Measurements of thermophysical properties of perfluorocarbons and ionic liquids

No presente trabalho propõe-se estudar a tensão superficial de vários perfluorocarbonetos lineares, cíclicos, aromáticos e [alfa]-substituídos bem como líquidos iónicos com o catião imidazolium em comum. Apesar do seu interesse inerente, informação sobre esta propriedade para os compostos seleccionados é escassa e quando disponível apresenta discrepâncias consideráveis entre si. As medições foram realizadas no intervalo de temperaturas (283 to 353) K usando o método do anel de Du Noüy. Para os fluorocarbonetos, os dados experimentais demonstram que a estrutura molecular é o factor primordial no comportamento da superfície uma vez que os fluorocarbonetos aromáticos apresentam a tensão superficial mais elevada, seguida pelos fluorocarbonetos cíclicos e substituídos. Os perfluorocarbonetos lineares apresentam os menores valores de tensão superficial, aumentando ligeiramente com o aumento do número de carbonos. Os líquidos iónicos estudados foram seleccionados com o objectivo de fornecerem um estudo compreensivo sobre a influência do tamanho da cadeia alquílica do catião, o número de substituições no catião e a influência do anião. A influência do conteúdo de água na tensão superficial foi estudada em função da temperatura e da fracção molar de água para o liquido iónico mais hidrofóbico, [omim][PF6], e para o mais higroscópico, [bmim][PF6]. As funções termodinâmicas de superfície, como a entropia e entalpia de superfície, foram derivadas a partir da dependência da tensão superficial com a temperatura. Os dados obtidos para o fluorocarbonetos foram comparados com a correlação proposta por Faizullin, apresentando um desvio inferior a 4 % e demonstrando a sua aplicabilidade para com esta classe de compostos. A metodologia adoptada neste trabalho requer o conhecimento das densidades dos compostos de modo a aplicar a necessária correcção hidrostática. Contudo, para os líquidos iónicos esta informação é limitada ou mesmo inexistente. Por este motivo realizaram-se medições de densidade em função da pressão (0.10 < p/MPa < 10.0) e da temperatura (293.15 < T/K < 393.15). Desta dependência, as propriedades termodinâmicas, tais como compressibilidade isotérmica, expansividade isobárica, coeficiente térmico da pressão e dependência da capacidade calorífica com a pressão foram investigadas. A influência do teor de água na densidade foi também estudada para o líquido iónico mais hidrofóbico, [omim][PF6]. Um modelo simples de volume-ideal foi aplicado de forma preditiva para os volumes molares dos líquidos iónicos, em condições ambientais, descrevendo bem os dados experimentais. ABSTRACT: This work aims at studying the surface tension of some linear, cyclic, aromatic, [alfa]-substituted perfluorocarbons and imidazolium based ionic liquids. Despite its fundamental interest, information about this property for these compounds is scarce and the available data present strong discrepancies among each other. The measurements were carried out in the temperature range (283 to 353) K with the Du Noüy ring method. For the fluorocarbons, the analysis of the experimental data shows that the molecular structure is the main factor in the surface since the aromatic fluorocompounds present the highest surface tensions, followed by the cyclic and substituted fluorocompounds. The linear n-perfluoroalkanes exhibit the lowest surface tension values, slightly increasing with the carbon number. The set of selected ionic liquids was chosen to provide a comprehensive study of the influence of the cation alkyl chain length, the number of cation substitutions and the anion on the properties under study. The influence of water content in the surface tension was studied for several ILs as a function of the temperature as well as a function of water mole fraction, for the most hydrophobic IL investigated, [omim][PF6], and one hygroscopic IL, [bmim][PF6]. The surface thermodynamic functions such as surface entropy and enthalpy were derived from the temperature dependence of the surface tension values. The perfluorocarbons experimental data were compared against the Faizullin correlation, and it is shown that this correlation describes the measured surface tensions with deviations inferior to 4 %. The methodology adopted in this work requires the knowledge of the densities of the compounds under study in order to apply an hydrostatic correction. However, for ionic liquids these information is scarse and in some cases unavailable. Therefore, experimental measurements of the pressure (0.10 < p/MPa < 10.0) and temperature (293.15 < T/K < 393.15) dependence of the density and derived thermodynamic properties, such as the isothermal compressibility, the isobaric expansivity, the thermal pressure coefficient, and the pressure dependence of the heat capacity of several imidazolium-based ionic were determined. The influence of water content in the density was also studied for the most hydrophobic IL used, [omim][PF6]. A simple ideal-volume model was employed for the prediction of the imidazolium molar volumes at ambient conditions, which proved to agree well with the experimental results.

