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La détermination des propriétés physiques de l’eau pure, notamment la pression de vapeur saturante en fonction de la température, est un enjeu majeur en humidité et identifié comme tel par le Comité Consultatif de Thermométrie (CCT-WG6) sous-groupe Humidité du Comité Technique de Température (TC-T) afin d’améliorer les incertitudes des références nationales en humidité. A cette fin, le LNE-CETIAT et le LNE-Cnam ont développé conjointement un dispositif expérimental permettant d’accéder au couple température / pression de vapeur saturante de l’eau pure. Le principe est basé sur une mesure statique de la pression et de la température dans une cellule d’équilibre associée à un calorimètre quasi-adiabatique. La gamme de température d’équilibre couverte s’étend de 193,15 K à 373,15 K, correspondant à une pression de vapeur saturante allant de 0,06 Pa à 105 Pa.Ce travail présente la description, la réalisation et la caractérisation métrologique de ce nouveau dispositif expérimentale. Les résultats des mesures expérimentales sont comparés avec les travaux théoriques et expérimentaux les plus récents. Le budget d'incertitude finale prend en compte la contribution de la mesure de pression, de la mesure de température et des effets parasites telles que la transpiration thermique et la pression aérostatique. Grace aux différentes solutions mises en œuvre, la contribution des mesures de température dans le bilan d’incertitude globale est réduite. La part prépondérante reste essentiellement associée à la mesure de pression. / The determination of the physical properties of pure water, especially the vapor-pressure curve, is one of the major issues identified by the Consultative Committee for Thermometry (CCT) of the technical committee in thermometry sub-field hygrometry to improve the accuracy of the national references in humidity.In order to achieve this objective, the LNE-CETIAT and the LNE-Cnam have jointly built a facility dedicated to the measurement of the saturation vapor pressure and temperature of pure water. The principle is based on a static measurement of the pressure and the temperature of pure water in a closed, temperature-controlled thermostat, conceived like a quasi-adiabatic calorimeter. The explored temperature range lies between 193,15 K and 373,15 K, and the pressure range between 0,06 Pa and 105 Pa.This work presents a full description of this facility and the preliminary results obtained for its characterization. The obtained results have been compared with available literature data. The final uncertainty budget took into account several components: pressure measurements, temperature measurements and environmental error sources such as thermal transpiration and hydrostatic pressure correction. Thanks to the employment of several technical solutions, the thermal contribution to the overall uncertainty budget is reduced, and the remaining major part is mainly due to pressure measurements.

Notre thèse de doctorat propose une analyse d’inspiration freudienne des œuvres romanesques du marquis de Sade. Elle relève, plus précisément, de la psychobiographie en ce qu’elle privilégie l’analyse des conflits des écrivains avec leurs parents, et les traumatismes psychiques subséquents. L’œuvre et l’écriture de Sade sont les résultats de nombreux facteurs : enfance multi-pathogène, personnalité borderline multi-pathologique (perverse et psychopathique), multi-récidiviste, incarcérations ou internements dans des asiles. Parmi tous ces paramètres psycho-socio-pathologiques, la prison est celui qui a aggravé, sous la forme d’une psychose carcérale réactionnelle, ses tendances morbides et la violence de son écriture. Se sentant menacé par une évolution de sa personnalité vers une psychose structurelle, Sade tente de prendre ses distances, en les rendant absurdes, avec les représentations pulsionnelles délirantes qu’il obtient grâce à ses rêves et à ses rêveries. C’est à ce moment-là qu’interviennent les procédés cathartiques et thérapeutiques de l’humour et/ou du comique pervers. Grâce à ces