When loss of material due to sliding of two solids is promoted/prevented, in the presence of chemically reacting liquid or gas, tribochemical wear is said to occur. Tribochemical wear, in which corrosive media promotes material loss, is a serious concern in a variety of applications like machining, bio-implants, gas turbine engines etc. The most pervasive corrosive media encountered in applications are water and air. Air also contains water vapour along with oxygen, both of which adsorb and react with most materials, thus influencing their wear behaviour. The need for higher operating temperatures and compression ratios in gas turbine engines require development of high temperature wear resistant coatings to protect their soft metallic components. Ti based nitride coatings with Ti, Al, Si, Cr, Ta, Nb, V are known for wear resistance because of their high hardness which is second only to diamond and c-BN. High O affinity of these elements, induce the coatings to form passive oxide scale up to reasonably high temperatures and offer superior corrosion and oxidation resistance. However, sliding can remove the passivating layer, exposing the native surface to the environment which can lead to enhanced tribochemical wear. Oxidation resistance under static conditions does not guarantee low tribochemical wear; however, the tribochemical reactions causing the corrosion are of interest. Another concern is that sliding in unison with high temperatures can activate processes like enhanced diffusion, phase transformations in nitride coatings as well as in the substrate. Hence one of our objectives is to perform wear tests at high temperatures to understand the dominant mechanisms that affect wear in nitride coatings. Wear tests in the range of room temperature up to the oxidation limit of these coatings are designed.In this study TiN and high aluminium containing TiAlN coatings are chosen to study understand the wear behaviour as function of temperature up to 800°C [1]–[3]. In order to study wear of coatings, it is necessary to identify the best possible materials and methods. Though under the targeted application the coatings have to perform under fretting tests, pin on disk configuration is used which simplifies the analysis and gives deeper insight into the wear mechanism. Coated ball is used as the pin which is stationary unlike many earlier studies where the coating is applied on the rotating disk. The purpose of keeping the pin stationary is to minimize the counter-face wear and, instead, accelerate wear in these hard coatings. This method also enables easy and accurate measurement of wear depth and volume by using an optical microscope, while the conventional coated disk method requires profilometry and statistically sound measurements. To enable coating performance, substrate should not undergo much loss of strength before 800°C and hence aerospace grade IN718 alloy is chosen as the substrate which softens slowly beyond 650°C. Alumina is used as counter-face, since it has high hardness, excellent mechanical, chemical and thermal stability. In the current study, TiAlN coating is tested for wear in the range of room temperature to 800°C. Figure 1 represents the data obtained from the wear experiments. It is found that the wear is higher with large scatter at room temperature while it remains constant from 200- 750°C. Two important observations are made, firstly that the TiAlN is susceptible to some kind of a corrosive wear at room temperature which depended on the timing of the tests and secondly that the coating shows a surprisingly constant wear behaviour over the temperature range of 200-750°C. The scatter at room temperature is found to be linked with seasonal fluctuation of humidity which is verified by performing tests under controlled humidity conditions. Water vapour and oxygen are potential reacting gases present in air. Oxidation and oxidative wear is known to occur in many materials as temperatures increase which seem to be linked to thermal activation of oxidation. However lower wear at 200°C and above compared to room temperatures suggests something else to be happening .It is evident then that between room temperature and 200°C lies a transition of some kind in the tribochemical reaction which is responsible for the observed wear behaviour of TiAlN. A detailed study to understand this transition is then undertaken for the composition of TiN coatings so that benchmarking and comparison with TiAlN is possible. Also if the wear behaviour of TiN is found similar to TiAlN then it would indicate a general phenomenon which can be extended to Ti based nitrides. Figure 1 Wear rate as a variation of temperature for TiAlN coatings In contrast to low temperature wear behaviour of TiAlN, a constant wear in the range of 200-750°C is surprising because the primary suspect which is oxidation is thermally activated. The oxide scale though expected to be thin at low