No description available.

No description available.

Metallic films are important in various applications, such as electric devices where it can act as contacts. In electrical devices, the substrate typically consists of silicon dioxide (SiO2) which is a temperature-sensitive substrate. Therefore, plasma enhanced chemical vapor deposition (PECVD) are better suited than thermally activated chemical vapor deposition (CVD). Depositing metallic films with PECVD demands co-reactants that act as reducing agents. However, these are not well-studied and do not always have the power enough to perform the reduction reaction for metals. Recently it has been concluded that electrons can act as reducing agents in the deposition of first row transition metallic films in a PECVD process. By supplying a positive bias to the substrate, the electrons got attracted to the surface of the substrate, which facilitated metal growth. The study concluded that metal growth only occurred at conductive -and semiconductive substrates and that the substrate bias and plasma power affected the metal growth. The process is however not well understood, which causes a knowledge gap, signifying that studies of the surface chemistry are needed. Here a new modified analytical method to study the surface chemistry in the newly developed process mentioned above is presented. The analytical method consists of an electrically modified quartz crystal microbalance (QCM) with gold electrodes as a conductive substrate. This allows the electron current to run through the QCM during the measurement. By supplying a DC-voltage to the front electrode it gets readily biased (negative and positive) and by placing a capacitor in the circuit, it connects the AC-circuit (oscillator circuit) and the DC-circuit (DC-voltage bias circuit). At the same time, it blocks the DC-current from going back to the oscillator but allows the high-frequency signal to pass from the QCM. The results in this thesis concluded that the QCM can be electrically modified to allow an electron flux to the QCM while using it as a substrate when electrons are used as reducing agents. Scanning electron microscopy (SEM) of a QCM crystal revealed that a 2 µm film had been deposited while SEM coupled with energy dispersive X-ray spectroscopy (EDS) showed that the film indeed contained iron. Further analysis was made by high-resolution X-ray photoelectron spectroscopy (HR-XPS) to find the elemental composition of the film, which revealed that the thin film contained 41 at.% iron. In addition, this study investigated if the QCM could be used to study CVD processes where electrons were used as reducing agents. The results indeed revealed that it is possible to study the surface chemistry where electrons are used as reducing agents with the electrically modified QCM to gain knowledge concerning film deposition. Initial results of the QCM showed that film growth could be studied when varying the plasma power between 5 W to 15 W and the QCM bias between -40 V to +40 V. The method generated easily accessible data concerning the process where electrons are used as reducing agents, which gained insight to the method that never has been disclosed before.

京都大学 / 新制・課程博士 / 博士(エネルギー科学) / 甲第24011号 / エネ博第447号 / 新制||エネ||84(附属図書館) / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 平藤 哲司, 教授 土井 俊哉, 教授 藤本 仁 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM

A novel fiber optic structure, termed stochastic ordered hole fibers, has been developed that contains an ordered array of six hollow tubes surrounding a hollow core, combined with a nanoporous glass creating a unique fully three dimensional pore/fiber configuration. The objective of this study is to increase the functionality of these stochastic ordered hole fibers, as well as porous clad fibers, by integrating electronic device components such as conductors, and semiconductors, and optically active materials on and in the optical fiber pore structures. Conductive copper pathways were created on/in the solid core fibers using an electroless deposition technique. A chemical vapor deposition system was built in order to attempt the deposition of silicon in on the porous clad fibers. Additionally, conductive poly(3,4-ethylenedioxythiophene)- poly(styrene sulfonate) (PEDOT:PSS) and photoactive polymer blend poly(3- hexylthiophene) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-)6,6)C61 (P3HT: PCBM) were deposited on the fibers using dip coating techniques. Quantum dots of Cadmium Selenide (CdSe) with particle sizes of ranging from 2- 10 nm were deposited in the stochastic ordered hole fibers. SEM and EDS analysis confirm that copper, polymer materials, and quantum dots were deposited in the pore structure and on the surface of the fibers. Finally, resistance measurements indicate that the electrolessly deposited copper coatings have sufficient conductivity to be used as metallic contacts or resistive heating elements. / Master of Science

No description available.