procédés symboliques, qu’il a mis au point dans sa correspondance avec sa femme et avec « Milly », l’une de ses amies, Sade se met en scène, lui et ses objets sexuels, dans des fantasmatiques pré-œdipiennes. Plus les décalages avec l’esthétique des réalités sexuelles œdipiennes (ou génitales) sont importants, plus l’humour pervers peut surgir. Grâce à l’humour pervers, Sade peut mimer une victoire narcissique illusoire. L’humour pervers facilite l’assassinat psychique, affectif et moral des lecteurs. Nous avons terminé notre étude en proposant l’analyse d’une forme extrême d’humour pervers, l’humour pervers nécrophile. / Our doctoral thesis suggests a Freudian analysis of Marquis de Sade novels. Our analysis is more precisely a work of psychobiography, which favours writers’ conflicts with their parents, and the subsequent psychological traumas. Sade novels and writing are the results of many parameters : a multi-pathogen childhood, a multi-pathological borderline personality (psychopathic and perverse), being a multi-recidivist, imprisonment or internment in asylums. Among all those psycho-socio-pathological parameters, prison, is the one that worsened his morbid tendencies and the violence of his writing, thus creating a prison psychosis. Threatened by the development of his personality towards a structural psychosis, Sade attempts to distance himself from those parameters, making them absurd, crazy instinctual representations coming from his dreams and reveries. The cathartic and therapeutic methods of humour and/or perverse comic played a part at that very moment. Owing to these symbolic methods he has developed in his correspondence with his wife and with « Milly », one of his friends, Sade stages himself and his sexual objects in pre-Oedipal fantasies. The stranger the aesthetics of Oedipal (or genital) sexuality are, the funnier it becomes. By means of perverse humour, Sade manages to mimic an illusory narcissistic victory. The perverse humour facilitates the psychic, emotional and moral murders of his readers. We completed our study by providing an analysis of an extreme form of perverse humour, necrophiliac perverse humour.

Au départ et de façon générale, on se propose ici une édification du concept d’autocensure. Mais le concept d’autocensure ne s’appréhende pas, à notre sens, sans l’élaboration simultanée d’un autre concept qu’est le sujet et particulièrement le sujet politique. En partant de la notion de refoulement et de sublimation chez Freud puis, en reconstituant les relations entre corps et monde nécessaires à la transformation de ce corps en sujet, nous proposons de comprendre la relation étroite entre une subjectivation historico-politique (souci de soi et ascèse chez Michel Foucault) et une autocensure c’est-à-dire une autoconstitution du sujet dans l’histoire par une interprétation symbolique incessante de l’homme et par un ensemble de technologies ( savoirs, vérités, pouvoirs). Celles-ci sont le support des réponses que le sujet, engagé dans l’histoire, se renvoie lui-même pour se déterminer à devenir un sujet politique. / In the beginning and in general, I here propose a construction of the concept of autocensorship. In the sense in which I employ the term, however, the concept of auto-censorship cannot be grasped without the simultaneous elaboration of another concept, namely, the subject and the political subject in particular. Beginning with the notions of repression and sublimation in Freud before reconstituting the relations between body and world necessary for the transformation of the body into a subject, I propose an understanding of the strict relation between a historico-political subjectification (care of the self and asceticism in Michel Foucault) and an auto-censorship, that is to say, an auto-constitution of the subject in history by an endless symbolic interpretation of the human and a complex of technologies (knowledge or expertise, truths, powers). These technologies constitute the underpinning of responses that the subject, engaged in history, returns to itself in order to become a political subject.

