X-ray diffraction, thermal analysis, and Raman scattering study of K2BeF4 and comparation to other member of the (beta)-K2SO4 family with ferroelectric -paraelectric transition

Thermal analysis, powder diffraction, and Raman scattering as a function of the temperature were carried out on K2BeF4. Moreover, the crystal structure was determined at 293 K from powder diffraction. The compound shows a transition from Pna21 to Pnam space group at 921 K with a transition enthalpy of 5 kJ/mol. The transition is assumed to be first order because the compound shows metastability. Structurally and spectroscopically the transition is similar to those observed in (NH4)2SO4, which suggests that the low-temperature phase is ferroelectric. In order to confirm it, the spontaneous polarization has been computed using an ionic model.

Effects of Nb doping on the TiO2 anatase-to-rutile phase transition

We study the influence of Nb doping on the TiO2 anatase-to-rutile phase transition, using combined transmission electron microscopy, Raman spectroscopy, x-ray diffraction and selected area electron diffraction analysis. This approach enabled anatase-to-rutile phase transition hindering to be clearly observed for low Nb-doped TiO2 samples. Moreover, there was clear grain growth inhibition in the samples containing Nb. The use of high resolution transmission electron microscopy with our samples provides an innovative perspective compared with previous research on this issue. Our analysis shows that niobium is segregated from the anatase structure before and during the phase transformation, leading to the formation of NbO nanoclusters on the surface of the TiO2 rutile nanoparticles.

Kinetics of martensitic transitions in Cu-Al-Mn under thermal cycling: Analysis at multiple length scales

In this paper we study the evolution of the kinetic features of the martensitic transition in a Cu-Al-Mn single crystal under thermal cycling. The use of several experimental techniques including optical microscopy, calorimetry, and acoustic emission, has enabled us to perform an analysis at multiple scales. In particular, we have focused on the analysis of avalanche events (associated with the nucleation and growth of martensitic domains), which occur during the transition. There are significant differences between the kinetics at large and small length scales. On the one hand, at small length scales, small avalanche events tend to sum to give new larger events in subsequent loops. On the other hand, at large length scales the large domains tend to split into smaller ones on thermal cycling. We suggest that such different behavior is the necessary ingredient that leads the system to the final critical state corresponding to a power-law distribution of avalanches.

Contexts and typologies in the analysis of welfare state legitimacy : a social psychological approach to political opinion formation

This dissertation analyses public opinion towards the welfare state across 29 European countries. Based on an interdisciplinary approach combining social psychological, sociological, and public opinion approaches to political opinion formation, it investigates how social position and shared beliefs shape perceived legitimacy of welfare institutions, and how social contexts impact on the processes of opinion formation. Drawing on social representations theory, as well as socialization and self-interest approaches, the dissertation analyses the role of social position in lay support for institutional solidarity. Normative beliefs-defined as preferred views regarding the organisation of social relations-mediate the effect of social position on welfare support. In addition, drawing on public opinion literature, the dissertation analyses opinion formation as a function of country-level structural (e.g., level of social spending, unemployment) and ideological factors (e.g., level of meritocracy). The dissertation comprises two theoretical and four empirical chapters. Three of the empirical chapters use data from the European Social Survey 2008. Using multilevel and typological approaches, the dissertation contributes to welfare attitude literature by showing that normative beliefs, such as distrust or egalitarianism, function as underlying mechanisms that link social position to policy attitudes (Chapter 3), and that characteristics of the national contexts influence the processes of political opinion formation (Chapters 3 and 4). Chapter 5 proposes and predicts a typology of the relationship between attitudes towards solidarity and attitudes towards control, reflecting the two central domains of government intervention. Finally, Chapter 6 examines welfare support in the realm of action and social protest, using data from a survey on Spanish Indigados activists. The findings of this dissertation inform contemporary debates about welfare state legitimacy and retrenchment. - Cette thèse avait pour but d'analyser l'opinion publique envers l'Etat social dans 29 pays européens. Basée sur une approche interdisciplinaire qui combine des perspectives psycho-sociales, sociologiques et d'opinion publique sur la formation d'opinion politique, la thèse étudie comment la position sociale et les croyances partagées façonnent la légitimité perçue des institutions de l'Etat social, et comment les contextes sociaux influencent les processus de formation d'opinion. Basée sur la théorie des représentations sociales, ainsi qu'une approche de socialisation et d'intérêt propre, cette thèse analyse le rôle des positions sociales dans le soutien envers la solidarité institutionnelle. Les croyances normatives-définies comme les visions préférées de l'organisation des rapports sociaux-médiatisent l'effet de la position sociale sur le soutien pour l'Etat social. De plus, s'inspirant de la littérature sur l'opinion publique, la thèse analyse la formation d'opinion en fonction des facteurs structurels (ex. le taux de dépenses sociales, le chômage) et idéologiques (ex. le degré de méritocratie). Cette thèse est composée de deux chapitres théoriques et quatre chapitres empiriques. Trois chapitres empiriques utilisent des données provenant de l'enquête European Social Survey 2008. Appliquant des approches multi-niveux et typoloqiques, la thèse contribue à la littérature sur les attitudes envers l'Etat social en montrant que les croyances normatives, telles que la méfiance ou l'égalitarisme, fonctionnent comme des mécanismes sous-jacents qui relient la position sociale aux attitudes politiques (Chapitre 3), et que les caractéristiques des contextes nationaux influencent les processus de formation d'opinion politique (Chapitres 3 et 4). Le chapitre 5 propose et prédit une typologie sur le rapport entre les attitudes envers la solidarité et celles envers le contrôle, renvoyant à deux domaines centraux de régulation étatique. Enfin, le chapitre 6 examine le soutien à l'Etat social dans le domaine de l'action protestataire, utilisant des données d'une enquête menée auprès des militants espagnols du mouvement des Indignés. Les résultats de cette thèse apportent des éléments qui éclairent les débats contemporains sur la légitimité de l'Etat social et son démantèlement.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

