket generates shock waves and triggers successive autoinflammations during their propagation. The shock coupling / reactive front causes the formation of the detonation. Different transition mechanisms to detonation have been observed and studied over a wide range of pressure, temperature, equivalence ratio and thermal gradient conditions. The obtained results will be useful to support the numerical studies carried out on the subject, which lacks experimental data in academic conditions.

Este trabalho apresenta uma análise do fenômeno da transição no regime de desgaste por deslizamento dos aços. Esta análise foi feita usando as abordagens termodinâmicas do desgaste e estudando tópicos como a temperatura superficial, o papel da remoção das partículas de desgaste e a evolução nas propriedades das superfícies desgastadas ao longo do ensaio de desgaste. Foram realizados ensaios de desgaste por deslizamento de pinos de aço AISI 4140 sobre discos de aço AISI H13. Foram usados dois níveis de dureza dos pinos e três níveis de dureza dos discos por cada condição dos pinos. Foi utilizada uma carga normal de 35 N, uma velocidade de deslizamento de 0,1 m/s e um tempo de deslizamento de 3600 s. Foram executados ensaios parciais, com tempos menores que 3600 s, para avaliar o estado das superfícies ao longo do ensaio, e ensaios com remoção das partículas de desgaste para analisar o seu papel na atuação dos regimes. A variação da força de atrito e da temperatura subsuperficial do pino foi monitorada durante os ensaios. A caracterização dos materiais antes e depois dos ensaios foi efetuada através da observação em lupa e em microscópio eletrônico de varredura, e de medições de perdas de massa, dureza, microdureza e rugosidade superficial. Os resultados mostraram que a operação dos regimes moderado e severo de desgaste foi influenciada pela dureza inicial dos materiais. Na condição de dureza alta dos pinos (serie a), a diminuição da dureza dos discos promoveu a operação de um regime severo de desgaste prévio à atuação de um regime moderado de desgaste (condições a2 e a3). Na condição da dureza baixa dos pinos (serie b) se observou um regime severo de desgaste que com o aumento da dureza dos discos resultou na transição para um regime moderado de desgaste (condições b2 e b1). Os ensaios com a remoção das partículas de desgaste mostraram que o terceiro corpo contribuiu com aproximadamente um 50% da força de atrito, mas não parece ter nenhuma influência sobre a operação dos regimes de desgaste. A caracterização das superfícies de desgaste sugeriu que a oxidação durante o regime moderado não foi originada pelo calor dissipado por atrito, e as altas temperaturas de contato, e sim preferivelmente pelo comportamento mecânico dos corpos deslizantes. Os resultados indicam que a transição no regime de desgaste foi causada pela mudança da natureza da deformação no contato entre as superfícies. Um contato predominantemente elástico e plástico resultou na atuação dos regimes de desgaste moderado e severo, respectivamente. / This work presents an analysis of the phenomenon of the sliding wear regime transition of steels. This analysis was made using the thermodynamic approaches of wear and studying topics such as the surface temperature, the role of wear debris removal and the evolution of worn surfaces properties during the wear tests. Sliding wear tests of AISI 4140 steel pins on AISI H13 steel disks were performed. Two levels of pin hardness and three levels of disk hardness for each condition of the pins were used. A normal load of 35 N, a sliding velocity of 0.1 m/s and a sliding time of 3600 s were applied. Tests interrupted at lower sliding times smaller than 3600 s were run to assess the worn surfaces state during tests. Tests with wear debris removal were executed to analyze its role on the wear regimes operation. The variation of the friction force and the pin subsurface temperature was monitored during tests. The characterization of materials before and after tests was performed by observation in stereoscopic and scanning electron microscopy, and by measurements of mass loss, hardness, microhardness and surface roughness. The results showed that the operation of mild and severe wear regimes was in_uenced by the initial hardness of materials. At the high pin hardness condition (run a), a decrease in disk hardness promoted the severe wear regime operation prior to the action of a mild wear regime (conditions a2 and a3). At the low pin hardness (run b) a severe wear regime, which resulted in the wear regime transition from mild to severe (conditions b2 and b1), was observed with the increase in disk hardness. Tests with removal of wear particles showed that the third body contributed with approximately 50% of the friction force, but seems to have no in_uence on the wear regimes operation. The characterization of worn surfaces suggested that the oxidation during mild wear regime was not caused by the dissipated heat by friction, and high contact temperatures, but by the mechanical behavior of the sliding bodies. The results indicate that the wear regime transition caused a change in the nature of deformation at the contacting surfaces. A predominantly elastic and plastic contact resulted in the action of mild and severe wear regime, respectively.