À partir d’un corpus ouvert de photographes et de cinéastes coloristes qui ont une fascination pour le nocturne, cette thèse explore les différentes gradations et significations de celui-ci, des plus évidentes aux plus abstraites. La thèse s’attache alors à démontrer que le régime nocturne transforme l’obscurité en valeurs chromatiques et qu’il éclaire, avec une subtilité qu’occulte la vision diurne, les aspects les plus complexes de la société et de l’esprit humain. La confrontation des analyses de séquences filmiques et de photographies dans une perspective articulant esthétique, philosophie et histoire de l’art, a permis de construire la thèse autour de trois grandes notions, Distorsion, Sublimation, Transfiguration, qui fondent le nocturne comme catégorie esthétique de l’image.Le corpus principal organisé sur des critères externes (nocturne, couleur post-années 1960-70) et internes (processus esthétiques conjoints) est composé de séquences de films en couleurs de Stanley Kubrick (1928-1999), de David Lynch (1946), de Brian de Palma (1940), de Francis Ford Coppola (1939) et de séries photographiques de Gregory Crewdson (1962), Bill Henson (1955), Rut Blees Luxemburg (1967) et Daniel Boudinet (1945-1990).Le corpus secondaire est constitué de séries photographiques de Darren Almond (1971), Jean-Christian Bourcart (1960), Nicolas Dhervillers (1981), Laurent Hopp (1974), Chrystel Lebas (1966), d’extraits d’un court métrage d’Antoine Barraud (1973) et d’une série TV de Nic Pizzolatto (1975) et Justin Lin (1973), nécessaire pour finaliser la démonstration. / Based on a large corpus of colorist film directors and photographers who share a fascination for the nocturne, this thesis explores the different gradations and meanings of this one, from the more obvious to the more abstracts. The thesis endeavours to demonstrate how the nocturne reasserts the darkness values to turn them into colors, and how it illuminates, with a subtlety absent in diurnal vision, the more complex aspects of society as well as the human mind.The confrontation between picture and film sequences analysis, with a perspective articulating aesthetic, philosophy and art history, leads to three main concepts: Distortion, Sublimation and Transfiguration. Thereby it establishes the nocturne as an image’s aesthetic category in cinema and photography.The main corpus in cinema and photography, organised by externals criteria (nocturne, post-1960-1970 years color) and internals criteria (similar operating processes aesthetic), is established with the movie extracts of Stanley Kubrick (1928-1999), David Lynch (1946), Brian de Palma (1940), Francis Ford Coppola (1939) as well as the photographic series of Gregory Crewdson (1962), Bill Henson (1955), Rut Blees Luxemburg (1967) and Daniel Boudinet (1945-1990).The second is based on the photographic series of Darren Almond (1971), Jean-Christian Bourcart (1960), Nicolas Dhervillers (1981), Laurent Hopp (1974) and Chrystel Lebas (1966), as well as Antoine Barraud’s (1973) movie extracts. Finally, for the requirement of the demonstration, a Nic Pizzolatto (1975) and Justin Lin (1973) TV show.

In this work cadmium telluride thin film photovoltaic devices have successfully been produced using a novel closed-field magnetron sputtering technique. This technique offers the possibility of producing cells in an all-in-one vacuum process with the potential to provide a new lower cost production route. The sputtered cadmium telluride layers were characterised in detail using a range of advanced microscopy based techniques both in the as deposited and after the cadmium chloride treated state, a treatment that is necessary to produce a working cell. In the as deposited condition the cadmium telluride layer was seen to have a fine-grained columnar structure containing a high density of stacking faults. After the cadmium chloride treatment these grains recrystallized and the new grains were equiaxed with a much lower density of intragranular defects. Similar effects were also observed in samples prepared using close space sublimation. To understand this recrystallization behaviour during the cadmium chloride treatment, the key treatment parameters were systematically varied. Chemical analysis in Scanning Transmission Electron Microscopy (STEM) showed that chlorine travelled down the cadmium telluride grain boundaries and accumulated adjacent to the cadmium telluride/cadmium sulphide interface. This interface is where the cadmium telluride grains were found to recrystallise first during interrupted cadmium chloride treatments. The nature of the stacking faults was examined using High Resolution Transmission Electron Microscopy (HR-TEM). This showed that in localised regions up to one plane of atoms per sequence was missing based on the expected zinc blende structure. This changed the packing of the atoms such that a local change in crystal structure occurred. This local change in phase was successfully mapped using Electron Backscatter Diffraction in planar section produced using Focused Ion Beam milling. This was subsequently studied in more detail using Transmission Electron Backscatter Diffraction in the Scanning Electron Microscope, where the intra-granular arrangement of the phases was observed. HR-TEM was used to quantitatively measure the linear defects in the cadmium telluride layer after thermal annealing with and without the cadmium chloride present. This showed that annealing alone resulted in only a modest reduction in the density of linear defects and grain recrysallisation only occurred in the presence of cadmium chloride. Cadmium magnesium telluride (CMT) was successfully grown epitaxially onto the cadmium telluride as an electron reflector layer to improve cell performance. During deposition the cell experienced high temperatures and this caused the stacking faults to return in a cell that had been previously cadmium chloride treated. This resulted in a reduction in cell efficiency, providing another link between linear defects and a degradation in cell performance.