There has been progress in the surface modification of low carbon steel in order to enhance its surface hardness. This study contributes to this by investigating the introduction of carbon nanotubes and amorphous carbon in the carburization of mild steel. In order to achieve the goal, carbon nanotubes were synthesized in a horizontal tubular reactor placed in a furnace also called the chemical vapor deposition process at a temperature of 700oC. Catalyst was produced from Iron nitrate Fe(NO3)3.9H2O and Cobalt nitrate Co(NO3)2.6H2O on CaCO3 support while acetylene C2H2 was used as the carbon source and nitrogen N2 was used as contaminant remover. The as-synthesized carbon nanotubes were purified using nitric acid HNO3 and characterized using scanning electron microscopy (SEM), thermo-gravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR). It was found that as-synthesized carbon nanotubes had varying lengths with diameters between 42-52 nm from the SEM and the TGA showed the as-synthesized CNTs with a mass loss of 78% while purified CNTs had 85% with no damage done to the structures after using the one step acid treatment. The as-synthesized and purified carbon nanotubes were used in carburizing low carbon steel (AISI 1018) at two austenitic temperatures of 750oC and 800oC and varying periods of 10-50 minutes while amorphous carbon obtained by pulverizing coal was also used as comparison. The mild steel samples were carburized with carbon nanotubes and amorphous carbon in a laboratory muffle furnace with a defined number of boost and diffusion steps. The carburizing atmosphere consisted of heating up to the varying temperatures at a speed of 10oC/minute, heating under this condition at varying periods, performing a defined number of boost and diffusion processes at the varying temperatures and cooling to room temperatures under the same condition. The carburized surfaces were observed with the Olympus SC50 optical microscope and the hardness distribution of the carburized layer was inspected with a Vickers FM 700 micro-hardness tester. The as-synthesized and purified CNT samples showed higher hardness on the surface of the mild steel than the amorphous carbon. In the same vein, the change in the microstructures of vi the steel samples indicated that good and improved surface hardness was obtained in this work with the reinforcements but with purified CNT having the highest peak surface hardness value of 191.64 ± 4.16 GPa at 800oC, as-synthesized CNT with 177.88 ± 2.35 GPa and amorphous carbon with 160.702 ± 5.79 GPa which are higher compared to the values obtained at 750oC and that of the original substrate which had a surface hardness of 145.188 ± 2.66 GPa. The percentage hardness obtained for the reinforcement with the amorphous carbon, the CNT and the pCNT showed an increase of 5.47%, 10.04% and 15.77% respectively at 750oC when compared to that of the normal substrate carburized without reinforcements. Furthermore, at 800oC, the reinforcement with the amorphous carbon, the CNT and the pCNT show a percentage hardness increase of 7.04%, 14.68% and 22.05% when compared to that of the normal substrate carburized without reinforcements. Comparing the reinforcement potential of the amorphous carbon, the CNT and the pCNT at 750oC, the percentage hardness reveal that using pCNT displayed an increase of 10.89% over that of amorphous carbon and of 6.37% over that of CNT. In addition, the use of CNT as reinforcement at 750oC displayed a percentage hardness increase of 4.83% over that of the amorphous carbon carburized at the same temperature / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Les composites carbone/carbone présentent de propriétés thermomécaniques à hautes températures qui les rendent particulièrement adaptés à l’ablation ou à la friction. Leur sensibilité à l’oxydation dès 400°C a conduit à envisager leur dopage en éléments réfractaires inoxydables ou à température d’oxydation élevée. Le procédé sol-gel a permis d’introduire environ 1 % volumique d’oxyde ou de nitrure de titane ou d’aluminium dans leur matrice. Les nitrures sont obtenus par nitruration carbothermique des films d’oxydes. Deux types de sols ont été utilisés : des sols « standard » et des sols enrichis en saccharose. Le saccharose est ajouté pour prévenir la consommation du pyrocarbone lors de la nitruration. Il a par ailleurs une influence sur l’avancement de la nitruration. Les composites chargés sont ensuite densifiés par voie gazeuse, ce qui induit des transformations de phases prévues par la thermodynamique : les films de nitrure de titane sont partiellement carburés (formation de carbonitrure), et les films d’oxyde de titane sont réduits (formation d’oxycarbure). Les dépôts à base d’aluminium sont plus stables et ne subissent aucune transformation. La diffusivité thermique des composites réalisés est faiblement impactée par les charges introduites, alors que les résistances en traction/compression sont sensiblement augmentées. Par ailleurs, une rigidification des composites est observée. Leur cinétique d’oxydation est ralentie. Les composites enrichis en alumine et nitrure d’aluminium présentent des vitesses de perte de masse divisées par 2 par rapport à la référence C/C. Toutes ces propriétés sont liées directement ou non à la composition des sols, et plus particulièrement à sa teneur en saccharose. Il a en effet été montré que les sols qui en contiennent ont tendance à gélifier en surface du composite, ce qui gêne la diffusion des gaz précurseurs au cœur du composite lors de la densification. La porosité finale s’en trouve modifiée. Cette dernière a une influence non négligeable sur le comportement en compression, la diffusivité thermique et la cinétique d’oxydation des composites élaborés. / Carbon/carbon composites exhibit excellent mechanical and thermal properties at high temperature that make them espe-cially suitable for ablation or friction pieces. Their sensitivity toward oxidation above 400°C has lead to the will of doping them with refractory ceramics that are nonoxidizable or with a high oxidation temperature. The sol-gel process allowed to introduce 1 % in volume of titanium or aluminum oxide or nitride in the matrix. Nitrides are obtained by carbothermal nitridation of the oxide films. Two types of sols were used: the “standard” ones and those with extra sucrose. Sucrose is added to prevent pyrocarbon consumption during the nitridation. Furthermore, it was shown that it has an impact on the nitridation rate. Charged composites are then densified by Chemical Vapor Infiltration, which induces phases transforma-tions that were predicted by thermodynamics: titanium nitride films are partially carburized (formation of titanium carbonitride) and titanium dioxide films are reduced (formation of titanium oxycarbide). Aluminum-based films are more stable and don’t undergo any transformation. Thermal diffusivity of the as-synthesized composites is not much modified by the addition of these ceramics while the tensile and compressive strength are slightly increased. By the way, composites are hardened. Their oxidation kinetics is slowed down. Aluminum-rich composites exhibit a weight loss divided by two compared to the C/C reference. All those properties are directly, or not, linked to the composition of the sols, in particular to their sucrose content. Indeed, it was shown that sucrose-containing sols rather jellify on the surface of the composite, thus preventing the diffusion of precursor gases to the heart of the pieces. The final porosity is then modified. The porosity has an important impact on the compressive strength, thermal diffusivity and oxidation kinetics of the synthesized composites.