Relatório de estágio no departamento central de investigação e acção penal

The means of obtaining evidence, the amount of evidence obtained, the number of defendants related to each criminal case and the gravity of the crimes for which the magistrates of the Department are holders of penal action, define its real importance to the Rule of Law. I have deeply studied the subject of the institution of hierarchical intervention required by the assistant and the application of an opening statement by the defendant, starting from a hypothetical case, provided when the query of an investigation with the subject of the crime of active corruption, where this institution was called as a reaction to the archiving dispatch delivered by the Public Ministry. I have study about the implementation of the institution of provisional suspension of the process, specifically in the scope of fiscal criminality, analyzing the effective satisfaction of the purposes of the sentences in two slopes: general prevention and special prevention. I went for my first time to a Central Court of Criminal Instruction, where I attended the measures of inquiry and instructive debate of a process that culminated with the prosecution and pronunciation of the defendants. In addition to this criminal experience, I have deepened and consolidated the academic knowledge with the study of various criminal cases from various fields in the scope of criminality investigated by the Department. I could therefore check the basis of procedural delays, regarding to our legal system, especially in this type of crime, raising issues that I analyzed and discussed, always in a critical and academic way. I had the opportunity to attend and witness a seminar in the Lisbon Directorate of Finance as well of entering the Centre for Judicial Studies to attend a conference on the International Anti-Corruption Day. Focus on the investigatory importance of the international judicial cooperation, through the various organs, with special interest to EUROJUST. I comprehended the organization and functioning of these communitarian organs and means of communication of procedural acts, in particular, the rogatory letters and european arrest warrants. This involvement is motivated by the moratorium factor of the investigations where rogatory letters are necessary for the acquisition of evidence or information relevant to the good continuation of the process. For this reason the judicial cooperation through the relevant communitarian organs, translates a streamlined response between the competent judicial authorities of the Member States, through the National Member that integrates EUROJUST. This report aims to highlight some of the difficulties and procedural issues that Public Prosecutors of DCIAP and criminal police bodies that assist them, face in combating violent and organized crime, of national and transnational nature, of particular complexity, according to the specifics of criminal types.

Efectividade e eficiência: médicos, gestores, informação e bom senso

RESUMO - Num contexto de escassez de recursos, agravado pelo aumento da procura de cuidados de saúde e pelo custo do imperativo tecnológico, muitas vezes erroneamente confundido com imperativo ético, a procura da eficiência é cada vez mais relevante. Para que esta se atinja e mantenha é preciso um conhecimento profundo dos efeitos das medidas eficazes, a verdadeira efectividade, numa perspectiva sistémica, o que implica uma partilha de saberes e acções concertadas entre médicos e gestores. A lógica económica não substitui o juízo clínico, mas reforça a necessidade de compatibilizar as intervenções úteis com o custo pessoal e social exigido. Precisa-se de boa informação que gere conhecimento e do insubstituível bom senso.

Toward a rational-choice foundation of non-additive theories

A classical argument of de Finetti holds that Rationality implies Subjective Expected Utility (SEU). In contrast, the Knightian distinction between Risk and Ambiguity suggests that a rational decision maker would obey the SEU paradigm when the information available is in some sense good, and would depart from it when the information available is not good. Unlike de Finetti's, however, this view does not rely on a formal argument. In this paper, we study the set of all information structures that might be availabe to a decision maker, and show that they are of two types: those compatible with SEU theory and those for which SEU theory must fail. We also show that the former correspond to "good" information, while the latter correspond to information that is not good. Thus, our results provide a formalization of the distinction between Risk and Ambiguity. As a consequence of our main theorem (Theorem 2, Section 8), behavior not-conforming to SEU theory is bound to emerge in the presence of Ambiguity. We give two examples of situations of Ambiguity. One concerns the uncertainty on the class of measure zero events, the other is a variation on Ellberg's three-color urn experiment. We also briefly link our results to two other strands of literature: the study of ambiguous events and the problem of unforeseen contingencies. We conclude the paper by re-considering de Finetti's argument in light of our findings.