temperatures, has to increase in thickness with temperature due to increased diffusion and reaction rates. The oxide scale also undergoes a change in morphology and composition which indicate a lower oxidation resistance as temperature increases. A preliminary characterization of the wear scar on the ball shows that the oxide inside the worn region is thinner than the oxide outside at 750°C. The amount of O within the wear scar is similar to levels observed on as deposited surface while the surface outside the wear scar shows oxidation and discolouration. The results suggest that oxidation inside worn region at high temperatures might be slower than the expected parabolic oxidation occurring outside the wear region. It is speculated that a double layer oxide is formed with TiO2 towards the surface and Al2O3 towards the nitride which is responsible for the lower wear at high temperature. This is supported by the fact that larger amount of Ti is found in the wear debris as temperature inceases. Superficial surface cracks appear at higher loads at temperatures as low as 600°C but they affect wear only above 800°C due to substrate softening. This shows that the coatings are still limited by the substrate softening temperature and could be used at higher temperatures. Tribo-reaction in metals, nitrides and carbides can be brought about in the presence of O2 or water vapour. Tribochemical wear of SiN, SiC, TiN, TiAlN, alumina and most other ceramics at room temperature are found to depend on humidity[4]–[6]. But only tribo-oxidation due to O2 is found to operate at high temperatures[7], [8]. Notwithstanding, it is known that SiC and SiN are more resistant to attack from O2 above 800°C than from steam. Hence the role played by water vapour is found to be convoluted. Moreover, relative humidity is the frequently mentioned quantity with regard tribochemical wear at room temperatures. It should be noted that relative humidity is not a measure of chemical activity of water vapour. Rather the water vapour pressure which represents the chemical activity of water, is not given much importance in the earlier studies. In this study, the importance of humidity, water vapour pressure and temperature in influencing wear, is studied by performing controlled wear tests on TiN. To explore the effect of temperature and water vapour pressure, TiN is tested varying temperature range of 28 °C to 90°C and water vapour pressure in the range of 3-35 mm-of-Hg. Wear tests are conducted keeping temperature constant with varying water vapour pressure and vice versa. The results show that, wear increased with humidity/vapour pressure at a fixed temperature but wear dropped drastically with increase in temperature at constant vapour pressure up to a critical temperature beyond which wear remained constant. This is one of the major unexpected findings since temperature is expected to increase wear volume. Also the critical temperature is found to shift to higher temperatures as water vapour pressures increased. It was suspected that capillary condensation was playing a role in the wear which was later verified. The whole wear behaviour is shown to be correlated with the amount of capillary condensed water. The large radius of curvature of the asperities on the polished coating surface and the smooth surface formed on the counter-face due to debris compaction form conditions favourable for capillary condensation. Any two hydrophilic surfaces which come in contact can form capillary condensation to occur at the cusps formed around the contact. However a threshold pore size of about 1nm existed below which condensation did not influence wear. Another observation is that the water vapour did not affect wear significantly in the absence of condensation for TiN coatings. As temperatures increased condensation became unfavourable, but the high vapour pressure present showed no signs of wear enhancement. This is surprising and unexpected compared to earlier reports.[9], [10] On contrary tests in liquid water showed expected behaviour for tribochemical reaction i.e wear increased with temperature. The wear in liquid water is highest when compared studies in air at any given temperature. The X-ray electron emission spectroscopy (XPS) analysis is performed to understand the surface reactions. It appears that O2 forms a barrier oxide which protects the nitride from reacting with water vapour. However when condensation occurs or in water, the oxygen and water collude into forming softer hydroxide layer which is easily removed. Though chemically water and water vapour are same, they affect wear in TiN very differently. Summarising the synopsis, exploration into high temperature wear of TiAlN reveals that it can handle oxidative wear upto 750°C showing constant wear over the temperature range of 200-750°C. Reduction in residual stresses and substrate softening may be responsible for higher wear at higher loads since