Este trabalho apresenta uma análise do fenômeno da transição no regime de desgaste por deslizamento dos aços. Esta análise foi feita usando as abordagens termodinâmicas do desgaste e estudando tópicos como a temperatura superficial, o papel da remoção das partículas de desgaste e a evolução nas propriedades das superfícies desgastadas ao longo do ensaio de desgaste. Foram realizados ensaios de desgaste por deslizamento de pinos de aço AISI 4140 sobre discos de aço AISI H13. Foram usados dois níveis de dureza dos pinos e três níveis de dureza dos discos por cada condição dos pinos. Foi utilizada uma carga normal de 35 N, uma velocidade de deslizamento de 0,1 m/s e um tempo de deslizamento de 3600 s. Foram executados ensaios parciais, com tempos menores que 3600 s, para avaliar o estado das superfícies ao longo do ensaio, e ensaios com remoção das partículas de desgaste para analisar o seu papel na atuação dos regimes. A variação da força de atrito e da temperatura subsuperficial do pino foi monitorada durante os ensaios. A caracterização dos materiais antes e depois dos ensaios foi efetuada através da observação em lupa e em microscópio eletrônico de varredura, e de medições de perdas de massa, dureza, microdureza e rugosidade superficial. Os resultados mostraram que a operação dos regimes moderado e severo de desgaste foi influenciada pela dureza inicial dos materiais. Na condição de dureza alta dos pinos (serie a), a diminuição da dureza dos discos promoveu a operação de um regime severo de desgaste prévio à atuação de um regime moderado de desgaste (condições a2 e a3). Na condição da dureza baixa dos pinos (serie b) se observou um regime severo de desgaste que com o aumento da dureza dos discos resultou na transição para um regime moderado de desgaste (condições b2 e b1). Os ensaios com a remoção das partículas de desgaste mostraram que o terceiro corpo contribuiu com aproximadamente um 50% da força de atrito, mas não parece ter nenhuma influência sobre a operação dos regimes de desgaste. A caracterização das superfícies de desgaste sugeriu que a oxidação durante o regime moderado não foi originada pelo calor dissipado por atrito, e as altas temperaturas de contato, e sim preferivelmente pelo comportamento mecânico dos corpos deslizantes. Os resultados indicam que a transição no regime de desgaste foi causada pela mudança da natureza da deformação no contato entre as superfícies. Um contato predominantemente elástico e plástico resultou na atuação dos regimes de desgaste moderado e severo, respectivamente. / This work presents an analysis of the phenomenon of the sliding wear regime transition of steels. This analysis was made using the thermodynamic approaches of wear and studying topics such as the surface temperature, the role of wear debris removal and the evolution of worn surfaces properties during the wear tests. Sliding wear tests of AISI 4140 steel pins on AISI H13 steel disks were performed. Two levels of pin hardness and three levels of disk hardness for each condition of the pins were used. A normal load of 35 N, a sliding velocity of 0.1 m/s and a sliding time of 3600 s were applied. Tests interrupted at lower sliding times smaller than 3600 s were run to assess the worn surfaces state during tests. Tests with wear debris removal were executed to analyze its role on the wear regimes operation. The variation of the friction force and the pin subsurface temperature was monitored during tests. The characterization of materials before and after tests was performed by observation in stereoscopic and scanning electron microscopy, and by measurements of mass loss, hardness, microhardness and surface roughness. The results showed that the operation of mild and severe wear regimes was in_uenced by the initial hardness of materials. At the high pin hardness condition (run a), a decrease in disk hardness promoted the severe wear regime operation prior to the action of a mild wear regime (conditions a2 and a3). At the low pin hardness (run b) a severe wear regime, which resulted in the wear regime transition from mild to severe (conditions b2 and b1), was observed with the increase in disk hardness. Tests with removal of wear particles showed that the third body contributed with approximately 50% of the friction force, but seems to have no in_uence on the wear regimes operation. The characterization of worn surfaces suggested that the oxidation during mild wear regime was not caused by the dissipated heat by friction, and high contact temperatures, but by the mechanical behavior of the sliding bodies. The results indicate that the wear regime transition caused a change in the nature of deformation at the contacting surfaces. A predominantly elastic and plastic contact resulted in the action of mild and severe wear regime, respectively.