Synthesis, Structure, and Solid-State Transformation Studies of Phosphonoacetate Based Hybrid Compounds of Uranium and Thorium

Three new phosphonoacetate hybrid frameworks based on the actinide elements uranium and thorium have been synthesized. The compounds [C4N2H14][(UO2)(2)(O3PCH2COO)(2)]center dot H2O, I,[C4N2H14][(UO2)(2)(C2O4)(O3PCH2COOH)(2)], II, and Th(H2O)(2)(O3PCH2COO)(C2O4)(0.5). H2O, III, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units. Compound II has been prepared using a solvent-free approach, by a solid state reaction at 150 degrees C. It has been shown that II can also be prepared through a room temperature mechanochemical (grinding) route. The layer arrangement in III closely resembles to that observed in I. The compounds have been characterized by powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and fluorescence studies.

Nanostructuration via solid state transformation as a strategy for improving the thermoelectric efficiency of PbTe alloys

The approach taken in this paper in order to modify the scattering features of electrons and phonons and improve the figure of merit (ZT) of thermoelectric PbTe is to alter the microstructure at constant chemistry. A lamellar pattern of PbTe/GeTe at the nano- and microscale was produced in Pb(0.36)Ge(0.64)Te alloy by the diffusional decomposition of a supersaturated solid solution. The mechanism of nanostructuration is most likely a discontinuous spinodal decomposition. A simple model relating the interface velocity to the observed lamellar spacing is proposed. The effects of nanostructuration in Pb(0.36)Ge(0.64)Te alloy on the electrical and thermal conductivity, thermopower and ZT were investigated. It was shown that nanostructuration through the formation of a lamellar pattern of PbTe/GeTe is unlikely to provide a significant improvement due to the occurrence of discontinuous coarsening. However, the present study allows an analysis of possible strategies to improve thermoelectric materials via optimal design of the microstructure and optimized heat treatment. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

State Transformation and the European Integration Project. Lessons from the financial crisis and the Greek paradigm. CEPS Special Report No. 130/February 2016

The financial crisis that erupted in the eurozone not only affected the EU’s financial governance mechanisms, but also the very nature of state sovereignty and balances in the relations of member states; thus, the actual inequalities between the member states hidden behind their institutional equality have deteriorated. This transformation is recorded in the case law of the Court of Justice of the European Union and the member states’ constitutional courts, particularly in those at the heart of the crisis, with Greece as the most prominent example. It is the issue of public debt (sovereign debt) of the EU member states that particularly reflects the influence of the crisis on state sovereignty as well as the intensely transnational (intergovernmental) character of European integration, which under these circumstances takes the form of a continuous, tough negotiation. The historical connection between public debt (sovereign debt) and state sovereignty has re-emerged because of the financial crisis. This development has affected not only the European institutions, but also, at the member state level, the actual institutional content of the rule of law (especially judicial review) and the welfare state in its essence, as the great social and political acquis of 20th century Europe. From this perspective, the way that the Greek courts have dealt with the gradual waves of fiscal austerity measures and structural reforms from 2010 to 2015 is characteristic. The effect of the financial crisis on the sovereignty of the member states and on the pace of European integration also has an impact on European foreign and security policy, and the correlations between the political forces at both the national and European level, thus producing even more intense pressures on European social democracy. In light of the experience of the financial crisis, the final question is whether the nation state (given the large real inequalities among the EU member states) currently functions as a brake or as an engine for future European integration.

Study of neutral Fe(III) complexes of pyridoxal-N-substituted thiosemicarbazone with desolvation induced spin-state transformation above room temperature

The preparation and characterization of two new neutral ferric complexes with desolvation-induced discontinuous spin-state transformation above room temperature are reported. The compounds, Fe(Hthpy)(thpy).CH3OH.3H2O (1) and Fe(Hmthpy)(mthpy).2H2O (2), are low-spin (LS) at room temperature and below, whereas their nonsolvated forms are high-spin (HS), exhibiting zero-field splitting. In these complexes, Hthpy, Hmthpy, and thpy, mthpy are the deprotonated forms of pyridoxal thiosemicarbazone and pyridoxal methylthiosemicarbazone, respectively; each is an O,N,S-tridentate ligand. The molecular structures have been determined at 100(1) K using single-crystal X-ray diffraction techniques and resulted in a triclinic system (space group P1) and monoclinic unit cell (space group P21/c) for 1 and 2, respectively. Structures were refined to the final error indices, where RF = 0.0560 for 1 and RF = 0.0522 for 2. The chemical inequivalence of the ligands was clearly established, for the "extra" hydrogen atom on the monodeprotonated ligands (Hthpy, Hmthpy) was found to be bound to the nitrogen of the pyridine ring. The ligands are all of the thiol form; the doubly deprotonated chelates (thpy, mthpy) have C-S bond lengths slightly longer than those of the singly deprotonated forms. There is a three-dimensional network of hydrogen bonds in both compounds. The discontinuous spin-state transformation is accompanied with liberation of solvate molecules. This is evidenced also from DSC analysis. Heat capacity data for the LS and HS phases are tabulated at selected temperatures, the values of the enthalpy and entropy changes connected with the change of spin state were reckoned at DeltaH = 12.5 0.3 kJ mol-1 and DeltaS = 33.3 0.8 J mol-1 K-1, respectively, for 1 and DeltaH = 6.5 0.3 kJ mol-1 and DeltaS = 17.6 0.8 J mol-1 K-1, respectively, for 2