House price dynamics and bank herding: European empirical evidence

This paper investigates the behavior of residential property and examines the linkages between house price dynamics and bank herding behavior. The analysis presents evidence that irrational behaviour may have played a significant role in several countries, including; United Kingdom, Spain, Denmark, Sweden and Ireland. In addition, we also provide evidence indicative of herding behaviour in the European residential mortgage loan market. Granger Causality tests indicate that non-fundamentally justified prices dynamics contributed to herding by lenders and that this behaviour was a response by the banks as a group to common information on residential property assets. In contrast, in Germany, Portugal and Austria, residential property prices were largely explained by fundamentals. Furthermore, these countries show no evidence of either irrational price bubbles or herd behaviour in the mortgage market. Granger Causality tests indicate that both variables are independent.

Adaptive communication: languages with more non-native speakers tend to have fewer word forms

Explaining the diversity of languages across the world is one of the central aims of typological, historical, and evolutionary linguistics. We consider the effect of language contact-the number of non-native speakers a language has-on the way languages change and evolve. By analysing hundreds of languages within and across language families, regions, and text types, we show that languages with greater levels of contact typically employ fewer word forms to encode the same information content (a property we refer to as lexical diversity). Based on three types of statistical analyses, we demonstrate that this variance can in part be explained by the impact of non-native speakers on information encoding strategies. Finally, we argue that languages are information encoding systems shaped by the varying needs of their speakers. Language evolution and change should be modeled as the co-evolution of multiple intertwined adaptive systems: On one hand, the structure of human societies and human learning capabilities, and on the other, the structure of language.

Grafisk profil till ett företag som tillverkar handgjorda textilprodukter av naturmaterial : Hur kan en hemsida kommunicera ett varumärke?

Målet med detta examensarbete var att skapa en grafisk profil till företaget Lyst Form AB som bedriver större delen av sin affärsverksamhet via en hemsida. Företaget säljer handgjorda kläder och accessoarer i lintyg. En teoretisk del i arbetet tar upp hur varumärket kan kommuniceras genom hemsidan. Den grafiska profilen utformades utifrån företagets identitet. Det är viktigt att företaget speglas på ett korrekt sätt. Ett företags identitet kan beskrivas som organisationens själ och den visas utåt i form av bland annat den grafiska profilen. Denna ses därför som en viktig identitetsbärare och den kan kallas för den visuella identiteten. En grafisk profil innehåller bland annat logotyp, profilfärger samt typografi. Företagets målgrupp ansågs vara en viktig del i hela processen eftersom de i slutändan ska tilltalas av den grafiska profilen. Först gjordes en grundlig undersökning och research av företaget för att få en god uppfattning av dess identitet. Även konkurrenterna granskades. En enkätundersökning gjordes för att kunna samla information utifrån målgruppens perspektiv. Denna informationsinsamling gav ett bra underlag och en riktlinje i framtagningen av den grafiska profilen.   Under designprocessens gång diskuterades de logotypförslag som togs fram med hjälp av en sammansatt fokusgrupp. Diskussionen var givande och var till stor nytta i designprocessen. Baserat på den grafiska profilen skapades en layout för hemsidan samt exempel på trycksaker för att visa hur den kan användas. En enklare grafisk manual skapades för att företaget ska kunna synas utåt på ett enhetligt sätt. En sista enkätundersökning gjordes för att se om målet uppnåtts. Resultatet visade att den nya framtagna grafiska profilen var en klar förbättring jämfört mot den nuvarande sett utifrån företagets identitet. I slutändan valde dock företaget en annan logotyp. Detta påvisar svårigheterna i processen att ta fram en grafisk profil. Alla delar i processen är viktiga och undersökningarna är bland annat en av de väsentliga delarna vilka bidrar med en större chans till ett bra slutresultat som tar hänsyn till både företagets och målgruppens åsikter.  