Les fibres à base de nanotubes de carbone (NTC), de par leurs propriétés électriques et mécaniques, sont des candidates potentielles pour des applications telles que les textiles fonctionnels ou les câbles conducteurs. A ce jour, deux familles de fibres, préparées selon des voies différentes, coexistent : les fibres contenant seulement des NTC et les fibres composites polymère/NTC. Les caractéristiques des NTC et les voies de mise en forme sont des facteurs reconnus pour impacter les propriétés électriques et mécaniques des fibres. Toutefois, compte tenu de la variabilité des sources de NTC et des conditions d’élaboration, il est difficile de dégager des relations entre caractéristiques des fibres et propriétés. C’est dans ce contexte que se situent ces travaux, avec comme objectifs la préparation de fibres à partir de NTC verticalement alignés selon deux voies d’élaboration et l’étude de leurs propriétés en fonction des caractéristiques des NTC. Une première partie de l’étude s’est focalisée sur la faisabilité de filage (voie sèche) à partir de tapis de NTC synthétisés par CCVD d’aérosol afin d’obtenir des fibres composée seulement de NTC. Même si l’ensemble des essais n’a pas abouti à un filage continu, ils ont permis de mettre en évidence un lien entre la faible tortuosité des NTC au sein du tapis et la capacité de ce dernier à former un réseau cotonneux qui semble être nécessaire à l’obtention d’une fibre. La seconde partie concerne l’étude de l’effet des caractéristiques des NTC (longueur, diamètre et structure) sur les propriétés électriques et mécaniques de fibres composites NTC/alcool polyvinylique (PVA) obtenues par voie humide à partir de suspensions de NTC. Or, la préparation de ces dernières engendre une rupture des NTC dont la longueur en suspension est limitée au micromètre. Un nouveau procédé de dispersion basé sur l’utilisation de cycles de gel/dégel a été développé, permettant d’aboutir à des longueurs de NTC en suspension de l’ordre de 4 à 6 µm. Ainsi, des suspensions concentrées en NTC de longueur, structure et diamètre différents ont été obtenues et ont permis d’élaborer avec succès des fibres composites. Les propriétés mécaniques des fibres brutes sont essentiellement modifiées par la longueur des NTC qui conduit à une amélioration du module de Young et de la contrainte à la rupture. Les propriétés électriques dépendent de la concentration en NTC dans la fibre et de la structure des NTC. Après traitement des fibres à 200 °C, l’augmentation de la longueur des NTC entraine une amélioration de la conductivité électrique. Par conséquent, l’utilisation de NTC longs dans des fibres composites s’avère bénéfique en termes d’augmentation des performances. / Carbon nanotube (CNT) based fibers, due to their interesting electrical and mechanical properties, exhibit a broad range of potential applications, such as functional textile or electrical wiring. To date, there are two families of fibers prepared according to different routes: pure CNT fibers and CNT composite fibers. The CNT characteristics and the elaboration process are known to impact their electrical and mechanical properties. However, the large diversity of manufactured CNT and spinning conditions used to elaborate these fibers are not favorable to establish clear relationship between fiber characteristics and their properties. In this context, the aim of the present work is to prepare fibers from vertically aligned CNT carpet according to two different elaboration process and to study their properties according to the CNT characteristics. A first part of this study was focused on the dry-spinning feasibility directly from CNT carpet synthesized by aerosol-assisted CCVD process in order to prepare fibers containing only of CNT. Even though all tests did not lead to a continuous spinning, a relation between the weak CNT tortuosity and the capacity of carpet to form fluffy network was established, which seems important for fiber continuous spinning. The second part is devoted to the study of the CNT characteristic effect (length, diameter and structure) on the electrical and mechanical properties of composite fibers obtained by wet spinning from CNT suspension. However, the preparation of these suspensions generates a CNT breakage by reducing their length to the micrometer range. A new dispersion process based on freezing/thawing cycles was developed and enables to keep CNT length in suspension of about 4 to 6 µm. Thus, concentrated suspensions with different CNT length, structure and diameter were obtained and successfully spun into fibers. The mechanical properties of raw fibers are essentially modified by CNT length which involves an improvement of the Young modulus and the tensile strength. The electrical properties depend on the CNT concentration in fiber and on the CNT structure. After a heat treatment of fiber at 200 °C, the increase of CNT length leads to an improvement of electrical conductivity. Consequently, the use of long CNT in composite fibers is beneficial to improve their performances.