An in situ electron microscope investigation of the icosahedral-to-decagonal quasicrystalline transformation in Al-20 at.% Mn

The solid-state transformation behaviour of the icosahedral phase in rapidly solidified Al-20 at.% Mn has been investigated by in situ heating experiments in the transmission electron microscope. As-rapidly-solidified Al-20 at.% Mn consists mainly of a dendritic icosahedral phase, with a small amount of interdendritic f.c.c. agr-Al. During subsequent heat treatment at temperatures below about 500°C, the dendritic icosahedral phase grows and consumes the interdendritic agr-Al. At about 500°C the decagonal phase nucleates near icosahedral dendrite and grain boundaries and then grows into the icosahedral matrix by lateral motion of ledges 10-20 nm high across facet planes normal to the twofold symmetry axes. At about 600°C the decagonal phase transforms into a crystalline phase. The present study suggests that solid-state decomposition of the icosahedral phase is the mechanism of decagonal phase formation in as-rapidly-solidified Al-Mn alloys.

Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130◦C, 138◦C, 140◦C and 150◦C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two C H bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid–gas–solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol−1 to 368 kJ mol−1 for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

Multiple Input-Output Bidirectional Solid State Transformer Based on a Series Resonant Converter

Las fuentes de alimentación de modo conmutado (SMPS en sus siglas en inglés) se utilizan ampliamente en una gran variedad de aplicaciones. La tarea más difícil para los diseñadores de SMPS consiste en lograr simultáneamente la operación del convertidor con alto rendimiento y alta densidad de energía. El tamaño y el peso de un convertidor de potencia está dominado por los componentes pasivos, ya que estos elementos son normalmente más grandes y más pesados que otros elementos en el circuito. Para una potencia de salida dada, la cantidad de energía almacenada en el convertidor que ha de ser entregada a la carga en cada ciclo de conmutación, es inversamente proporcional a la frecuencia de conmutación del convertidor. Por lo tanto, el aumento de la frecuencia de conmutación se considera un medio para lograr soluciones más compactas con los niveles de densidad de potencia más altos. La importancia de investigar en el rango de alta frecuencia de conmutación radica en todos los beneficios que se pueden lograr: además de la reducción en el tamaño de los componentes pasivos, el aumento de la frecuencia de conmutación puede mejorar significativamente prestaciones dinámicas de convertidores de potencia. Almacenamiento de energía pequeña y el período de conmutación corto conducen a una respuesta transitoria del convertidor más rápida en presencia de las variaciones de la tensión de entrada o de la carga. Las limitaciones más importantes del incremento de la frecuencia de conmutación se relacionan con mayores pérdidas del núcleo magnético convencional, así como las pérdidas de los devanados debido a los efectos pelicular y proximidad. También, un problema potencial es el aumento de los efectos de los elementos parásitos de los componentes magnéticos - inductancia de dispersión y la capacidad entre los devanados - que causan pérdidas adicionales debido a las corrientes no deseadas. Otro factor limitante supone el incremento de las pérdidas de conmutación y el aumento de la influencia de los elementos parásitos (pistas de circuitos impresos, interconexiones y empaquetado) en el comportamiento del circuito. El uso de topologías resonantes puede abordar estos problemas mediante el uso de las técnicas de conmutaciones suaves para reducir las pérdidas de conmutación incorporando los parásitos en los elementos del circuito. Sin embargo, las mejoras de rendimiento se reducen significativamente debido a las corrientes circulantes cuando el convertidor opera fuera de las condiciones de funcionamiento nominales. A medida que la tensión de entrada o la carga cambian las corrientes circulantes incrementan en comparación con aquellos en condiciones de funcionamiento nominales. Se pueden obtener muchos beneficios potenciales de la operación de convertidores resonantes a más alta frecuencia si se emplean en aplicaciones con condiciones de tensión de entrada favorables como las que se encuentran en las arquitecturas de potencia distribuidas. La regulación de la carga y en particular la regulación de la tensión de entrada reducen tanto la densidad de potencia del convertidor como el rendimiento. Debido a la relativamente constante tensión de bus que se encuentra en arquitecturas de potencia distribuidas los convertidores resonantes son adecuados para el uso en convertidores de tipo bus (transformadores cc/cc de estado sólido). En el mercado ya están disponibles productos comerciales de transformadores cc/cc de dos puertos que tienen muy alta densidad de potencia y alto rendimiento se basan en convertidor resonante serie que opera justo en la frecuencia de resonancia y en el orden de los megahercios. Sin embargo, las mejoras futuras en el rendimiento de las arquitecturas de potencia se esperan que vengan del uso de dos o más buses de distribución de baja tensión en vez de una sola. Teniendo eso en cuenta, el objetivo principal de esta tesis es aplicar el concepto del convertidor resonante serie que funciona en su punto óptimo en un nuevo transformador cc/cc bidireccional de puertos múltiples para atender las necesidades futuras de las arquitecturas de potencia. El nuevo transformador cc/cc bidireccional de puertos múltiples se basa en la topología de convertidor resonante serie y reduce a sólo uno el número de componentes magnéticos. Conmutaciones suaves de los interruptores hacen que sea posible la operación en las altas frecuencias de conmutación para alcanzar altas densidades de potencia. Los problemas posibles con respecto a inductancias parásitas se eliminan, ya que se absorben en los Resumen elementos del circuito. El convertidor se caracteriza con una muy buena regulación de la carga propia y cruzada debido a sus pequeñas impedancias de salida intrínsecas. El transformador cc/cc de puertos múltiples opera a una frecuencia de conmutación fija y sin regulación de la tensión de entrada. En esta tesis se analiza de forma teórica y en profundidad el funcionamiento y el diseño de la topología y del transformador, modelándolos en detalle para poder optimizar su diseño. Los resultados experimentales obtenidos se corresponden con gran exactitud a aquellos proporcionados por los modelos. El efecto de los elementos parásitos son críticos y afectan a diferentes aspectos del convertidor, regulación de la tensión de salida, pérdidas de conducción, regulación cruzada, etc. También se obtienen los criterios de diseño para seleccionar