Manual for the compilation of science and technology indicators in the Caribbean

Includes bibliography

A documentação patrimonial: gênese e fluxo dos processos de tombamento do Museu Prudente de Moraes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Combining ALOS/PALSAR derived vegetation structure and inundation patterns to characterize major vegetation types in the Mamiraua Sustainable Development Reserve, Central Amazon floodplain, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Supramolecular hybrid organic-inorganic multicomponent architectures in solution and on surface

Supramolecular architectures can be built-up from a single molecular component (building block) to obtain a complex of organic or inorganic interactions creating a new emergent condensed phase of matter, such as gels, liquid crystals and solid crystal. Further the generation of multicomponent supramolecular hybrid architecture, a mix of organic and inorganic components, increases the complexity of the condensed aggregate with functional properties useful for important areas of research, like material science, medicine and nanotechnology. One may design a molecule storing a recognition pattern and programming a informed self-organization process enables to grow-up into a hierarchical architecture. From a molecular level to a supramolecular level, in a bottom-up fashion, it is possible to create a new emergent structure-function, where the system, as a whole, is open to its own environment to exchange energy, matter and information. “The emergent property of the whole assembly is superior to the sum of a singles parts”. In this thesis I present new architectures and functional materials built through the selfassembly of guanosine, in the absence or in the presence of a cation, in solution and on the surface. By appropriate manipulation of intermolecular non-covalent interactions the spatial (structural) and temporal (dynamic) features of these supramolecular architectures are controlled. Guanosine G7 (5',3'-di-decanoil-deoxi-guanosine) is able to interconvert reversibly between a supramolecular polymer and a discrete octameric species by dynamic cation binding and release. Guanosine G16 (2',3'-O-Isopropylidene-5'-O-decylguanosine) shows selectivity binding from a mix of different cation's nature. Remarkably, reversibility, selectivity, adaptability and serendipity are mutual features to appreciate the creativity of a molecular self-organization complex system into a multilevelscale hierarchical growth. The creativity - in general sense, the creation of a new thing, a new thinking, a new functionality or a new structure - emerges from a contamination process of different disciplines such as biology, chemistry, physics, architecture, design, philosophy and science of complexity.

Oblique ionograms automatic scaling and eikonal based ray tracing

A method for automatic scaling of oblique ionograms has been introduced. This method also provides a rejection procedure for ionograms that are considered to lack sufficient information, depicting a very good success rate. Observing the Kp index of each autoscaled ionogram, can be noticed that the behavior of the autoscaling program does not depend on geomagnetic conditions. The comparison between the values of the MUF provided by the presented software and those obtained by an experienced operator indicate that the procedure developed for detecting the nose of oblique ionogram traces is sufficiently efficient and becomes much more efficient as the quality of the ionograms improves. These results demonstrate the program allows the real-time evaluation of MUF values associated with a particular radio link through an oblique radio sounding. The automatic recognition of a part of the trace allows determine for certain frequencies, the time taken by the radio wave to travel the path between the transmitter and receiver. The reconstruction of the ionogram traces, suggests the possibility of estimating the electron density between the transmitter and the receiver, from an oblique ionogram. The showed results have been obtained with a ray-tracing procedure based on the integration of the eikonal equation and using an analytical ionospheric model with free parameters. This indicates the possibility of applying an adaptive model and a ray-tracing algorithm to estimate the electron density in the ionosphere between the transmitter and the receiver An additional study has been conducted on a high quality ionospheric soundings data set and another algorithm has been designed for the conversion of an oblique ionogram into a vertical one, using Martyn's theorem. This allows a further analysis of oblique soundings, throw the use of the INGV Autoscala program for the automatic scaling of vertical ionograms.

Bulk chemical analysis of sediments ODP Hole 110-671B and 110-672A

Chemical analyses for calcium carbonate, organic carbon, and major constituents (Al, Ti, Ca, Mg, K, Fe) of bulk sediments collected in Hole 671B have been carried out. Organic carbon contents in Pleistocene through middle Miocene sediments above the zone of decollement are very low (<0.1%); below the decollement considerably higher concentrations of organic carbon occur (up to 1 %). Changes in Ti/Al and Fe/Al ratios are minor, but K/Al and Mg/Al ratios show clear trends with the age of the sediments. Preliminary comparisons of these ratios with mineralogic information on clays indicate good correspondence with clay abundances. Calculations of the mass flux of magnesium from the overlying ocean into the pore fluids suggest that addition of magnesium to the sediments is difficult to detect, especially in the absence of a background reference concentration.

