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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
511

Electrical and optical properties of hydrogen-related complexes and their interplay in ZnO / Elektrische und optische Eigenschaften von Wasserstoff-korrelierten Komplexen und ihre Wechselwirkung in ZnO

Koch, Sandro 16 November 2015 (has links) (PDF)
The commercial breakthrough of ZnO-based devices is hampered mainly by the unipolar n-type conductivity of this material. Hydrogen, which is known to form both electrically active and inactive complexes in ZnO, is considered as a main cause of this behavior. However, the existing literature is incomplete and partly contradictory. The object of the present thesis is a comprehensive investigation of the properties of two hydrogen-induced shallow donors HBC and HO, the hydrogen molecule H2, and a hydrogen-related defect, which gives rise to local vibrational modes (LVMs) at 3303 and 3320 cm-1, in ZnO and their interaction. The defects are characterized by Raman spectroscopy, infrared absorption spectroscopy, photoconductivtity (PC) and photoluminescence measurements. Based on the PC technique, a novel and highly sensitive spectroscopic approach is established, which is applicable for probing LVMs in strongly absorbing spectral regions. This technique enables the detection of the local modes of HO at 742 and 792 cm-1 in the neutral charge state. In consequence, earlier theoretical predictions regarding the microscopic structure of this shallow donor can be verified. In Raman measurements the electronic 1s→2s transition of HO is identified at 273 cm-1. This quantity is found to blue-shift with the HO defect concentration. A similar blue-shift of the 1s→2s(2p) donor transition of HBC is assigned to local lattice strain which was generated during high temperature processes. A Raman study of the H2 molecule covers its formation, stability, lattice position and interplay with the ZnO host. In particular, the role of H2 for the continuous generation of HO and HBC and the related n-type behavior is elaborated. The analysis unambiguously confirms that the so-called “hidden hydrogen” species is indeed H2. Moreover, the observation of the ortho-para-conversion process and the coupling to the host phonons contribute to a general understanding of H2 in semiconductors. Experimental results of the LVMs of 3303 and 3320 cm-1 in conjunction with model calculations yield an underlying defect containing three hydrogen atoms. This complex Y–H3 exhibits two configurations, which differ only in the orientation of one chemical bond. The findings are consistent equally with a zinc vacancy decorated with three hydrogen atoms and an ammonia molecule, respectively. Earlier models proposed in the literature are discarded. Measurements of concentration profiles by using Raman spectroscopy reveal the local distribution of the hydrogen-related defects as well as lattice imperfections. At the surface, where oxygen vacancies are present, HO is identified as the dominant shallow donor. Below, in parts of the crystal with low damage, HBC is the prevalent defect. In the sample center, characterized by a significant amount of zinc vacancies, the concentrations of H2 and Y–H3 show their maxima. By recording concentration profiles after thermal treatments a spatially resolved investigation of