the cracking is observed at 5N is absent at 3N. The substrate is expected to soften above 650°C but this does not necessarily affect wear until the load is increased or the temperature is sufficiently high. However TiAlN and TiN coatings showed susceptibility to tribo-corrosion in water and high humidity at room temperature. At high humidity, condensation of water leads to increase in wear. The dependence of wear on humidity is found to be because of capillary condensation. The negligible dependence of wear on humidity in the absence of condensation is ascribed to formation of oxide layer due to reaction with O2 and coating. The oxide barrier formed due to atmospheric O2 protects the coating from reacting with the water vapour. The oxide barrier on TiN forms faster indicating O2 reaction to be faster than the reaction with water vapour. In the presence of capillary condensation or water, O2 is depleted from contacting surfaces thus hindering the formation of the barrier oxide, increasing wear. As temperature increases the condensation becomes unfavourable and barrier oxide dominates the wear mechanism upto high temperatures which is dominated by oxidative wear.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T14:30:57Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T14:30:57Z (GMT). No. of bitstreams: 0 / Os aços inoxidáveis ferríticos são naturalmente ferromagnéticos, o que impossibilita sua utilização em próteses ortopédicas. Apesar disso, em algumas aplicações específicas, faz-se necessário o uso de um biomaterial ferromagnético, como nas próteses odontológicas e faciais com conectores magnéticos. Este trabalho apresenta o estudo da resistência à corrosão e citotoxicidade do aço inoxidável ferrítico AISI 444, para avaliar seu potencial de uso como um biomaterial. O aço AISI 444 possui baixo teor de níquel, teores extrabaixos de intersticiais (C e N) e é estabilizado com Ti e Nb. Como materiais de referência foram utilizados o aço inoxidável austenítico ISO 5832-1 (ASTM F-138), por ser o biomaterial metálico mais empregado na fabricação de próteses ortopédicas, e uma base ferromagnética do sistema de fixação de próteses odontológicas, feita em aço inoxidável ferrítico (NeoM). O ensaio de citotoxicidade in vitro, pelo método de incorporação do corante vermelho neutro, revelou que o aço inoxidável AISI 444 não apresentou citotoxicidade. O comportamento frente à corrosão foi estudado por meio de curvas de polarização anódica potenciodinâmicas e espectroscopia de impedância eletroquímica (EIE). O meio de ensaio foi uma solução salina tamponada de fosfato (PBS), em condição naturalmente aerada e em fresta, a temperatura de 37 ºC. Para simular a condição de fresta dos ensaios eletroquímicos foi desenvolvido um novo equipamento. As propriedades eletrônicas do filme passivo foram avaliadas pela técnica de Mott-Schottky. Em meio aerado, os resultados de EIE indicaram que todos os materiais se mostraram passivos. As curvas de polarização indicaram que a resistência à corrosão por pite do aço AISI 444 foi equivalente à do aço ISO 5832-1, porém superior à do NeoM. Pelos diagramas de Mott-Schottky, conclui-se que o filme óxido no aço AISI 444 possui menor concentração de dopantes que o aço NeoM. Isto sugere que o aço AISI 444 apresenta maior resistência à transferência de carga através do filme passivo. Em condição de fresta, as polarizações indicaram taxas de corrosão baixas para ambos os aços, porém superiores para o aço ISO 5832-1, em comparação ao aço AISI 444. As micrografias das superfícies dos aços, após polarização, revelaram um maior ataque corrosivo no aço ISO 5832-1 do que no aço AISI 444. O aço NeoM apresentou composição química fora da especificação da norma. Os baixos teores de Cr e de Mo, além das altas concentrações de sulfetos, foram as prováveis causas da menor resistência à corrosão do NeoM, indicada pelos ensaios eletroquímicos. O equipamento proposto para avaliação da resistência à corrosão, em condição de fresta, mostrou boa reprodutibilidade de resultados. O aço inoxidável AISI 444 apresentou alta potencialidade para uso como biomaterial, especialmente na fabricação de componentes protéticos com fixação magnética. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T18:22:46Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-22T18:22:46Z (GMT). No. of bitstreams: 0 / A liga Ti-6Al-4V é uma das ligas de titânio mais suas aplicações estruturais em temperaturas elevadas são limitadas devido a sua afinidade pelo oxigênio. Um tratamento superficial que melhore a resistência à oxidação desta liga permitindo a substituição de peças que atualmente são produzidas com superligas de Ni por este material, poderia reduzir significativamente o peso destes componentes. O objetivo deste trabalho é melhorar a resistência à fluência desta liga utilizando nitretação por plasma. Para homogeneizar a microestrutura do material, foi realizado um tratamento térmico