X-ray diffraction, thermal analysis, and Raman scattering study of K2BeF4 and comparation to other member of the (beta)-K2SO4 family with ferroelectric -paraelectric transition

Thermal analysis, powder diffraction, and Raman scattering as a function of the temperature were carried out on K2BeF4. Moreover, the crystal structure was determined at 293 K from powder diffraction. The compound shows a transition from Pna21 to Pnam space group at 921 K with a transition enthalpy of 5 kJ/mol. The transition is assumed to be first order because the compound shows metastability. Structurally and spectroscopically the transition is similar to those observed in (NH4)2SO4, which suggests that the low-temperature phase is ferroelectric. In order to confirm it, the spontaneous polarization has been computed using an ionic model.

Reconstruction of the recent history of a large deep prealpine lake (Lake Bourget, France) using subfossil chironomids, diatoms, and organic matter analysis: towards the definition of a lake-specific reference state

This paper presents the recent history of a large prealpine lake (Lake Bourget) using chironomids, diatoms and organic matter analysis, and deals with the ability of paleolimnological approach to define an ecological reference state for the lake in the sense of the European Framework Directive. The study at low resolution of subfossil chironomids in a 4-m-long core shows the remarkable stability over the last 2.5 kyrs of the profundal community dominated by a Micropsectra-association until the beginning of the twentieth century, when oxyphilous taxa disappeared. Focusing on this key recent period, a high resolution and multiproxy study of two short cores reveals a progressive evolution of the lake's ecological state. Until AD 1880, Lake Bourget showed low organic matter content in the deep sediments (TOC less than 1%) and a well-oxygenated hypolimnion that allowed the development of a profundal oxyphilous chironomid fauna (Micropsectra-association). Diatom communities were characteristic of oligotrophic conditions. Around AD 1880, a slight increase in the TOC was the first sign of changes in lake conditions. This was followed by a first limited decline in oligotrophic diatom taxa and the disappearance of two oxyphilous chironomid taxa at the beginning of the twentieth century. The 1940s were a major turning point in recent lake history. Diatom assemblages and accumulation of well preserved planktonic organic matter in the sediment provide evidence of strong eutrophication. The absence of profundal chironomid communities reveals permanent hypolimnetic anoxia. From AD 1995 to 2006, the diatom assemblages suggest a reduction in nutrients, and a return to mesotrophic conditions, a result of improved wastewater management. However, no change in hypolimnion benthic conditions has been shown by either the organic matter or the subfossil chironomid profundal community. Our results emphasize the relevance of the paleolimnological approach for the assessment of reference conditions for modern lakes. Before AD 1900, the profundal Micropsectra-association and the Cyclotella dominated diatom community can be considered as the Lake Bourget reference community, which reflects the reference ecological state of the lake.