the interplay of these hydrogen-related defects is possible. / Der kommerzielle Durchbruch von ZnO-basierten Bauelementen ist hauptsächlich durch die beständige n-Typ Leitung des Materials eingeschränkt. Wasserstoff, der sowohl elektrisch aktive als auch inaktive Komplexe in ZnO formt, gilt als ein Hauptverursacher dieses Verhaltens. Jedoch ist die bestehende Literatur zu derartigen Defekten unvollständig, teils auch widersprüchlich. Gegenstand der vorliegenden Arbeit sind umfassende Untersuchungen der beiden wasserstoffinduzierten Donatoren HBC und HO, des Wasserstoffmoleküls H2 und eines Wasserstoffdefekts mit lokalen Schwingungsmoden (LSMn) bei 3303 und 3320 cm-1 in ZnO hinsichtlich ihrer Eigenschaften und gegenseitigen Wechselwirkung. Die Charakterisierung der Komplexe erfolgt mit Hilfe von Raman-Spektroskopie, Infrarot-Absorptionsspektroskopie, Photoleitfähigkeits- (PC) und Photolumineszenzmessungen. Basierend auf der PC Technik wird eine neuartige, hochsensitive Spektroskopiemethode etabliert, welche auch in stark absorbierenden Spektralbereichen anwendbar ist. Diese Technik ermöglicht erstmals die Detektion der LSMn von HO bei 742 und 792 cm-1 im neutralen Ladungszustand. Das experimentelle Ergebnis verifiziert theoretische Vorhersagen zur mikroskopischen Struktur dieses flachen Donators. In Raman-Messungen wird der elektrische 1s→2s Übergang von HO bei 273 cm-1 identifiziert und eine Blauverschiebung dieser Größe mit zunehmender HO-Konzentration beobachtet. Der Donator HBC zeigt ebenfalls eine Blauverschiebung des elektrischen 1s→2s(2p) Übergangs, welche durch lokale Gitterverzerrungen nach Hochtemperaturbehandlungen bedingt ist. Eine Raman-Studie charakterisiert das H2-Molekül in Bezug auf seine Bildung, Stabilität, Gitterposition und die Wechselwirkung mit dem ZnO-Kristall. Insbesondere wird seine Rolle für die fortwährende Bildung der Donatoren HO und HBC und des damit verbundenen n-Typ Verhaltens herausgearbeitet. Die Analyse ergibt die eindeutige Identifizierung der in der Literatur mit „hidden hydrogen“ bezeichneten Spezies als H2. Darüber hinaus tragen die beobachteten Umwandlungsprozesse zwischen ortho-H2 und para-H2 sowie die Kopplung an das Phononenspektrum zu einem generellen Verständnis von Wasserstoffmolekülen in Halbleitern bei. Die experimentellen Ergebnisse der LSMn bei 3303 und 3320 cm-1 in Kombination mit Modellrechnungen ergeben einen zugrundeliegenden Defekt mit drei Wasserstoffatomen. Dieser Komplex Y–H3 weist zwei Konfigurationen auf, welche sich durch die Orientierung von nur einer chemischen Bindung unterscheiden. Die Beobachtungen sind mit einer Zinkvakanz besetzt mit drei Wasserstoffatomen bzw. einem Ammoniakmolekül als mikroskopische Struktur gleichermaßen erklärbar. Bisherige Modelle aus der Literatur können damit widerlegt werden. Messungen von Konzentrationsprofilen mit Raman-Spektroskopie offenbaren die lokale Verteilung der Wasserstoffdefekte sowie von Gitterstörungen. An der Oberfläche, im Beisein von Sauerstoffvakanzen, ist HO der dominante flache Donator. In dem sich anschließenden ungestörten Kristallverbund ist hingegen der Donator HBC vorherrschend. In Zentrum, welches von Zinkvakanzen geprägt ist, sind die Konzentrationen von H2 und Y–H3 maximal. In Verbindung mit Temperaturbehandlungen ist eine räumlich aufgelöste Untersuchung der Wechselwirkung möglich.
512