a 1050ºC por 30 minutos para obtenção da microestrutura de Widmanstätten que foi a que apresentou melhor resistência à fluência no material sem tratamento. A nitretação foi realizada variando parâmetros de processo como tempo, temperatura e mistura de gases na atmosfera. A partir dos resultados obtidos, a mistura de gás de Ar:N2:H2 (0,49:0,49:0,03) a 700°C por 4 horas foi a condição escolhida. A caracterização da camada nitretada foi realizada por técnicas de microscopia ótica e eletrônica de varredura, além de difração de raios X. As fases da amostra nitretada detectadas por DRX foram o ε-Ti2N e δ-TiN, além das fases α e β da matriz. A espessura da camada nitretada foi de cerca de 1 μm. Os ensaios de tração a quente foram realizados em temperaturas entre 500°C e 700°C no material com e sem nitretação e mostraram um aumento na resistência da liga nitretada de até 29% nos limites de escoamento e resistência. Os ensaios de fluência foram realizados variando a temperatura também entre 500 e 700ºC e tensão aplicada entre 125 e 319 MPa. O resultado foi um aumento na resistência à fluência do material nitretado. Isto foi evidenciado pela diminuição da taxa de fluência secundária e também pelo aumento do tempo de ruptura do material. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Alisson Mota (alisson.davidbeckam@gmail.com) on 2015-07-17T18:46:47Z No. of bitstreams: 1 Dissertação - Maria Oneide Silva de Moraes.pdf: 9993702 bytes, checksum: d0ede70d56d052b19d6265bf315f6128 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T14:16:31Z (GMT) No. of bitstreams: 1 Dissertação - Maria Oneide Silva de Moraes.pdf: 9993702 bytes, checksum: d0ede70d56d052b19d6265bf315f6128 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T14:20:29Z (GMT) No. of bitstreams: 1 Dissertação - Maria Oneide Silva de Moraes.pdf: 9993702 bytes, checksum: d0ede70d56d052b19d6265bf315f6128 (MD5) / Made available in DSpace on 2015-07-20T14:20:29Z (GMT). No. of bitstreams: 1 Dissertação - Maria Oneide Silva de Moraes.pdf: 9993702 bytes, checksum: d0ede70d56d052b19d6265bf315f6128 (MD5) Previous issue date: 2013-03-25 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The absolute values of the photoabsorption cross section of compounds are of great importance in the fields of physics, chemistry, biology, therapy and related fields. Studies of natural products are also of great importance several areas of science and innovation, however, information related to the values of the photoabsorption cross section in the vacuum ultraviolet region are scarce in the literature. In this paper a study of the electronic excitations of the molecule isoprene using a spectrometer energy loss of electrons from low-resolution (0,8– 1,0 eV FWHM) at the Laboratory for Photon and Electron Impact (LIFE-UFRJ). The energy loss spectra of electrons were obtained in the range 3-100 eV at various angles of scattering with incident energy of 1 keV. The spectra of generalized oscillator strength (GOS) for the isoprene molecule were obtained by the Bethe-Born conversion. The spectrum GOS obtained in the angle of impact 2o was extrapolated to the strength oscillator photoabsorption optical using the universal formula Msezane and Sakmar (1997). The photoabsorption cross sections on an absolute scale were determined by of the static polarizability of isoprene applying the sum rule S(-2) in the photoabsorption spectrum. The contributions of the inner layer photoabsorption above 100 eV were estimated from a fit polynomial curve. Other sum rules were used to estimate the values of physical properties isoprene as sum rule S(0) is equal to the number of electrons on the target (36,45 a. u.), the rule logarithmic L(0) is the stopping power of the molecule (18,05 a.u.), the rule logarithmic L(1) is related to the effect straggling referring to fluctuations of the incident beam (22,49 a.u.) and rule logarithmic L(2) for the Lamb shift (55,27 a.u.). The set of spectra GOS obtained at different scattering angles were presented in Bethe surface to isoprene. Two regions stand out: a region dominated by the optical selection rules for electronic transitions of the absorption, and the other region, we observed a strong angular dependence on the momentum of the incident electrons becomes significant.The Bethe surface and the sum rules are unpublished experimental data in the literature. The absolute values of the cross section and the Bethe surface can contribute to a complete understanding of the electronic excitations of the molecule isoprene induced by collisions of charged particles. It is expected that these absolute valuesmay be useful as references to theoretical calculations and experimental in the electronic spectra of isoprene. / Os dados de seção de choque de fotoabsorção de compostos são de grande importância nas áreas de física, química, biologia, terapia e áreas afins. Os estudos de produtos naturais também são de grande importância