abstract: Flame retardants (FRs) are applied to variety of consumer products such as textiles and polymers for fire prevention and fire safety. Substantial research is ongoing to replace traditional FRs with alternative materials that are less toxic, present higher flame retardancy and result in lower overall exposure as there are potential health concerns in case of exposure to popular FRs. Carbonaceous nanomaterials (CNMs) such as carbon nanotubes (CNTs) and graphene oxide (GO) have been studied and applied to polymer composites and electronics extensively due to their remarkable properties. Hence CNMs are considered as potential alternative materials that present high flame retardancy. In this research, different kinds of CNMs coatings on polyester fabric are produced and evaluated for their use as flame retardants. To monitor the mass loading of CNMs coated on the fabric, a two-step analytical method for quantifying CNMs embedded in polymer composites was developed. This method consisted of polymer dissolution process using organic solvents followed by subsequent programmed thermal analysis (PTA). This quantification technique was applicable to CNTs with and without high metal impurities in a broad range of polymers. Various types of CNMs were coated on polyester fabric and the efficacy of coatings as flame retardant was evaluated. The oxygen content of CNMs emerged as a critical parameter impacting flame retardancy with higher oxygen content resulting in less FR efficacy. The most performant nanomaterials, multi-walled carbon nanotubes (MWCNTs) and amine functionalized multi-walled carbon nantoubes (NH2-MWCNT) showed similar FR properties to current flame retardants with low mass loading (0.18 g/m2) and hence are promising alternatives that warrant further investigation. Chemical/physical modification of MWCNTs was conducted to produce well-dispersed MWCNT solutions without involving oxygen for uniform FR coating. The MWCNTs coating was studied to evaluate the durability of the coating and the impact on the efficacy during use phase by conducting mechanical abrasion and washing test. Approximately 50% and 40% of MWCNTs were released from 1 set of mechanical abrasion and washing test respectively. The losses during simulated usage impacted the flame retardancy negatively. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

Metamorphic processes can transform the organic matter in sedimentary rocks into structurally organized carbonaceous matter, in ideal conditions to graphite. In the centre of West Alpine arch, the metasedimentary rocks are rich in dispersed carbonaceous matter and were used in this thesis to specify the thermal range of metamorphism based on the structural state. Previous studies have used mainly the Raman spectrometers to determine the structural state of carbonaceous matter. Unfortunately this method doesn't allow in-situ analyses which, in addition to Earth studies, can be essential for studying other planetary bodies and moons of our solar system. As only the smallest and lightest instruments are required for analyses during potential planetary missions to Mars, it is important to verify that the small instruments are able to detect even the small concentrations of carbonaceous matter. Currently available miniature and portable Raman spectrometers have started to become more precise but are still not as precise as laboratory Raman microspectrometers. This thesis is divided into two parts. First part aims to duplicate the results from previous studies by Raman microspectrometers in the West Alpine arch. Furthermore, the excitation laser wave length dependence of spectral signs in carbonaceous...