Luminescence investigation of zinc oxide nanoparticles doped with rare earth ions

Kabongo, Guy Leba 11 1900 (has links)
Un-doped, Tb3+ as well as Yb3+ doped ZnO nanocrystals with different concentrations of RE3+ (Tb3+, Yb3+) ions were successfully synthesized via sol-gel method to produce rare earth activated zinc oxide nanophosphors. The phosphor powders were produced by drying the precursor gels at 200˚C in ambient air. Based on the X-ray diffraction results, it was found that the pure and RE3+ doped ZnO nanophosphors were highly polycrystalline in nature regardless of the incorporation of Tb3+ or Yb3+ ions. Moreover, the diffraction patterns were all indexed to the ZnO Hexagonal wurtzite structure and belong to P63mc symmetry group. The Raman spectroscopy confirmed the wurtzitic structure of the prepared samples. Elemental mapping conducted on the as prepared samples using Scanning electron microscope (SEM) equipped with energy dispersive X-ray spectrometer (EDX) revealed homogeneous distribution of Zn, O, and RE3+ ions. The high resolution transmission electron microscope (HR-TEM) analyses indicated that the un-doped and RE3+ doped samples were composed of hexagonal homogeneously dispersed particles of high crystallinity with an average size ranging from 4 to 7 nm in diameter, which was in agreement with X-ray diffraction (XRD) analyses. ZnO:Tb3+ PL study showed that among different Tb3+ concentrations, 0.5 mol% Tb3+ doped ZnO nanoparticles showed clear emission from the dopant originating from the 4f-4f intra-ionic transitions of Tb3+ while the broad defects emission was dominating in the 0.15 and 1 mol% Tb3+doped ZnO. Optical band-gap was extrapolated from the Ultraviolet Visible spectroscopy (UV-Vis) absorption spectra using TAUC‟s method and the widening of the optical band-gap for the doped samples as compared to the un-doped sample was observed. The PL study of ZnO:Yb3+ samples was studied using a 325 nm He-Cd laser line. It was observed that the ZnO exciton peak was enhanced as Yb3+ions were incorporated in ZnO matrix. Furthermore, UV-VIS absorption spectroscopic study revealed the widening of the band-gap in Tb3+ doped ZnO and a narrowing in the case of Yb3+ doped ZnO system. X-ray photoelectron spectroscopy demonstrated that the dopant was present in the doped samples and the result was found to be consistent with PL data from which an energy transfer was evidenced. Energy transfer mechanism was evidenced between RE3+ and ZnO nanocrystals and was discussed in detail. / Physics / M.Sc. (Physics)
513

Παρασκευή και μελέτη ευαισθητοποιημένων ηλιακών κυψελίδων (DSSCs) με μείγματα οργανικών χρωστικών

Τζιογκίδου, Γεωργία 17 July 2014 (has links)
Αντικείμενο της διπλωματικής εργασίας είναι μελέτη της ευαισθητοποίησης από κοινού (co-sensitization) με την χρήση απλών οργανικών χρωστικών με παρόμοιο φάσμα απορρόφησης. Για το λόγο αυτό αναπτύχθηκαν μείγματα διαφόρων χρωστικών ουσιών τα οποία χρησιμοποιήθηκαν για την ευαισθητοποίηση ηλιακών κυψελίδων (DSSCs) με ημιαγωγό νανοδομημένου ZnO. Οι χρωστικές που χρησιμοποιήθηκαν για την ευαισθητοποίηση ήταν απλές οργανικές, όπως η Rose-Bengal, η Rhodamine-B, η Eosin-B, η Coumarin 343 και η Malachite Green. Παρασκευάστηκαν μείγματα δυο και τριών χρωστικών ουσιών με σκοπό την επίτευξη υψηλότερης απόδοσης της ευαισθητοποιημένης ηλιακής κυψελίδας. / In this work we investigate co-sensitization effects by using simple organic dyes with complimentary absorption spectra. A combination of different organic dyes was used in this work to sensitize nanostructured ZnO films for Dye Sensitized Solar Cell (DSSC) devices. The dyes used to sensitize the films were the simple organic molecules Bengal Rose, Rhodamine B, Eosin B, Coumarin 343 and Malachite Green. Binary and ternary blends of these dyes were used in order to enhance the performance of ZnO DSSCs.
514