Carbon nanotubes (CNTs) have become a popular area of materials science research due to their outstanding material properties coupled with their small size. CNTs are expected to be included in a wide variety of applications and devices in the near future. Among these devices which are nearing mass production are electrochemical double layer (ECDL) supercapacitors. The current methods to produce CNTs are numerous, with each synthesis variable resulting in changes in the physical properties of the CNT. A wide array of studies have focused on the effects of specific synthesis conditions. This research expands on earlier work done using bulk nickel catalyst, alumina supported iron catalyst, and standard chemical vapor deposition (CVD) synthesis methods. This work also investigates the effect of an applied voltage to the CVD chamber during synthesis on the physical nature of the CNTs produced. In addition, the work analyzes a novel nickel catalyst system, and the CNTs produced using this catalyst. The results of the effects of synthesis conditions on resultant CNTs are included. Additionally, CNT based ECDL supercapacitors were manufactured and tested. Scanning electron microscope (SEM) analysis reveals that catalyst choice, catalyst thickness, synthesis temperature, and applied voltage have different results on CNT dimensions. Nanotube diameter distribution and average diameter data demonstrate the effect of each synthesis condition. Additionally, the concept of an alignment parameter is introduced in order to quantify the effect of an electric field on CNT alignment. CNT based ECDL supercapacitors testing reveals that CNTs work well as an active material when a higher purity is achieved. The molarity of the electrolyte also has an effect on the performance of CNT based ECDL supercapacitors. On the basis of this research, we conclude that CNT physical dimensions can be moderately controlled based on the choice of synthesis conditions. Also, the novel nickel catalyst system investigated in this research has potential to produce bulk quantities of CNT under specific conditions. Finally, purified CNTs are recommended as a suitable active material for ECDL supercapacitors.