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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.
171

Nanostructured Materials for Pseudocapacitors and Single-Electron Devices

Pu, Long January 2014 (has links)
As a result of increasing demand of power in the modern society, energy storage/consumption is playing a more important role on future economics. Therefore energy storage systems which are more environmentally friendly, low-cost and high-performance have attracted much attention. Among electrochemical systems, supercapacitors are considered as a prominent candidate for the modern energy storage systems due to the high power density, high charge/discharge rate, and long lifetimes. Nevertheless, the performance of supercapacitors is limited by the significant disadvantage of low energy density. Metal oxides with high pseudocapacitance such as MnO2 are used as the electrode materials for supercapacitors to resolve the lack of energy density in supercapacitors. The specific capacitance is notably enhanced by the metal oxides because of the reversible redox reactions. Previous studies confirmed that only a thin layer of MnO2 is involved in the redox process and is electrochemically active, which makes surface area a critical factor of energy storage. To increase surface area of MnO2, ZnO nanostructure is introduced in the electrode material as a template for electrodeposition of MnO2. In the first part of the research, we synthesize a nanomaterial which combines 0-1-2 dimensional properties of different nanostructures and significantly increases the energy capacity of MnO2. iv In the second part of the research, we demonstrate an in situ synthesis of a hybrid device that combines two materials to investigate the individual characteristic of two nanomaterials. In this study, a ZnO nanorod interface on Au nanoparticle arrays is fabricated, and results in the photo-modulation of the array characteristics. We find the use of nanoparticle arrays as electrochemical systems by electrodepositing ZnO on Au nanoparticle arrays. The method expands their potential use in sensors, multifunctional materials, single electron transistors and nanoscale energy systems. Characteristic behavior of Au nanoparticle arrays including Coulomb blockade at room temperature, single electron charging effects and a power law dependence in current-voltage were observed, and Schottky behavior and photocurrent generation due to the ZnO nanorods were also proved. From the modulation of the threshold voltage of the Au array due to the electron-hole pairs generated by photo excitation in the ZnO rods, it can be seen that the system also has coupling between the Au nanoparticles and ZnO rods other than the individual characteristics. Au nanoparticles can be used as electrochemical systems with both structural and spatial confinement of the synthesized material. The possibility of using Au nanoparticle chains as electroactive sites significantly expands their potential use in sensors, multifunctional materials, single electron transistors and nanoscale energy systems.
172

Adsorption of Hydrogen onto Bare and Metal Decorated Metal Oxides

Landry, Paige Elizabeth 01 December 2011 (has links)
Catalytically relevant metal clusters were deposited on metal oxide supports. Palladium and gold were deposited on mixed morphology ZnO, and palladium was deposited on MgO(100). The materials were characterized with electron microscopy, photoluminescent spectroscopy, and X-ray photoelectron spectroscopy. The behavior of hydrogen on these materials, as well as bare ZnO, was studied using volumetric isotherms. The isotherms were used to determine the monolayer gas coverage, surface area, and heats of adsorption of hydrogen on these materials over the temperature range of approximately 8-13 K. At the temperatures and pressures studied, hydrogen physically adsorbed onto the materials. Additional investigations with inelastic neutron scattering were conducted on palladium decorated ZnO and bare ZnO. These revealed that hydrogen molecules on bare ZnO act as three dimensional free rotors, but hydrogen on palladium decorated ZnO acts as a two-dimensional planar molecule and undergoes a 6.2% bond length extension.
173

Effects of ultraviolet illumination and a parylene-A activation layer on the gas phase sensing characteristics of ZnO nanobridges

Mason, Ashley D. 01 July 2011 (has links)
ZnO nanowires (NWs) are good candidates for chemical sensing because of their high surface-to-volume ratio. In this work, ZnO nanobridge sensors were fabricated utilizing a novel method which uses carbonized photoresist (C-PR) as a nucleation layer. The use of C-PR allows simultaneous growth and integration of NWs to lithographically-defined features. The nanobridge sensors are shown to be sensitive to the presence of O₂, H₂O, CO, and H₂/N₂ gas. However, since ZnO dissolves in water, a protective layer is necessary for these sensors to be used in the liquid or vapor phase. A chemical vapor deposition (CVD) process for amino-[2,2]paracyclophane (parylene-A) was developed and used to successfully protect the NWs. Gas sensing measurements were performed on bare and parylene-A coated devices with and without UV illumination. The parylene-A layer was found to attenuate sensitivity to O₂ and H₂O, and UV illumination was found to decrease the response time. / Graduation date: 2012
174