An investigation into the mechanism of toxicity of zinc oxide nanoparticles

Sharma, Vyom January 2011 (has links)
The wide scale use of ZnO nanoparticles (NPs) in the world consumer market has resulted in likelihood of exposure to human beings. The present study was aimed to assess the in vitro and in vivo interactions of ZnO NPs in the mammalian system and to elucidate the possible mechanism of their toxicity. Our in vitro results using human epidermal cells (A431), primary human epidermal keratinocytes and human liver cells (HepG2) demonstrated that cells exposed to ZnO NPs exhibit a decrease in cell viability which was independent of NP dissolution. ZnO NPs also induced oxidative DNA damage as evidenced by an increase in the Fpg sensitive sites. The reactive oxygen species triggered a decrease in mitochondrial membrane potential and an increase in the ratio of Bax/Bcl2 leading to apoptosis through the intrinsic pathway. In addition, ZnO NPs induced phosphorylation of JNK, P38 and P53ser15. The results from our in vivo studies using a mouse model showed that ZnO NPs induce lipid peroxidation, oxidative DNA damage and apoptosis in liver which further confirmed our in vitro findings. The data from the present study provide valuable insights into the cellular interactions of ZnO NPs and the underlying molecular mechanism of their toxicity. The results also stress the need for a comprehensive environmental health and safety assessment of engineered nanomaterials to ensure safer nanotechnology based products.
515

Zinc tin oxide thin-film transistor circuits

Heineck, Daniel Philip 23 December 2008 (has links)
The primary objective of this thesis is to develop a process for fabricating integrated circuits based on thin-film transistors (TFTs) using zinc tin oxide (ZTO) as the channel layer. ZTO, in contrast to indium- or gallium-based amorphous oxide semiconductors (AOS), is perceived to be a more commercially viable AOS choice due to its low cost and ability to be deposited via DC reactive sputtering. In the absence of an acceptable ZTO wet etch process, a plasma-etching process using Ar/CH₄ is developed for both 1:1 and 2:1 ZTO compositions. An Ar/CH₄ plasma etch process is also designed for indium gallium oxide (IGO), indium gallium zinc oxide (IGZO), and indium tin oxide (ITO). Ar/CH₄ dry etches have excellent selectivity with respect to SiO₂, providing a route for obtaining patterned ZTO channels. A critical asset of ZTO process integration involves removing polymer deposits after ZTO etching without active layer damage. A ZTO process is developed for the fabrication of integrated circuits which use ZTO channel enhancement-mode TFTs. Such ZTO TFTs exhibit incremental and average mobilities of 23 and 18 cm²V⁻¹s⁻¹, respectively, turn-on voltages approximately 0 to 1.5 V and subthreshold swings below 0.5 V/dec when annealed in air at 400 °C for 1 hour. Several types of ZTO TFT circuits are realized for the first time. Despite large parasitic capacitances due to large gate-source and gate-drain overlaps, AC/DC rectifiers are fabricated and found to operate in the MHz range. Thus, they are usable for RFID and other equivalent-speed applications. Finally, a ZTO process for simultaneously fabricating both enhancement-mode and depletion-mode TFTs on a single substrate using a single target and anneal step is developed. This dual-channel process is used to build a high-gain two-transistor enhancement/depletion inverter. At a rail voltage of 10 V, this inverter has a gain of 10.6 V/V, the highest yet reported for an AOS-based inverter. This E/D inverter is an important new functional block which will enable the realization of more complex digital logic circuits. / Graduation date: 2009
516

Development of high efficiency dye sensitized solar cells : novel conducting oxides, tandem devices and flexible solar cells