Raman-Spektroskopie an kohligem Material (RSCM) ist eine häufig verwendete Methode, um die maximale Temperatur der Metamorphose oder die thermische Reife von Kohlen und organikreichen Sedimenten zu bestimmen. Für die Temperaturabschätzung wurden bereits mehrere Kalibrationskurven ermittelt, jedoch wird die Übertragbarkeit dieser Kalibrationen auf andere Labore durch methodische Aspekte eingeschränkt und die Vergleichbarkeit zwischen den Laboren dadurch reduziert. Die subjektive Auswertung von Spektren, das verwendete Messsystem und die Probenheterogenität bedingen die größte Streuung der Ergebnisswerte und ein Ansatz, mit dem Ziel die Vergleichbarkeit zu erhöhen, wurde formuliert. Um die Subjektivität der spektralen Auswertung zu veringern, wurde das ’IFORS’ (Iterative Fitting Of Raman Spectra) Programm geschrieben, das die automatische, Benutzer-unabhängige Auswertung von Raman-Spektren ermöglicht. Um die Streuung aufgrund des verwendeten Messsystems zu reduzieren, wurde ein Referenzprobensatz zusammengestellt, der einen Temperaturbereich von 160 °C bis 600 °C abdeckt. Während der Probenaufbereitung wurde Resonanz-Raman- Spektroskopie mit mehreren Anregungswellenlängen an dispersen Vitriniten durchgeführt, die diagenetische bis epizonale Druck- und Temperaturbedingungen erfahren hatten, um die Gleichwertigkeit der RSCM-Methode und Vitrinitreflexion zu ermitteln. Mit Hilfe des IFORS Programms wurde der ’scaled total area’ (STA) Raman Parameter ermittelt, der das Raman Spektrum von kohligem Material präzise beschreibt. Auf Grundlage der Resonanz-Raman Daten konnte gezeigt werden, dass die Methodiken der STA-Raman Spektroskopie und Vitrinitreflexion analog zueinander sind, dass die STA-RSCM Methode gegenüber der Probenaufbereitung, insbesondere dem Polieren, robust ist, und dass die Resonanz-Raman Spektren der Vitrinite eine zweistufige molekulare Entwicklung während der Inkohlung und Graphitisierung aufzeichnen. Während der ersten Stufe, die kurz nach dem Durchschreiten des Gas-Fensters endet, wachsen vor allem lineare, polyzyklische, aromatische Kohlenwasserstoffe, während in der anschließenden zweiten Stufe kondensierte Formen von polyzyklischen, aromatischen Kohlenwasserstoffen wachsen. Um die Raman Spektren von metamorphem, kohligem Material zu beschreiben, wurde die STA-RSCM Methodik erweitert und erfolgreich gegen die Temperaturinformation des Referenzprobensatzes kalibriert, so dass ein neues, überarbeitetes RSCM-Geothermometer vorgestellt werden konnte, das über einen Temperaturbereich von 160°C bis 600°C zulässig ist. Der Referenzprobensatz steht öffentlich zur Verfügung und es wird erwartet, dass der Probensatz verbessert werden kann, wenn er um Proben aus der wissenschaftilchen Gemeinschaft erweitert wird. Wenn beide Ansätze, die STA-RSCM Methodik und der Referenzprobensatz, miteinander kombiniert werden, erhöht sich die Vergleichbarkeit zwischen den Laboren und gleichzeitig steht diese geothermometrische Methode allen Laboren zur Verfügung.

Les météorites carbonées sont les objets les plus primitifs du système solaire. Ils contiennent jusqu'à 4 % de carbone, principalement présent sous forme de matière organique insoluble (MOI). Celle-ci contient des informations essentielles sur les processus d’organo-synthèse qui se déroulent dans le système solaire, qui sont jusqu'ici mal compris. Un modèle statistique a été récemment proposé pour la structure moléculaire de la MOI ainsi qu'une voie de synthèse possible pour le squelette hydrocarboné de cette macromolécule (Derenne et Robert, 2010). Le premier objectif de ce travail était de tester expérimentalement cette voie avec un plasma organique comme source de radicaux CHx. Ce dispositif a permis la formation de matière organique soluble et insoluble. La MOI a été analysée par les mêmes techniques que celles utilisées précédemment pour la MOI chondritique, révélant de nombreuses similitudes entre les deux matériaux et validant le mécanisme proposé. En outre, des analyses NanoSIMS ont révélé, à une résolution spatiale sub-micrométrique, de grandes variations isotopiques qui sont du même ordre de grandeur que celles observées dans la MOI chondritique. Ensuite, la source des hétéroatomes (N et O) dans la MOI a été expérimentalement étudiée en ajoutant des précurseurs contenant des heteroelements aux radicaux hydrocarbonés. En ce qui concerne l'azote, deux types de précurseurs ont été considérés : l’hexylamine comme source d'hydrures et l'azote moléculaire N2. Bien que les deux précurseurs conduisent à l'incorporation d'azote dans la MOI, les hydrures d'azote semblent être plus pertinents, d’après la nature des fonctions azotées formées. Deux types d'expériences ont été effectuées afin d'étudier la source potentielle d'oxygène dans la MOI chondritique. Elles ont été conçues pour tester les deux principaux scénarios proposés pour rendre compte de la présence d’oxygène dans la MOI chondritique : soit l’altération aqueuse sur le corps parent ou l’incorporation d’oxygène pendant l’organo- synthèse dans la nébuleuse solaire primitive. Lors de l’expérience simulant l'altération aqueuse, la composition chimique de la matière organique soluble et insoluble est en accord avec ce qui est observé dans la matière organique des météorites. En revanche, aucun élément en faveur de l'incorporation directe d’oxygène par des radicaux OH n’a pu être apporté. / Carbonaceous meteorites are the most primitive objects of the solar system. They contain up to 4% of carbon, mainly occurring as insoluble organic matter (IOM). This IOM contains key information about the organo-synthesis processes taking place in the Solar System, which are so far poorly understood. A statistical model was recently proposed for the IOM molecular structure along with a possible synthesis pathway for its hydrocarbon backbone (Derenne and Robert, 2010).The first aim of this work was to test experimentally this pathway using an organic plasma as a source of CHx radicals. This device allowed the formation of both soluble and insoluble OM. The IOM was analyzed through the same techniques as those previously used for the chondritic IOM, revealing numerous similarities between both materials and thus supporting the proposed pathway. Moreover, NanoSIMS analyses revealed large isotopic variations at a sub-micrometric spatial resolution that are commensurable with those observed in chondritic IOM.Then, the source of heteroatoms (N and O) into the IOM was experimentally investigated through the addition of heteroelement-containing precursors to the hydrocarbonaceous radicals. As for nitrogen, two types of precursors were considered: hexylamine as a source of nitrogen hydrides and N2. Although both precursors led to nitrogen incorporation in the IOM, nitrogen hydrides seem to be more relevant based on the nitrogen speciation. Two types of experiments were performed to investigate the potential source of oxygen in the chondritic IOM. They were designed to address the two main scenarios proposed in the literature to account for the origin of the oxygen in the chondritic IOM: either aqueous alteration on the asteroidal parent body or O incorporation during the organo-synthesis in the primitive solar nebula. When the aqueous alteration is mimicked, the chemical composition of the SOM and IOM makes this pathway a reasonable source of the chondrite oxygen moieties. In contrast, no evidence for direct incorporation of O from OH radicals could be brought.