Fyziologické a molekulární odezvy vodních organizmů na účinky chemických látek

CHUPANI, Latifeh January 2017 (has links)
The biochemical and physiological responses of organisms to xenobiotic chemicals have been investigated for many years as general indicators of organism health. These markers have been used in the development of the synthetic pharmaceuticals and screening of effects of environmental pollutant on biological systems, and in clarifying their modes of action. Recently, use of "OMICS" approaches has received great attentions in exploring the effects of chemical contaminants at the molecular level and is one of the rapidly developing areas in the field of toxicology. Use of molecular response within aquatic organisms has been reviewed and are considered as early changes occurring in response to chemical exposure. ZnO NPs are widely used and possess great potentials in food industry and agriculture. Their subsequent release into environment has raised concerns about their potential effects on aquatic organisms. Although, the dietary exposure perhaps is the main route to expose aquatic animals to nanomaterials, the majority of studies are focused on assessment of waterborne exposure. The molecular mechanisms inducing their toxicity on biological system even less investigated. The present study was conducted to explore weather ZnO NPs can be accumulated in internal organs of carp, as a model fish, as well as to assess fish responses to the presence of ZnO NPs in the feed at protein, biochemical, and histological levels. Our results showed nor apparent accumulation of ZnO NPs neither major changes in haematological parameters, lipid peroxidation level, and histology of internal tissues. Our observations showed that 500 mg ZnO NPs per kg of feed caused changes in pathways and the level of proteins associated with cell motility, immune system response, protein synthesis, cell metabolism, and cell survival in intestine as well as it affected the proteins related to immune system in serum. Treated fish underwent these physiological and molecular changes probably attempted to adjust to ZnO NPs as an external stressor. These changes can be considered as compensatory mechanisms to maintenance homeostasis which have an associated energetic cost. If energetic demands to cope with stress exceeds the capacity of limit, then organism's health will be negatively affected. In the second part of study, peracetic acid in tested therapeutic doses (1 and 3 mg L-1 in grass carp and 10 mg L-1 in signal crayfish) caused some histological alterations in gills as well as changes in the activities of antioxidant enzyme in treated animals. It seems that the observed changes were not large enough to induce mortality in treated animals. According our observation after recovery period, it seems that those changes are reversible if it is followed by a sufficient recovery period allowing animals to restore their disturbed homeostasis. However, species-specific differences should be considered while treating more sensitive species. Toward establishing a safe application guideline, more studies will be required to investigate the given issues.
175