Bowers, Jake January 2011 (has links)
Photovoltaic technologies use light from the sun to create electricity, using a wide range of materials and mechanisms. The generation of clean, renewable energy using this technology must become price competitive with conventional power generation if it is to succeed on a large scale. The field of photovoltaics can be split into many sub-groups, however the overall aim of each is to reduce the cost per watt of the produced electricity. One such solar cell which has potential to reduce the cost significantly is the dye sensitised solar cell (DSC), which utilises cheap materials and processing methods. The reduction in cost of the generated electricity is largely dependent on two parameters. Firstly, the efficiency that the solar cell can convert light into electricity and secondly, the cost to deposit the solar cell. This thesis aims to address both factors, specifically looking at altering the transparent conducting oxide (TCO) and substrate in the solar cell. One method to improve the overall conversion efficiency of the device is to implement the DSC as the top cell in a tandem structure, with a bottom infra-red absorbing solar cell. The top solar cell in such a structure must not needlessly absorb photons which the bottom solar cell can utilise, which can be the case in solar cells utilising standard transparent contacts such as fluorine-doped tin oxide. In this work, transparent conducting oxides with high mobility such as titanium-doped indium oxide (ITiO) have been used to successfully increase the amount of photons through a DSC, available for a bottom infra-red sensitive solar cell such as Cu(In,Ga)Se2 (CIGS). Although electrically and optically of very high quality, the production of DSCs on this material is difficult due to the heat and chemical instability of the film, as well as the poor adhesion of TiO2 on the ITiO surface. Deposition of a interfacial SnO2 layer and a post-deposition annealing treatment in vacuum aided the deposition process, and transparent DSCs of 7.4% have been fabricated. The deposition of a high quality TCO utilising cheap materials is another method to improve the cost/watt ratio. Aluminium-doped zinc oxide (AZO) is a TCO which offers very high optical and electronic quality, whilst avoiding the high cost of indium based TCOs. The chemical and thermal instability of AZO films though present a problem due to the processing steps used in DSC fabrication. Such films etch very easily in slightly acidic environments, and are susceptible to a loss of conductivity upon annealing in air, so some steps have to be taken to fabricate intact devices. In this work, thick layers of SnO2 have been used to reduce the amount of etching on the surface of the film, whilst careful control of the deposition parameters can produce AZO films of high stability. High efficiency devices close to 9% have been fabricated using these stacked layers. Finally, transferring solar cells from rigid to flexible substrates offers cost advantages, since the price of the glass substrate is a significant part of the final cost of the cell. Also, the savings associated with roll to roll deposition of solar cells is large since the production doesn't rely on a batch process, using heavy glass substrates, but a fast, continuous process. This work has explored using the high temperature stable polymer, polyimide, commonly used in CIGS and CdTe solar cells. AZO thin films have been deposited on 7.5um thick polyimide foils, and DSCs of efficiency over 4% have been fabricated on the substrates, using standard processing methods.
517

Microfabricated Gas Sensors Based on Hydrothermally Grown 1-D ZnO Nanostructures

Jiao, Mingzhi January 2017 (has links)
In this thesis, gas sensors based on on-chip hydrothermally grown 1-D zinc oxide (ZnO) nanostructures are presented, to improve the sensitivity, selectivity, and stability of the gas sensors. Metal-oxide-semiconductor (MOS) gas sensors are well-established tools for the monitoring of air quality indoors and outdoors. In recent years, the use of 1-D metal oxide nanostructures for sensing toxic gases, such as nitrogen dioxide, ammonia, and hydrogen, has gained significant attention. However, low-dimensional nanorod (NR) gas sensors can be enhanced further. Most works synthesize the NRs first and then transfer them onto electrodes to produce gas sensors, thereby resulting in large batch-to-batch difference. Therefore, in this thesis six studies on 1-D ZnO NR gas sensors were carried out. First, ultrathin secondary ZnO nanowires (NWs) were successfully grown on a silicon substrate. Second, an on-chip hydrothermally grown ZnO NR gas sensor was developed on a glass substrate. Its performance with regard to sensing nitrogen dioxide and three reductive gases, namely, ethanol, hydrogen, and ammonia, was tested. Third, three 1-D ZnO nanostructures, namely, ZnO NRs, dense ZnO NWs, and sparse ZnO NWs, were synthesized and tested toward nitrogen dioxide. Fourth, hydrothermally grown ZnO NRs, chemical vapor deposited ZnO NWs, and thermal deposited ZnO nanoparticles (NPs) were tested toward ethanol. Fifth, the effect of annealing on the sensitivity and stability of ZnO NR gas sensors was examined. Sixth, ZnO NRs were decorated with palladium oxide NPs and tested toward hydrogen at high temperature. The following conclusions can be drawn from the work in this thesis: 1) ZnO NWs can be obtained by using a precursor at low concentration, temperature of 90 °C, and long reaction time. 2) ZnO NR gas sensors have better selectivity to nitrogen dioxide compared with ethanol, ammonia, and hydrogen. 3) Sparse ZnO NWs are highly sensitive to nitrogen dioxide compared with dense ZnO NWs and ZnO NRs. 4) ZnO NPs have the highest sensitivity to ethanol compared with dense ZnO NWs and ZnO NRs. The sensitivity of the NPs is due to their small grain sizes and large surface areas. 5) ZnO NRs annealed at 600 °C have lower sensitivity toward nitrogen dioxide but higher long-term stability compared with those annealed at 400 °C. 6) When decorated with palladium oxide, both materials form alloy at a temperature higher than 350 °C and decrease the amount of ZnO, which is the sensing material toward hydrogen. Thus, controlling the amount of palladium oxide on ZnO NRs is necessary.
518