1 Abstract In recent years, the term small carbonaceous fossils (SCFs) has been established to accomodate fragile organic-walled fossils of micro- to mesoscopic size that are usually extracted by means of the 'low-manipulation HF extraction' method. This method has so far only been utilized by several authors and no reports have been published on the usage of the method on samples from the Barrandian area. To test the applicability of the method, samples from the Barrandian area were processed. The samples came from eleven localities representing six stratigraphic units (Paseky Shale, Jince Formation, Letná Formation, Kosov Formation, Daleje Shale and Roblín Member). All the units have been studied before by 'standard' methods of palynological processing. Various previously unreported fossils are described, including wiwaxiid sclerites, putative chaetognath remains and acritarch clusters. Furthermore, it is discovered, that the 'low-manipulation HF extraction' can also be used for extraction of originally calcareous fossils. The pilot study provides a further proof that the 'low-manipulation HF extraction' is a useful tool with the potential to significantly expand our knowledge of fossil assemblages. Key words: Small carbonaceous fossils, Cambrian, Ordovician, Devonian, Barrandian area

Research in superconductivity is heading towards overcoming the limitations imposed by extreme conditions, and promising candidates in this pursuit are superconductors made from hydrides. Carbonaceous Sulfur Hydride (CSH) was reported in Nature 586, 373-377 (2020) as a room-temperature superconductor in the pressure range of 140-267 GPa; however, there is controversy in the literature regarding these results. Here, we use density functional theory to confirm the hypothesis of Nature 596, E9-E10 (2021) that a metallic path is the reason for the sharp drop in resistance interpreted in Nature 586, 373-377 (2020) as indicative of a weak type 2 superconductor. We find that the metallic behavior of CSH is dominated by sulfur p-orbitals, and not by metallization of hydrogen. If CSH would be a superconductor, the predicted Ginzburg Landau parameter would be 1356.9, reflecting an unusually strong type 2 superconductor and thus contradicting the interpretation of Nature 586, 373-377 (2020). The fact that we find no metallic states below 220 GPa casts doubts on the onset of superconductivity at 140 GPa reported in Nature 586, 373-377 (2020). Additionally, the small fraction of active hydrogen density of states at the Fermi level shows that CSH is not a high-temperature superconductor.