em diversas áreas científicas e de inovação, porém, informações relacionadasaos valores de seção de choque de fotoabsorção na região ultravioleta de vácuo são incipientes na literatura. Neste trabalho foi feito um estudo das excitações eletrônicas da molécula isopreno utilizando um espectrômetro de perda de energia de elétrons de baixa resolução (0,8 – 1,0 eV FWHM) no Laboratório de Impacto de Fótons e Elétrons (LIFE-UFRJ). Os espectros de perda de energia de elétrons foram obtidos na faixa de 3 a 100 eV em vários ângulos de espalhamentos com energia incidente de 1 keV. Os espectros de força do oscilador generalizado (FOG) para a molécula isopreno foram obtidos pela conversão de Bethe-Born. O espectro de FOG obtido no ângulo de impacto de 2o foi extrapolado para força do oscilador de fotoabsorção ótico utilizando a fórmula universal de Msezane e Sakmar (1997). As seções de choque de fotoabsorção em escala absoluta foram determinadas por meio da polarizabilidade estática do isopreno aplicando a regra de soma S(-2) no espectro de fotoabsorção. As contribuições da fotoabsorção da camada interna acima de 100 eV foram estimadas com o ajuste de uma curva polinomial.Outras regras de somas foram utilizadas para estimar os valores de propriedades físicas para o isopreno como a regra de soma S(0) que é igual ao número de elétrons no alvo (36,45 u. a., unidades atômicas), a regra de soma logarítmica L(0) é o stopping power da molécula (18,05 u. a.), a regra de soma logarítmica L(1) é o efeito straggling referente às flutuações estáticas do feixe incidente (22,49 u. a.) e a regra de soma logarítmica L(2) referente ao deslocamento de Lamb (55,27 u. a.). O conjunto de espectros de FOG obtidos em diferentes ângulos de espalhamento foi apresentado na Superfície de Bethe para o isopreno. Duas regiões se destacaram: uma região dominada pelas regras de seleção ópticas de transições eletrônicas dos processos de absorção, e a outra região, foi observado uma forte dependência angular em que o momento linear dos elétrons incidentes torna-se significativo. A Superfície de Bethe e as regras de somas são resultados experimentais inéditos na literatura. Os valores absolutos de seção de choque e a Superfície de Bethe podem contribuir para um entendimento completo das excitações eletrônicas da molécula isopreno induzidas por colisões de partículas carregadas. É esperado que estes valores absolutos possam ser úteis como referências em cálculos teóricos e experimentais para o espectro eletrônico do isopreno.

The recent development of free-electron lasers operating at XUV and X-ray wavelengths are proving vital for the exploration of matter in extreme conditions. The ultra-short pulse length and high peak brightness these light sources provide, combined with a tunable X-ray wavelength range, makes them ideally suited both for creating high energy density samples and for their subsequent study. In this thesis I describe the work done on the XUV free-electron laser FLASH in Hamburg, aimed at creating homogeneous samples of warm dense matter through the process of volumetric XUV photo-absorption, and the theoretical work undertaken to understand the process of high-intensity laser-matter interactions. As a first step, we have successfully demonstrated intensities above 10¹⁷ Wcm-2 at a wavelength of 13.5 nm, by focusing the FEL beam to micron and sub-micron spot sizes by means of a multilayer-coated off-axis parabolic mirror. Using these record high intensities, we have demonstrated for the first time saturable absorption in the XUV. The effect was observed in aluminium and magnesium samples and is due to the bleaching of a core-state absorption channel by the intense radiation field. This result has major implications for the creation of homogeneous high energy density systems, as a saturable absorption channel allows for a more homogeneous heating mechanism than previously thought possible. Further, we have conducted soft X-ray emission spectroscopy measurements which have delivered a wealth of information on the highly photo-excited system under irradiation, immediately after the excitation pulse, yet before the system evolves into the warm dense matter state. Such strongly photo-excited samples have also been studied theoretically, by means of density functional theory coupled to molecular dynamics calculations, yielding detailed electronic structure information. The use of emission spectroscopy as a probe for solid-density and finite-temperature systems is discussed in light of these results. Theoretical efforts have further been made in the study of the free-free absorption of aluminium as the system evolves from the solid state to warm dense matter. We predict an absorption peak in temperature as the system heats and forms a dense plasma. The physical significance of this effect is discussed in terms of intense light-matter interactions on both femtosecond and picosecond time-scales.