los valores de los condensadores de resonancia para lograr diferentes objetivos de diseño, tales como pérdidas de conducción mínimas, la eliminación de la regulación cruzada o conmutación en apagado con corriente cero en plena carga de todos los puentes secundarios. Las conmutaciones en encendido con tensión cero en todos los interruptores se consiguen ajustando el entrehierro para obtener una inductancia magnetizante finita en el transformador. Se propone, además, un cambio en los señales de disparo para conseguir que la operación con conmutaciones en apagado con corriente cero de todos los puentes secundarios sea independiente de la variación de la carga y de las tolerancias de los condensadores resonantes. La viabilidad de la topología propuesta se verifica a través una extensa tarea de simulación y el trabajo experimental. La optimización del diseño del transformador de alta frecuencia también se aborda en este trabajo, ya que es el componente más voluminoso en el convertidor. El impacto de de la duración del tiempo muerto y el tamaño del entrehierro en el rendimiento del convertidor se analizan en un ejemplo de diseño de transformador cc/cc de tres puertos y cientos de vatios de potencia. En la parte final de esta investigación se considera la implementación y el análisis de las prestaciones de un transformador cc/cc de cuatro puertos para una aplicación de muy baja tensión y de decenas de vatios de potencia, y sin requisitos de aislamiento. Abstract Recently, switch mode power supplies (SMPS) have been used in a great variety of applications. The most challenging issue for designers of SMPS is to achieve simultaneously high efficiency operation at high power density. The size and weight of a power converter is dominated by the passive components since these elements are normally larger and heavier than other elements in the circuit. If the output power is constant, the stored amount of energy in the converter which is to be delivered to the load in each switching cycle is inversely proportional to the converter’s switching frequency. Therefore, increasing the switching frequency is considered a mean to achieve more compact solutions at higher power density levels. The importance of investigation in high switching frequency range comes from all the benefits that can be achieved. Besides the reduction in size of passive components, increasing switching frequency can significantly improve dynamic performances of power converters. Small energy storage and short switching period lead to faster transient response of the converter against the input voltage and load variations. The most important limitations for pushing up the switching frequency are related to increased conventional magnetic core loss as well as the winding loss due to the skin and proximity effect. A potential problem is also increased magnetic parasitics – leakage inductance and capacitance between the windings – that cause additional loss due to unwanted currents. Higher switching loss and the increased influence of printed circuit boards, interconnections and packaging on circuit behavior is another limiting factor. Resonant power conversion can address these problems by using soft switching techniques to reduce switching loss incorporating the parasitics into the circuit elements. However the performance gains are significantly reduced due to the circulating currents when the converter operates out of the nominal operating conditions. As the input voltage or the load change the circulating currents become higher comparing to those ones at nominal operating conditions. Multiple Input-Output Many potential gains from operating resonant converters at higher switching frequency can be obtained if they are employed in applications with favorable input voltage conditions such as those found in distributed power architectures. Load and particularly input voltage regulation reduce a converter’s power density and efficiency. Due to a relatively constant bus voltage in distributed power architectures the resonant converters are suitable for bus voltage conversion (dc/dc or solid state transformation). Unregulated two port dc/dc transformer products achieving very high power density and efficiency figures are based on series resonant converter operating just at the resonant frequency and operating in the megahertz range are already available in the market. However, further efficiency improvements of power architectures are expected to come from using two or more separate low voltage distribution buses instead of a single one. The principal objective of this dissertation is to implement the concept of the series resonant converter operating at its optimum point into a novel bidirectional multiple port dc/dc transformer to address the future needs of power architectures. The new multiple port dc/dc transformer is based on a series resonant converter topology and reduces to only one the number of magnetic components. Soft switching commutations make possible high switching frequencies to be adopted and high power densities to be achieved. Possible problems regarding stray inductances are eliminated since they are absorbed into the circuit elements. The converter features very good inherent load and cross regulation due to the small output impedances. The proposed multiple port dc/dc transformer operates at fixed switching frequency without line regulation. Extensive theoretical analysis of the topology and modeling in details are provided in order to compare with the experimental results. The relationships that show how the output voltage regulation and conduction losses are affected by the circuit parasitics are derived. The methods to select the resonant capacitor values to achieve different design goals such as minimum conduction losses, elimination of cross regulation or ZCS operation at full load of all the secondary side bridges are discussed. ZVS turn-on of all the switches is achieved by relying on the finite magnetizing inductance of the Abstract transformer. A change of the driving pattern is proposed to achieve ZCS operation of all the secondary side bridges independent on load variations or resonant capacitor tolerances. The feasibility of the proposed topology is verified through extensive simulation and experimental work. The optimization of the high frequency transformer design is also addressed in this work since it is the most bulky component in the converter. The impact of dead time interval and the gap size on the overall converter efficiency is analyzed on the design example of the three port dc/dc transformer of several hundreds of watts of the output power for high voltage applications. The final part of this research considers the implementation and performance analysis of the four port dc/dc transformer in a low voltage application of tens of watts of the output power and without isolation requirements.