Les effets de revêtements de surface sur la dissolution et la bioaccumulation de nanoparticules d'oxyde de zinc par l'algue unicellulaire, C. reinhardtii

Merdzan, Vladimir 12 1900 (has links)
Au cours de la dernière décennie, les nanoparticules ont connu un essor sans précédent dans plusieurs domaines. On peut retrouver ces nanoparticules dans des secteurs aussi variés tels que la médecine, l’électronique, les écrans solaires, les cosmétiques et les plastiques, pour ne nommer que ceux-là. Cette utilisation massive a eu un effet pervers sur l’environnement, sachant qu’une grande partie de ces produits se sont retrouvés inévitablement dans les milieux naturels. Plusieurs études révèlent qu’autant la présence des nanoparticules que leurs produits de dissolution sont à prendre en considération lorsque des travaux toxicologiques ou le devenir de ces matériaux sont étudiés. Il est désormais clair que les propriétés de surface de ces nanoparticules jouent un rôle central sur leur comportement dans les solutions aqueuses; que ce soit les interactions avec des organismes ou entre les particules elles-mêmes. Afin d’évaluer le devenir de nZnO, une étude sur la dissolution ainsi que la bioaccumulation a été réalisée avec l’algue modèle Chlamydomonas reinhardtii en présence de nanoparticules ayant différents enrobages. Les nanoparticules d’oxyde de zinc suivantes ont été étudiées : (i) nZnO sans enrobage (nZnO); (ii) nZnO avec enrobage d’acide polyacrylique (nZnO-PAA) et (iii) nZnO avec enrobage d’hexamétaphosphate de sodium (nZnO-HMP). La dissolution était mesurée à l’aide de trois techniques : ultrafiltration par centrifugation (CU); technique potentiométrique (scanned stripping chronopotentiometry, SSCP) et spectrométrie de masse – plasma à couplage inductif couplé à une résine échangeuse d’ions (resin-based inductively coupled plasma-mass spectrometry, resin-based ICP-MS). Les résultats obtenus démontrent une grande tendance à la dissolution pour le nZnO (presque totale) tandis que pour le nZnO-PAA et le nZnO-HMP, la dissolution est dépendante de la nature de l’enrobage le composant. Pour la bioaccumulation sur l’algue testée, les données montrent une grande dépendance au zinc libre issu de la dissolution pour nZnO et nZnO-PAA. À l’inverse, le nZnO-HMP démontre une bioaccumulation plus élevée par comparaison aux mêmes concentrations d’expositions du zinc libre, expliquée par la stimulation de l’internalisation du zinc provoqué par la présence de phosphate constituant l’enrobage de nZnO-HMP. / Over the last decade, the use of nanoparticles (NP) has been increasing exponentially in numerous sectors, leading to their massive release into the environment. For example, zinc oxide nanoparticles (nZnO) can be found in areas such as medicine, electronics, sunscreens, cosmetics and plastics. Concerns have therefore been raised about the impacts of the NP on the natural environment, as well as their consequences for humans. Multiple studies reveal that not only the NP but also their dissolution products may have impacts on environmental systems. It is well understood that surface properties of engineered nanoparticles in aqueous solution play a pivotal role in nanoparticle behavior, including their interactions with organisms. Therefore, in order to assess the behavior of nZnO, this study focuses on their dissolution and evaluates the bioaccumulation of 3 nanoparticles with different surface stabilizations by the freshwater algae Chlamydomonas reinhardtii. The following NP were studied: (i) bare nZnO, (ii) polyacrylic acid coated (nZnO-PAA) and (iii) sodium hexametaphosphate coated (nZnO-HMP). Three different techniques were used to quantify dissolution of the nZnO: centrifugal ultrafiltration (CU), scanned stripping chronopotentiometry (SSCP) and resin-based inductively coupled plasma-mass spectrometry (resin-based ICP-MS). The results reveal a high dissolution of the bare nZnO (nearly total) while the dissolution of the polyacrylate coated and hexamataphosphate coated nZnO were highly dependent on the nature of the stabilizer. As a consequence, bioaccumulation in model algae C. reinhardtii was strongly related to the release of free zinc in the bare nZnO and the nZnO-PAA. On the other hand, algae exposed to nZnO-HMP appeared to be stimulated by the phosphate coating, leading to higher bioaccumulation than for the free zinc, once again demonstrating the importance of the nature of the stabilizer.
519