Cette thèse s’intéresse aux signatures spectroscopiques des nano-particules carbonées dans l’infrarouge proche et moyen dans les disques protoplanétaires. Ces signatures sont largement observées dans le milieu interstellaire et les galaxies et représentent ainsi un outil essentiel pour étudier les conditions physiques qui y règnent. Notamment, leur étude dans les environnements circumstellaires d’étoiles de type Herbig contribue à notre connaissance de la formation des systèmes planétaires et du cycle de la matière dans la Voie lactée. Même si la poussière ne représente qu’un faible pourcentage de la matière galactique, elle est essentielle dans la formation d’espèces chimiques complexes, le chauffage photo-électrique du gaz, la balance énergétique ou ladynamique des structures. Ainsi, elle participe directement à l’évolution des disques protoplanétaires.Ce travail s’appuie notamment sur les données d’observations spectroscopiques résolues spatialement obtenues avec l’instrument NaCo au VLT dans l’infrarouge proche entre 3 et 4 μm. Le modèle THEMIS fournit un cadre d’interprétation pour les observations en proposant un modèle physique de la poussière dans lequel les propriétés optiques sont calculées en considérant la composition, la structureet la taille de populations de grains. THEMIS propose un scénario d’évolution de celle-ci au travers des différentes phases du milieu interstellaire.Les résultats obtenus montrent que des particules carbonées sub-nanométriques ayant une forte aromaticité sont présentes de manière étendue et structuréeà la surface des disques protoplanétaires. Leur degré d’aromaticité augmente avec l’intensité du champ de rayonnement de l’étoile. De plus, l’observation de ces particules près de l’étoile suggère leur renouvellement continu. La odélisation de l’émission de la poussière dans les conditions des disques met enévidence les contributions des différentes populations selon la longueur d’onde et les conditions d’irradiation.Ce travail s’inscrit dans la préparation de la mission du James Webb Space Telescope qui permettra d’observer notamment les disques ptrotoplanétaires surune large gamme infrarouge (0.6-28 μm). Ce travail a également conduit à la production de deux articles, un publié et l’autre soumis dans la revue Astronomy & Astrophysics. / This thesis focuses on spectroscopic signatures of carbon nanoparticles in the near and mid-infrared in protoplanetary disks. These signatures are widely observed in the interstellar medium and galaxies and thus represent an essential tool for studying their physical conditions. In particular, their study in the circumstellar environments of Herbig stars contributes to our knowledge of the formation of planetary systems and the dust cycle in the MilkyWay. Even if dust represents only a small percentage of galactic matter, it is key to the formation of complex chemical species, photoelectric gas heating, energy balance or structural dynamics. Thus, it participates directly in the evolution of protoplanetary disks.This work is based in particular on spatially resolved spectroscopic observation data obtained with the NaCo instrument at the VLT in the near infrared between 3 and 4 μm. The THEMIS model provides an interpretative framework for observations by proposing a physical dust model in which optical properties are calculated by considering the composition, structure and size of grain populations. THEMIS proposes a scenario of its evolution through the different phasesof the interstellar medium.The results obtained show that carbon sub-nanoparticles with high aromaticity are present in a widespread and structured manner at the surface ofprotoplanetary disks. Their degree of aromaticity increases with the intensity of the stellar radiation field. Moreover, the observation of these particles close to the star suggests their continuous replenishment. Modelling the dust emission under disk conditions highlights the contributions of dust populations according to the wavelength and the radiation field.This work is related to the preparation of the James Webb Space Telescope mission which will allow to observe protoplanetary disks over a wide infrared range (0.6-28 μm) with a resolution of 0.1”. This work also led to the production of two articles, one published and the other submitted to the journal Astronomy & Astrophysics.

Summary Combination of PANI and the cost-effective graphite can obtain composites with good electrochemical performance. For the synthesis method of in-situ polymerization of aniline in presence of GNP, the type and content of oxidant can affect the electrochemical properties of PANI/GNP composites. Besides, the addition of excess dopant can influence the electrochemical properties of a PANI-dominated system. The two eco-friendly reduction ways, namely polymerization of dopamine and adding TA, both produced graphite with good dispersion stability and enhanced interaction with PANI. But the reduction effect of dopamine polymerization was weak, and the non-conductivity of PDA has negative effect on the electrochemical performance of the composites. Using the environmental friendly TA is an effective and facile way to produce cost-effective PANI/graphite composites for supercapacitor purpose. Comparing the two types of graphite, rGO showed lower conductivity and more defects in the carbonaceous structure compared to GNP. In my study, the PANI/(GNP-TA) (1:0.1) composites, which was prepared by using APS as oxidant and without dopant, exhibited the highest capacitive ability. In a three-electrode testing system, the PANI/(GNP-TA) composite showed a high specific capacitance of 351.2 F g-1 at 10 mV s 1. The corresponding two-electrode solid-state supercapacitor device exhibited a promising energy density of 2.3 Wh kg-1 at 0.5 A g-1, which was comparable to the commercially available supercapacitors (around 5 Wh kg-1). But for application the rate capability of the composite needs to be enhanced, in order to maintain the good capacitive performance at high current density.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24643号 / 工博第5149号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 河瀬 元明, 教授 大嶋 正裕, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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