Effect of laser processing parameters on the structure of ductile iron

Laser processing of structure sensitive hypereutectic ductile iron, a cast alloy employed for dynamically loaded automative components, was experimentally investigated over a wide range of process parameters: from power (0.5-2.5 kW) and scan rate (7.5-25 mm s(-1)) leading to solid state transformation, all the way through to melting followed by rapid quenching. Superfine dendritic (at 10(5) degrees C s(-1)) or feathery (at 10(4) degrees C s(-1)) ledeburite of 0.2-0.25 mu m lamellar space, gamma-austenite and carbide in the laser melted and martensite in the transformed zone or heat-affected zone were observed, depending on the process parameters. Depth of geometric profiles of laser transformed or melt zone structures, parameters such as dendrile arm spacing, volume fraction of carbide and surface hardness bear a direct relationship with the energy intensity P/UDb2, (10-100 J mm(-3)). There is a minimum energy intensity threshold for solid state transformation hardening (0.2 J mm(-3)) and similarly for the initiation of superficial melting (9 J mm(-3)) and full melting (15 J mm(-3)) in the case of ductile iron. Simulation, modeling and thermal analysis of laser processing as a three-dimensional quasi-steady moving heat source problem by a finite difference method, considering temperature dependent energy absorptivity of the material to laser radiation, thermal and physical properties (kappa, rho, c(p)) and freezing under non-equilibrium conditions employing Scheil's equation to compute the proportion of the solid enabled determination of the thermal history of the laser treated zone. This includes assessment of the peak temperature attained at the surface, temperature gradients, the freezing time and rates as well as the geometric profile of the melted, transformed or heat-affected zone. Computed geometric profiles or depth are in close agreement with the experimental data, validating the numerical scheme.