Combustion auto-propagée et mécanosynthèse de ZnS : étude des conversions ZnS <->ZnO et application à la désulfuration des gaz. / Self-propagating High temperature Synthesis (SHS) and mechanical alloying of ZnS : study of ZnS<->ZnO conversions and application to gas desulfurization.

Perraud, Igor 20 December 2012 (has links)
Aujourd'hui, l'impact environnemental de chaque technologie fait l'objet de toutes les attentions. L'élimination des composés soufrés et surtout de H2S dans les gaz entre dans cet aspect écologique au sein de plusieurs processus industriels. L'oxyde de zinc est utilisé comme adsorbant régénérable pour la désulfuration. Le but de ce travail est la préparation de filtres monolithiques macroporeux et de nanopoudres de ZnO avec une forte capacité en soufre et facilement régénérable, ainsi que l'optimisation de leurs propriétés.Des matériaux composites ZnS/NaCl sont tout d'abord synthétisés par combustion auto-propagée à partir de mélanges de zinc, de soufre et de chlorure de sodium. NaCl est éliminé par lixiviation dans l'eau après la synthèse. Les nanopoudres de ZnS sont préparées par mécanosynthèse à partir de mélanges de zinc et de soufre. Les deux matériaux préparés ont des structures cristallines différentes, de type würtzite pour les filtres de ZnS et de type sphalerite pour les poudres. Cette différence est due aux deux voies de synthèse. Monolithes et poudres ZnS sont ensuite convertis en ZnO par traitement thermique sous air à 700 °C.Les transformations macro- et microstructurales des filtres et des poudres ont été étudiées au cours de cycles de sulfuration-oxydation par les méthodes de caractérisation telles que la diffraction des rayons X, la microscopie électronique à balayage et la porosimétrie au mercure. Les résultats montrent que les propriétés des matériaux restent très stables au cours des conversions successives. Enfin, les filtres et nanopoudres de ZnO ont été utilisés comme adsorbants au cours d'essais de désulfuration. La capacité massique en soufre des filtres est assez faible, 6,4 mg S/g ads. montrant que la porosité doit être améliorée. Quant aux nanopoudres, la capacité massique en soufre est très élevée, 272 mg S/g ads, prouvant que la surface spécifique est très importante pour ce type d'application. / Today, we have to take care of every technology's environmental effects. The removal of H2S and other sulfur compounds in hot gas enters this ecological aspect in several industrial processes. Zinc oxide is used here as a regenerable sorbent for gas desulfurization. The goal of this work is, the preparation of macroporous ZnO monolithic filters and nanopowders with high sulfur capacity and easily regenerable, and their optimization with the control of their properties. ZnS/NaCl composite materials are first obtained by Self-propagating High temperature Synthesis from mixtures of zinc, sulfur and sodium chloride powders. NaCl is then removed by lixiviation with water. ZnS nanopowders are prepared by mechanical alloying from mixtures of zinc and sulfur. The two materials have different crystalline structure, würtzite type for ZnS filters and sphalerite type for powders, because of the way of synthesis. Then, they are converted into ZnO by thermal treatment under air at 700 °C. Next, the macro- and microstructure transformations of both filter and powders during sulfidation-oxidation cycles are thus considered. Results of all characterizations like X-ray diffraction, scanning electron microscopy and Hg porosimetry show that materials properties are very stable against conversions. Afterwards, ZnO filters and nanopowders are used as adsorbent in desulfurization trials. The sulfur capacity of filters is not so high, 6,4 mg S/g ads and shows that porosity has to be improved. Regarding nanopowders, the sulfur capacity is very high, 272 mg S/g ads, proving that surface area is very important in this application.
520