Patterns and transitions in substance use among young Swiss men: a latent transition analysis approach

This study investigates the potential stages of drug use. Data from the longitudinal Cohort Study on Substance Use Risk Factors were used (N = 5,116). Drug use (alcohol, tobacco, and 16 illicit drugs) over the previous 12 months was assessed at two time points. Patterns and trajectories of drug use were studied using latent transition analysis (LTA). This study's substantive contributions are twofold. First, the pattern of drug use displayed the well-known sequence of drug involvement (licit drugs to cannabis to other illicit drugs), but with an added distinction between two kinds of illicit drugs ("middle-stage" drugs: uppers, hallucinogens, inhaled drugs; and "final-stage" drugs: heroin, ketamine, GHB/GBL, research chemicals, crystal meth, and spice). Second, subgroup membership was stable over time, as the most likely transition was remaining in the same latent class.

The Fairness of Media Coverage in Question: An Analysis of Referendum Campaigns on Welfare State Issues in Switzerland

The mass media are assigned an important role in political campaigns on popular votes. This article asks how the press communicates political issues to citizens during referendum campaigns, and whether some minimal criteria for successful public deliberation are met. The press coverage of all 24 ballot votes on welfare state issues from 1995 to 2004 in Switzerland is examined, distinguishing seven criteria to judge how news coverage compares to idealized notions of the media's role in the democratic process: coverage intensity, time for public deliberation, balance in media coverage, source independence and inclusiveness, substantive coverage, and spatial homogeneity. The results of our quantitative analysis suggest that the press does fulfil these normative requirements to a reasonable extent and that fears about biased or deceitful media treatment of ballot issues are not well-founded. However, some potential for optimizing the coverage of referendum campaigns by the Swiss press does exist

Life cycle analysis and life cyle impact assessment methodologies: a state of the art

Life cycle analysis (LCA) is a comprehensive method for assessing the environmental impact of a product or an activity over its entire life cycle. The purpose of conducting LCA studies varies from one application to another. Different applications use LCA for different purposes. In general, the main aim of using LCA is to reduce the environmental impact of products through guiding the decision making process towards more sustainable solutions. The most critical phase in an LCA study is the Life Cycle Impact Assessment (LCIA) where the life cycle inventory (LCI) results of the considered substances related to the study of a certain system are transformed into understandable impact categories that represent the impact on the environment. In this research work, a general structure clarifying the steps that shall be followed ir order to conduct an LCA study effectively is presented. These steps are based on the ISO 14040 standard framework. In addition, a survey is done on the most widely used LCIA methodologies. Recommendations about possible developments and suggetions for further research work regarding the use of LCA and LCIA methodologies are discussed as well.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Bayesian Networks for the Age Classification of Living Individuals: a Study on Transition Analysis

Over the past few decades, age estimation of living persons has represented a challenging task for many forensic services worldwide. In general, the process for age estimation includes the observation of the degree of maturity reached by some physical attributes, such as dentition or several ossification centers. The estimated chronological age or the probability that an individual belongs to a meaningful class of ages is then obtained from the observed degree of maturity by means of various statistical methods. Among these methods, those developed in a Bayesian framework offer to users the possibility of coherently dealing with the uncertainty associated with age estimation and of assessing in a transparent and logical way the probability that an examined individual is younger or older than a given age threshold. Recently, a Bayesian network for age estimation has been presented in scientific literature; this kind of probabilistic graphical tool may facilitate the use of the probabilistic approach. Probabilities of interest in the network are assigned by means of transition analysis, a statistical parametric model, which links the chronological age and the degree of maturity by means of specific regression models, such as logit or probit models. Since different regression models can be employed in transition analysis, the aim of this paper is to study the influence of the model in the classification of individuals. The analysis was performed using a dataset related to the ossifications status of the medial clavicular epiphysis and results support that the classification of individuals is not dependent on the choice of the regression model.

Análisis de los apoyos que reciben los jóvenes con discapacidad intelectual en su transición a la vida adulta en España: una investigación a partir de experiencias de profesionales y personas con discapacidad = Analysis of support received by young people with intellectual disabilities in their transition to adulthood in Spain: an investigation based on the experiences of professionals and people with disabilities

The objective of this study is to gather information regarding the adaptation of the range of socio educational projects and services aimed at the transition to an adult life of young persons with intellectual disabilities in Spain. The research of the study has been done in three stages. During each stage, a specific tool has been used. One to one in-depth interviews have been undertaken with 45 professionals and 20 individuals with intellectual disabilities. The Delphi method has been applied to two panels consisting of 20 experts each. Firstly, results focus on the approach to different issues related to the devices. Secondly, the training opportunities that these individuals receive to ease the transition period is addressed. And finally, the study refers to the participation of the individuals themselves and their families in the process. The developed analysis allows us to propose strategies to improve the transition to adult life

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric matrix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.