Conditions for the local manipulation of all bipartite Gaussian states

We provide a general, necessary, and sufficient condition for the possibility of transforming a mixed bipartite Gaussian state with arbitrarily many modes to another one under arbitrary local Gaussian channels, which do not include classical communication. Moreover, by means of this condition we present a necessary criterion that can be used to check the possibility of a state transformation between two mixed Gaussian states. At the same time, we prove that our criterion can be reduced to the Eisert-Plenio criterion when the mode number is chosen as 1 per side.

Conditions for the local manipulation of tripartite Gaussian states

We present the normal form of the covariance matrix for three-mode tripartite Gaussian states. By means of this result, the general form of a necessary and sufficient criterion for the possibility of a state transformation from one tripartite entangled Gaussian state to another with three modes is found. Moreover, we show that the conditions presented include not only inequalities but equalities as well.

Colombia: compromise or containment?

The design, reformulation, and final signing of Plan Colombia by the then US President, Bill Clinton, on the 13 July 2000 initiated in a new era of the US State´s involvement in supposedly sovereign-territorial issues of Colombian politics. The implementation of Plan Colombia there-on-after brought about a major realignment of political-military scales and terrains of conflict that have renewed discourses concerning the contemporary imperialist interests of key US-based but transnationally-projected social forces, leading to arguments that stress the invigorated geo-political dimension of present-day strategies of capitalist accumulation. With the election of Álvaro Uribe Vélez as Colombian President in May 2002 and his pledge to strengthen the national military campaign aganist the region´s longest-surviving insurgency guerrilla group, Las FARC-EP, as well as other guerrilla factions, combined with a new focus on establishing the State project of “Democratic Security”; the military realm of governance and attempts to ensure property security and expanding capitalist investment have attained precedence in Colombia´s national political domains. This working paper examines the interrelated nature of Plan Colombia -as a binational and indeed regional security strategy- and Uribe´s Democratic Security project as a means of showing the manner in which they have worked to pave the way for the implementation of a new “total market” regime of accumulation, based on large-scale agro-industrial investment which is accelerated through processes of accumulation via dispossession. As such, the political and social reconfigurations involved manifest the multifarious scales of governance that become intertwined in incorporating neoliberalism in specific regions of the world economy. Furthermore, the militarisation-securitisation of such policies also illustrate the explicit contradictions of neoliberalism in a peripheral context, where coercion seems to prevail, something which leads to a profound questioning of the extent to which neoliberalism can be thought of as a hegemonic politico-economic project.

Modeling of hybrid systems by piecewise decomposition

Piecewise linear models systems arise as mathematical models of systems in many practical applications, often from linearization for nonlinear systems. There are two main approaches of dealing with these systems according to their continuous or discrete-time aspects. We propose an approach which is based on the state transformation, more particularly the partition of the phase portrait in different regions where each subregion is modeled as a two-dimensional linear time invariant system. Then the Takagi-Sugeno model, which is a combination of local model is calculated. The simulation results show that the Alpha partition is well-suited for dealing with such a system

Helices, chirality and interpenetration: the versatility and remarkable interconversion of silver-copper cyanide frameworks

The structural transformations between cesium silver-copper cyanides under modest conditions, both in solution and in the solid state, are described. Three new cesium silver(I) copper(I) cyanides with three-dimensional (3-D) framework structures were prepared as single crystals from a one-pot reaction initially heated under hydrothermal conditions. The first product to appear, Cs3Ag2Cu3(CN)(8) (I), when left in contact with the supernatant produced CsAgCu(CN)(3) (II) and CsAgCu(CN)(3)center dot 1/3H(2)O (III) over a few months via a series of thermodynamically controlled cascade reactions. Crystals of the hydrate (III) can be dehydrated to polycrystalline CsAgCu(CN)(3) (II) on heating at 100 degrees C in a remarkable solid-state transformation involving substantial breaking and reconnection of metal-cyanide linkages. Astonishingly, the conversion between the two known polymorphs of CsAg2Cu(CN)(4), which also involves a major change in connectivity and topology, occurs at 180 degrees C as a single-crystal to single-crystal transformation. Structural features of note in these materials include the presence of helical copper-cyanide chains in (I) and (II), which in the latter compound produce a chiral material. In (II) and (III), the silver-copper cyanide networks are both self- and interpenetrating, features also seen in the known polymorphs of CsAg2Cu(CN)(4).

Two-dimensional similarity between forms I and II of cytenamide, a carbamazepine analogue

Cytenamide form I (R (3) over bar) undergoes a solid-state transformation upon heating to form II (P (1) over bar), with the structures exhibiting the same two-dimensional similarity that exists between the R (3) over bar and P (1) over bar forms of carbamazepine.