Suivi par methode optique du frittage micro-ondes d'oxydes ceramiques. / In-situ monitoring of ceramic microwave sintering using optical method.

Zymelka, Daniel 13 January 2012 (has links)
Le frittage micro-ondes est connu pour être une technique de frittage prometteuse. En effet, ce procédé présente comme avantages une réduction de la durée des traitements thermiques et un gain énergétique important par rapport aux procédés conventionnels. D'année en année, le frittage dans un environnement micro-ondes est étudié par un nombre croissant de chercheurs. Cependant, les raisons de l’effet bénéfique de ce type de frittage ne sont pas clairement identifiées.Dans ce contexte, l’objectif de ce travail a été de vérifier l’influence d’un champ électromagnétique à la fréquence de 2,45 GHz sur la densification de matériaux céramiques. Cet objectif passe donc par une étude comparative du frittage dans une enceinte micro-ondes et dans un four conventionnel. Cependant, la présence du champ électromagnétique dans un four micro-ondes ne permet pas l’utilisation des méthodes conventionnelles pour suivre le frittage. Ainsi, pour comparer les résultats, un dispositif expérimental original contenant un dilatomètre sans contact de haute résolution a été spécifiquement développé. Ce dispositif, permet aussi un suivi de la distribution de température à la surface de la pièce.Pour des cycles thermiques identiques, obtenus en frittage conventionnel et par micro-ondes, l’évolution de la densification de matériaux aux propriétés différentes a été comparée. Ces matériaux sont : l’alumine pure et dopée par 800ppm d’oxyde de magnésium, l’oxyde de zinc et l’hydroxyapatite silicatée. Pour chacun de ces matériaux, le couplage avec les micro-ondes et la répartition du chauffage à la surface de l’échantillon sont aussi discutés. Un effet bénéfique des micro-ondes sur l’évolution de la densification a été mis en évidence pour l’alumine avec ajout de MgO et de manière plus prononcée pour l’oxyde de zinc. / Microwave sintering is known to be a promising sintering technology. Indeed, this method has advantages such as reducing the duration of heat treatment and a significant energy saving compared with conventional processes. Year after year, sintering in a microwave environment is studied by a growing number of researchers. However, the reasons for the beneficial effect of this type of sintering are not clearly identified.In this context, the objective of this work was to verify the influence of an electromagnetic field at a frequency of 2.45 GHz on the densification of ceramic materials. This objective therefore involves a comparative study of sintering in a microwave chamber and in a conventional oven. However, the presence of electromagnetic field in a microwave oven does not allow the use of conventional methods to monitor the sintering. Thus, to compare the results, an experimental system containing a high resolution contactless dilatometer has been specifically developed. This system also allows monitoring of the temperature distribution on the sample surface.For identical thermal cycles, obtained by conventional and microwave sintering, the densification evolution of materials with different properties was compared. These materials are: pure alumina and doped with 800ppm magnesium oxide, zinc oxide and silicon-substituted hydroxyapatite. For each material, the coupling with the microwaves and the temperature distribution on the surface sample are also discussed. A beneficial effect of microwaves on the evolution of densification has been identified for alumina with addition of MgO and more pronounced for zinc oxide.

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