Le projet SPIRAL2 permettra de produire au GANIL des faisceaux radioactifs et stables très intenses. Repoussant les limites actuelles de nos connaissances, il constitue une opportunité pour de nombreux domaines de la physique nucléaire. Le Super Séparateur Spectromètre S3 et son système de détection au plan focal SIRIUS ont été conçus afin de tirer le meilleur parti de ces faisceaux stables intenses notamment au profit des recherches sur les éléments N=Z proches de l'étain-100 et des noyaux super lourds. Ce travail de thèse portent sur les détecteurs silicium Tunnel de SIRIUS, avec d'un côté des simulations GEANT4 de l'ensemble de SIRIUS et d'un autre côté son pendant expérimental avec l'étude des prototypes des Tunnel de SIRIUS. Les simulations ont permis, outre la caractérisation de l'efficacité de détection et des limites induites en terme de conception mécanique, de mettre en lumière le bond en avant permis par l'avènement de détecteurs silicium presque sans zones mortes. La partie dédiée aux manipulations commence par la présentation du banc de test mis en place à l'IPHC pour recevoir et tester les détecteurs prototypes et pré-série. Le détecteur Tunnel est également présenté dans son contexte scientifique et technique. Les études des prototypes de détecteurs Tunnel et les résultats obtenus sont détaillés. Enfin, l'évolution vers les détecteurs de série est présentée sur la base des améliorations réalisées et constatées pour le détecteur de pré-série. / The SPIRAL2 project will enable the production at GANIL of very intense radioactive and stable beams. Pushing the present-day limits of knowledge, it represents an opportunity for several fields of nuclear physics. The Super Separator Spectrometer S3 associated to its focal-plane detection system SIRIUS will take the best possible benefit of these intense stable beams especially for researches on the N=Z nuclei close to Tin-100 and on the super heavy elements. This thesis is dedicated to the SIRIUS Tunnel silicon detectors, with GEANT4 simulations and their corresponding experimental study of the SIRIUS Tunnel detectors prototypes. In addition to the detection efficiency characterization and the setting of corresponding limits on mechanical conceptual drawings, the simulations have enabled to shed light on the major forward step brought by zero dead-layer silicon detectors. The section dedicated to the manipulations starts with the presentation of the test bench set up at IPHC in order and test the prototypes and pre-series detectors. The Tunnel detector is also presented in its scientific and technical context. The Tunnel detector prototypes studies and the results obtained are detailed. Finally, the evolution toward series detectors is presented on the basis of the improvements done with the pre-series detector.