Agreement Abstractions in Anonymous and Homonymous Distributed Systems Prone to Failures

The distributed computing models typically assume every process in the system has a distinct identifier (ID) or each process is programmed differently, which is named as eponymous system. In such kind of distributed systems, the unique ID is helpful to solve problems: it can be incorporated into messages to make them trackable (i.e., to or from which process they are sent) to facilitate the message transmission; several problems (leader election, consensus, etc.) can be solved without the information of network property in priori if processes have unique IDs; messages in the register of one process will not be overwritten by others process if this process announces; it is useful to break the symmetry. Hence, eponymous systems have influenced the distributed computing community significantly either in theory or in practice. However, every thing in the world has its own two sides. The unique ID also has disadvantages: it can leak information of the network(size); processes in the system have no privacy; assign unique ID is costly in bulk-production(e.g, sensors). Hence, homonymous system is appeared. If some processes share the same ID and programmed identically is called homonymous system. Furthermore, if all processes shared the same ID or have no ID is named as anonymous system. In homonymous or anonymous distributed systems, the symmetry problem (i.e., how to distinguish messages sent from which process) is the main obstacle in the design of algorithms. This thesis is aimed to propose different symmetry break methods (e.g., random function, counting technique, etc.) to solve agreement problem. Agreement is a fundamental problem in distributed computing including a family of abstractions. In this thesis, we mainly focus on the design of consensus, set agreement, broadcast algorithms in anonymous and homonymous distributed systems. Firstly, the fault-tolerant broadcast abstraction is studied in anonymous systems with reliable or fair lossy communication channels separately. Two classes of anonymous failure detectors AΘ and AP∗ are proposed, and both of them together with a already proposed failure detector ψ are implemented and used to enrich the system model to implement broadcast abstraction. Then, in the study of the consensus abstraction, it is proved the AΩ′ failure detector class is strictly weaker than AΩ and AΩ′ is implementable. The first implementation of consensus in anonymous asynchronous distributed systems augmented with AΩ′ and where a majority of processes does not crash. Finally, a general consensus problem– k-set agreement is researched and the weakest failure detector L used to solve it, in asynchronous message passing systems where processes may crash and recover, with homonyms (i.e., processes may have equal identities), and without a complete initial knowledge of the membership.

Agreement Abstractions in Anonymous and Homonymous Distributed Systems Prone to Failures

The distributed computing models typically assume every process in the system has a distinct identifier (ID) or each process is programmed differently, which is named as eponymous system. In such kind of distributed systems, the unique ID is helpful to solve problems: it can be incorporated into messages to make them trackable (i.e., to or from which process they are sent) to facilitate the message transmission; several problems (leader election, consensus, etc.) can be solved without the information of network property in priori if processes have unique IDs; messages in the register of one process will not be overwritten by others process if this process announces; it is useful to break the symmetry. Hence, eponymous systems have influenced the distributed computing community significantly either in theory or in practice. However, every thing in the world has its own two sides. The unique ID also has disadvantages: it can leak information of the network(size); processes in the system have no privacy; assign unique ID is costly in bulk-production(e.g, sensors). Hence, homonymous system is appeared. If some processes share the same ID and programmed identically is called homonymous system. Furthermore, if all processes shared the same ID or have no ID is named as anonymous system. In homonymous or anonymous distributed systems, the symmetry problem (i.e., how to distinguish messages sent from which process) is the main obstacle in the design of algorithms. This thesis is aimed to propose different symmetry break methods (e.g., random function, counting technique, etc.) to solve agreement problem. Agreement is a fundamental problem in distributed computing including a family of abstractions. In this thesis, we mainly focus on the design of consensus, set agreement, broadcast algorithms in anonymous and homonymous distributed systems. Firstly, the fault-tolerant broadcast abstraction is studied in anonymous systems with reliable or fair lossy communication channels separately. Two classes of anonymous failure detectors AΘ and AP∗ are proposed, and both of them together with a already proposed failure detector ψ are implemented and used to enrich the system model to implement broadcast abstraction. Then, in the study of the consensus abstraction, it is proved the AΩ′ failure detector class is strictly weaker than AΩ and AΩ′ is implementable. The first implementation of consensus in anonymous asynchronous distributed systems augmented with AΩ′ and where a majority of processes does not crash. Finally, a general consensus problem– k-set agreement is researched and the weakest failure detector L used to solve it, in asynchronous message passing systems where processes may crash and recover, with homonyms (i.e., processes may have equal identities), and without a complete initial knowledge of the membership.