This thesis covers a range of methodologies to provide an account of the current (2010-2014) state of the art and to develop new methods for solubility prediction. We focus on predictions of intrinsic aqueous solubility, as this is a measure commonly used in many important industries including the pharmaceutical and agrochemical industries. These industries require fast and accurate methods, two objectives which are rarely complementary. We apply machine learning in chapters 4 and 5 suggesting methodologies to meet these objectives. In chapter 4 we look to combine machine learning, cheminformatics and chemical theory. Whilst in chapter 5 we look to predict related properties to solubility and apply them to a previously derived empirical equation. We also look at ab initio (from first principles) methods of solubility prediction. This is shown in chapter 3. In this chapter we present a proof of concept work that shows intrinsic aqueous solubility predictions, of sufficient accuracy to be used in industry, are now possible from theoretical chemistry using a small but diverse dataset. Chapter 6 provides a summary of our most recent research. We have begun to investigate predictions of sublimation thermodynamics. We apply quantum chemical, lattice minimisation and machine learning techniques in this chapter. In summary, this body of work concludes that currently, QSPR/QSAR methods remain the current state of the art for solubility prediction, although it is becoming possible for purely theoretical methods to achieve useful predictions of solubility. Theoretical chemistry can offer little useful additional input to informatics models for solubility predictions. However, theoretical chemistry will be crucial for enriching our understanding of the solvation process, and can have a beneficial impact when applied to informatics predictions of properties related to solubility.

No description available.

Small water ice crystals are the main component of cold tropospheric clouds such as cirrus. Because these clouds cover large areas of our planet, their role in the radiation budget of incoming and outgoing radiation to the planet's surface is important. At present, the representation of these clouds in climate and weather models is subject to improvements: a large part of the uncertainty error stems from the lack of precise micro-physical and radiation model schemes for ice crystal clouds. To improve the cloud representations, a better understanding of the life time dynamics of the clouds and their composition is necessary, comprising a detailed understanding of the ice particle genesis, and development over their lifetime. It is especially important to understand how the development of ice crystals over time is linked to the changes in observable variables such as water vapour content and temperature and how they change the light scattering properties of the crystals. Recent remote and aircraft based in-situ measurements have shown that many ice particles show a light scattering behaviour typical for crystals having rough surfaces or being of complex geometrical shapes. The aim of this thesis was to develop the experimental setup and experiments to investigate this further by studying the surface morphology of small water ice crystals using scanning electron microscopy (SEM). The experiments I developed study the growth of water ice crystals inside an SEM chamber under controlled environmental conditions. The influence of water vapour supersaturation, pressure and temperature is investigated. I demonstrate how to retrieve the surface topology from observed crystals for use as input to computational light scattering codes to derive light scattering phase functions and asymmetry parameters, which can be used as input into atmospheric models. Difficulties with the method for studying the growth of water ice crystals, such as the effect of the electron beam-gas ionization and charging effects, the problem of facilitating repeated and localized ice growth, and the effect of radiative influences on the crystal growth are discussed. A broad set of nucleation target materials is studied. In a conclusion, I demonstrate that the method is suitable to study the surface morphologies, but is experimentally very challenging and many precautions must be taken, such as imaging only once and preventing radiative heat exchange between the chamber walls and the crystals to avoid unwanted effects on the crystal morphology. It is also left as a question if a laboratory experiment, where crystals will need to be grown in connection to a substrate, can represent the real world well enough. Deriving the required light scattering data in-situ might be an alternative, easier way to collect data for modelling use.