Le rayonnement synchrotron dans la gamme d'énergie des rayons X tendres (2-13 keV) permet l'excitation/ionisation d'atomes et de molécules en couche profonde. Les états ainsi peuplés ont des durées de vie ultra-courtes, de l'ordre de la femtoseconde. Les atomes vont alors se relaxer par émission d'un photon ou d'un électron. Dans cette thèse, nous avons utilisé la spectroscopie d'électrons afin d'étudier les différents processus induits par l'interaction entre la matière et un rayonnement très énergétique. Dans la première partie, la durée de vie des états électroniques excités est utilisée comme une horloge interne permettant la mesure du mouvement nucléaire à l'échelle de temps sub-femtoseconde. Les élargissements naturels dus à la durée de vie des états électroniques peuplés sont suffisamment grands pour que ces états se recouvrent, permettant l'excitation simultanée de plusieurs états intermédiaires pouvant causer des phénomènes d'interférences lors de l'étape de relaxation. C'est le sujet de la deuxième partie de cette thèse, où nous présentons un modèle permettant d'extraire ces termes d'interférences. Dans la dernière partie, nous montrons qu'il est également possible de peupler des états électroniques multiplement excités/ionisés, et que notre dispositif expérimental permet d'en extraire les durées de vie, ainsi que de résoudre toutes les contributions se recouvrant dans les spectres d'électrons. Le fil d'Ariane de ce travail est de tenter d'appréhender les différents processus de corrélations électroniques suite à l'excitation du système étudié via un photon de haute énergie, comme le partage d'excès d'énergie ou de moment angulaire entre plusieurs électrons. / Synchrotron radiation in the tender x-ray energy range (2-13 keV) allows deep core-shell excitation/ionization of atoms and molecules. The electronic states populated have ultrashort lifetimes, in the order of one femtosecond. The atoms will then relax through emission of a photon or an electron. In this thesis, we used electron spectroscopy as a tool to study the different processes implied by the interaction between the matter and highly energetic radiation. In the first part, the lifetime of the excited electronic states is used as an intern clock allowing to measure nuclear dynamics in the sub-femtosecond timescale. The lifetime broadenings of the populated electronic states are large enough so that these states overlap, thus allowing their coherent excitation which may lead to interferences phenomena during the relaxation step. This is the subject of the second part of this work, in which we present a model that allows the extraction of these interference terms. In the last part, we show it is also possible to form multiply excited/ionized electronic states, and that our experimental setup allows to measure their lifetimes, and the disentanglement of the many contributions overlapping in the electron spectra. The Ariadne’s thread of this work is to try to apprehend the different electronic correlation processes following the excitation of the studied system by a highly energetic photon, such as how electrons share the incident excess energy or the angular momentum transferred by the incident photon.

J'ai réalisé pour cette thèse des travaux expérimentaux à l'aide de la microscopie et de la spectroscopie électronique portant sur l'étude de nanostructures plasmoniques et de nanocristaux semi-conducteurs. Le but étant d'etudier leurs propriétés optiques sur des dimensions spatiales de l'ordre du nm. A cette échelle il est possible d'observer le champs proche électrique associé aux modes de résonances plasmons de surface supportées par des nanostructures métalliques. Ainsi j'ai pu étudier l'effet de la présence de rugosités sur des nano-bâtonnets d'or et constater que leur présence modifiait localement la structure du champs proche électrique. Des mesures combinées par spectroscopie de perte d'énergie des électrons (EELS) et de cathodoluminescence ont permis de comparer les réponses mesurées en champs proches à celle effectuées en champs lointain. Une étude faite par EELS portant sur le couplage entre deux nano-bâtonnets métalliques positionnés bout à bout et séparés par une distance de quelques dizaines de nanomètres a permis de cartographier la localisation de modes hybridés séparément sur chaque branche. Enfin des études comparatives de cathodoluminescence et de photoluminescence sur des points quantiques isolés ont permis de constater l'équivalence de l'information collectées par ces deux techniques sur ce type d'émetteurs de lumière / For this thesis, I have realised some experimental works using electron microscopy and electron spectroscopies for the study of plasmonic nanostructures and semiconductor nanocrystals . The aim being to study their optical properties with spatial resolutions of the order of a few nm. At this level it is possible to observe the electric near-field associated to the localised surface plasmon resonances supported by metallic nanostructures . So I was able to study the effect due to the presence of roughness on single gold nanorods and I have found that their presence locally alterate the structure of the electric near-field . Combined measurement of electron energy loss spectroscopy (EELS ) and cathodoluminescence spectroscopy were used to compare the near-field and far-field responses respectively. A study by EELS on the coupling between two metal nanorods positioned end to end and separated by a disance of tens of nanometers was used to map the localisation of hybridised modes separately on each branch of the dimers. Finally, comparative studies of cathodoluminescence and photoluminescence on single quantum dots have shown the equivalence of the information collected by these two techniques for such light emitters

The work described herein deals with the synthesis and characterization of lead chalcogenide thin films and nanocrystals. The first part of thesis describes the properties of semiconductors followed by an analysis on the chemical vapour deposition and nanoparticulate formation. In the next part of thesis, single-source precursors of type thioselenophosphinato, selenoureato, dithiocarbamato and dithiocarbanato complexes of lead have been synthesised and characterised. As-synthesised compounds have been utilised for the fabrication of lead sulfide and lead selenide thin films by aerosol-assisted chemical vapour deposition as well as nanocrystals by colloidal injection method. Lead sulfide thin films were also deposited by liquid-liquid interface from lead dithiocarbanato at room temperature. The as grown thin films of lead sulfide and lead selenide have been characterised by XRD, SEM and energy dispersive x-ray (EDX) analysis. In the second part of the thesis, preparation of lead sulfide and lead selenide nanocrystals in olive oil at low growth temperatures (50-60°C) is described and have shown that by controlling experimental conditions, well-defined particles with tunable emission in mid and far-infrared region can be synthesised. Furthermore, compositionally-tuned PbSxSe1-x nanocrystals has also been prepared by adding controlled amount of sulur and selenium ingredients into lead oxide. Homogenous distribution of sulfur and selenium within alloyed nanocrystals is confirmed by transmission electron microscope studies. Moreover, attempts have been made to prepare quaternary (PbTe/Se/S) nanocrystals of lead chalcogenides and depth (1.9-5.8 nm) profile analysis by x-ray photoelectron spectroscopy confirmed the formation of core/shell/shell type structure i.e. PbTe/S/Se.