Este trabalho investiga como um processo de silenciamento imposto historicamente às mulheres foi capaz de inseri-las parcialmente no mundo da cultura e ao mesmo tempo segregá-las em modos específicos de apropriação, por um triplo processo de apolitização, dessexuação e tutela intelectual, que ao mesmo tempo restringiu-a a campos marginais do consumo e da produção cultural. Analisa também como a via emancipadora da psicanálise, liberando a sexualidade mas privilegiando a lógica fálica obscureceu o papel da mãe, filiandose ao dispositivo foucaultiano da aliança e suas estratégias de poder, especialmente a histerização do corpo da mulher. A inserção feminina no processo de aculturação ressentiu-se de uma aprendizagem e de um ensino excessivamente investidos na escrita e na ausência de oralidade. Ao mesmo tempo surgia uma pretensão à escrita literária não submetida aos processos formais de pertencimento a escolas e a uma sólida tradição na escrita. Esse modo específico de apropriação delimitou para as mulheres gêneros, temas e estilos específicos, tal como aconteceu historicamente em suas práticas de leitura. Desse modo, pela lógica da distinção e pelas suas condições de possibilidade específicas de produção, coube às mulheres produzir diários, correspondência privada, literatura de viagem e romances em profusão de teor sentimental e social, lidos especialmente por mulheres. A escrita feminina inscreveu-se primeiro pelos rodapés dos jornais, com seus fait-divers e os romances-folhetim. A produção literária encontra na teoria psicanalítica sua forma de sublimação por excelência. Cotejando a história da leitura e da produção literária das mulheres e as interpretações freudianas e lacanianas dos processos psíquicos associados à sublimação, este trabalho aponta para duas vertentes: de um lado, em uma abordagem ontogenética, propõe que se pense a sexualidade, a educação e a sociabilidade das meninas futuras mães sob uma ótica da maternação não exclusiva, centrada nas relações de objeto. De outro, de um ponto de vista sociogenético, conclui que as lentas transformações nas estruturas psíquicas do superego feminino conducentes à sublimação estão diretamente associadas às transformações culturais implicadas na ordem do sexo/gênero. / This work investigates how a muting process historically imposed to women was capable of partially introduce them in the world of the culture and at the same time to segregate them in specific ways of appropriation, by a triple process of apoliticization, asexuation and intellectual guardianship, in a way that restricted them to secondary fields of consumption and cultural production. It also analyzes how psychoanalysis emancipatory trend, liberating the sexuality but privileging the falic logic, overshadowed the paper of the mother, joining itself to the foucaultian alliances device and its strategies of power, especially the histerization of womens body. The feminine introduction in the aculturalization process resented a learning and an education processes excessively invested in writing and in the absence of orality. At the same time, appeared a pretension to a literary writing not submitted to formal processes from specific literary schools and neither to a solid tradition in writing. This specific way of appropriation delimited for women specific themes, subjects and styles, as well as it has happened historically with their practices of reading. In this manner, for the logic of the distinction and their specific conditions for literary written production, it remained to women the production of daily, private correspondence, literature of trip and a profusion of sentimental and social romances, read especially by women. The feminine writing was firstly enrolled by periodicals baseboards, with its fait-divers and the feuilleton-romances. The literary production finds in the psychoanalytic theory its form of subliming by excellence. Comparing womens history of reading and literary production to freudian and lacanian interpretations of psychic processes associated to the subliming, this work points to two directions: of one side, in an ontogenetic approach, it proposes that sexuality, education and sociability of girls - future mothers should be considered under an optics of non-exclusive mothering, centered in the object relations. In the other hand, from a sociogenetics point of view, it concludes that the slow transformations in the psychic structures of feminine superego that conduces to the subliming are directly associated to the cultural transformations implied in the order of sex/gender.