Le travail réalisé au cours de cette thèse concerne l’analyse des conséquences de l’oxydation à 950°C des alliages base Ni sur la composition de l’alliage à proximité de l’interface alliage/oxyde. Deux catégories d’alliages ont été analysées : alliages à faible teneur en chrome conduisant à l’oxydation interne et l’alliage chromino-formeur Ni-16Cr-9Fe.Une description complète des mécanismes de l’oxydation interne du chrome est obtenue à partir du développement du modèle analytique de Wagner d’oxydation interne et du développement du modèle numérique de Feulvarch. Ces modèles décrivent l’évolution de l’oxydation interne jusqu’à la transition oxydation interne / oxydation externe à 11 %poids de chrome environ.L’analyse par la spectroscopie d’électrons Auger de l’alliage modèle Ni-16Cr-9Fe à 950°C oxydé pendant 10 heures a permis d’explorer la zone à proximité immédiate de l’interface alliage/oxyde et de déterminer la concentration en chrome à l’interface à 0,5%poids (i.e. dans 20 premiers nanomètres), ce qui est en accord avec le modèle analytique de Wagner d’oxydation en couche compacte. La description des profils de déchromisation et des profils de cavités pour plusieurs temps d’exposition allant de 100h à 5000h a permis de mettre en évidence une corrélation forte entre ces deux phénomènes (même constante parabolique). Pour ces durées d’oxydation les profils de déchromisation présentent un point d’inflexion ce qui se traduit par l’augmentation de la teneur en chrome à l’interface. Les résultats sont interprétés dans le cadre d’un nouveau modèle analytique avec l’hypothèse d’injection des lacunes produites par l’effet Kirkendall au point d’inflexion. / The present work is focused on the consequences of oxidation at 950°C on the nature of a chromium-depleted area in Ni-based alloys. Two classes of alloys were analysed : low chromium Ni-Cr alloys and a typical chromia-former Ni-16Cr-9Fe.A complete description of the mechanisms of nodular oxidation is obtained from the development of both the Wagner’s analytical model of internal oxidation and the Feulvarch’s numerical model. These models describe the evolution of nodular oxidation up to the transition between internal to external oxidation which happens at around 11 wt%Cr.Auger Electron Spectroscopy (AES) measurements on a model Ni-16Cr-9Fe alloy oxidised at 950°C during 10 hours has allowed a detailed analysis in the immediate vicinity of the oxide/alloy interface and resulted in a very low Cr content in first 20 nm of the subsurface layer. This result is in agreement with Wagner’s theory of external oxidation of binary alloys. Higher oxidation times, from 100h to 5000h, have resulted in extensive cavitation and chromium depletion, both quantified respectively by image analysis and EDX. These profiles appear to be strongly correlated (same parabolic constant). Higher oxidation times result in an inflection point on chromium depletion profile and higher Cr interface content, which are due to the increased chromium diffusivity. The overall results are interpreted in the frame of a new analytical model based on the assumption of Kirkendall vacancy injection at the inflection point.