Produção fotocatalítica de hidrogênio a partir de soluções de etanol em água

Espindola, Juliana da Silveira January 2010 (has links)
O presente trabalho tem o objetivo de investigar a obtenção de hidrogênio a partir de soluções de etanol em água, por fotocatálise, usando-se catalisadores a base de óxido de zinco (ZnO). Nestes estudos foram empregados cinco catalisadores ZnO, sendo um comercial e os demais preparados através de diferentes metodologias encontradas na literatura. Os catalisadores foram caracterizados por área BET, DRX e FRX, e a investigação preliminar da atividade destes catalisadores foi feita através de ensaios de degradação fotocatalítica de rodamina B em reator slurry em batelada, onde foram avaliadas a taxa de reação e a remoção de corante. Os ensaios para a produção fotocatalítica de hidrogênio foram realizados em um reator de quartzo, operado em batelada com catalisador em suspensão e atmosfera inerte de nitrogênio. A solução foi irradiada por uma série de seis lâmpadas compactas de luz negra. Ao longo dos testes, amostras das fases líquida e gasosa foram coletadas e analisadas para identificação do consumo de etanol e produção de hidrogênio usando-se, respectivamente, Carbono Orgânico Total (TOC) e Cromatografia Gasosa (GC). Resultados preliminares mostraram que os catalisadores ZnO comercial e sintetizado (ZnO Merck e ZnO-B) apresentam atividade fotocatalítica e desempenho similares aos do TiO2 para a degradação da rodamina B. Contudo, estes mesmos catalisadores mostraram-se pouco ativos para a produção fotocatalítica de hidrogênio, com desempenho bastante inferior ao do TiO2 nas mesmas condições. Foi possível observar que o maior rendimento em hidrogênio ocorre para baixas concentrações de catalisador (0,05 gL[elevado a potência menos]1) e elevadas concentrações de etanol, sendo pouco dependente do pH. / This work aims to investigate the hydrogen production from ethanol-water solutions through photocatalysis, using zinc oxide catalysts (ZnO). Five ZnO catalysts were employed in this work; one was a commercial catalyst, while the others were prepared according to different methodologies reported in the literature. The catalysts were characterized by BET, XRD and XRF, and the preliminary investigation of their activity was done by photocatalytic degradation of rhodamine B, through the evaluation of the reaction rate and dye removal. Tests for photocatalytic hydrogen production were carried out in a quartz slurry batch reactor under nitrogen, irradiated by a set of six compact UV light bulbs. During the tests, gas and liquid samples were collected and analyzed in order to identify the consumption of ethanol and hydrogen production using, respectively, Total Organic Carbon (TOC) and Gas Chromatograph (GC). Preliminary results showed that the synthesized and commercial ZnO catalysts (ZnO-B and ZnO Merck) present photocatalytic activity and performance similar to TiO2 for the rhodamine B degradation. However, the ZnO catalysts presented lower performance when compared with TiO2 for hydrogen production, under the same conditions. It was observed that the highest hydrogen yield occurs for low concentrations of catalyst (0.05 gL1) and high concentrations of ethanol, being less dependent on pH.
176

Produção fotocatalítica de hidrogênio a partir de soluções de etanol em água

Espindola, Juliana da Silveira January 2010 (has links)
O presente trabalho tem o objetivo de investigar a obtenção de hidrogênio a partir de soluções de etanol em água, por fotocatálise, usando-se catalisadores a base de óxido de zinco (ZnO). Nestes estudos foram empregados cinco catalisadores ZnO, sendo um comercial e os demais preparados através de diferentes metodologias encontradas na literatura. Os catalisadores foram caracterizados por área BET, DRX e FRX, e a investigação preliminar da atividade destes catalisadores foi feita através de ensaios de degradação fotocatalítica de rodamina B em reator slurry em batelada, onde foram avaliadas a taxa de reação e a remoção de corante. Os ensaios para a produção fotocatalítica de hidrogênio foram realizados em um reator de quartzo, operado em batelada com catalisador em suspensão e atmosfera inerte de nitrogênio. A solução foi irradiada por uma série de seis lâmpadas compactas de luz negra. Ao longo dos testes, amostras das fases líquida e gasosa foram coletadas e analisadas para identificação do consumo de etanol e produção de hidrogênio usando-se, respectivamente, Carbono Orgânico Total (TOC) e Cromatografia Gasosa (GC). Resultados preliminares mostraram que os catalisadores ZnO comercial e sintetizado (ZnO Merck e ZnO-B) apresentam atividade fotocatalítica e desempenho similares aos do TiO2 para a degradação da rodamina B. Contudo, estes mesmos catalisadores mostraram-se pouco ativos para a produção fotocatalítica de hidrogênio, com desempenho bastante inferior ao do TiO2 nas mesmas condições. Foi possível observar que o maior rendimento em hidrogênio ocorre para baixas concentrações de catalisador (0,05 gL[elevado a potência menos]1) e elevadas concentrações de etanol, sendo pouco dependente do pH. / This work aims to investigate the hydrogen production from ethanol-water solutions through photocatalysis, using zinc oxide catalysts (ZnO). Five ZnO catalysts were employed in this work; one was a commercial catalyst, while the others were prepared according to different methodologies reported in the literature. The catalysts were characterized by BET, XRD and XRF, and the preliminary investigation of their activity was done by photocatalytic degradation of rhodamine B, through the evaluation of the reaction rate and dye removal. Tests for photocatalytic hydrogen production were carried out in a quartz slurry batch reactor under nitrogen, irradiated by a set of six compact UV light bulbs. During the tests, gas and liquid samples were collected and analyzed in order to identify the consumption of ethanol and hydrogen production using, respectively, Total Organic Carbon (TOC) and Gas Chromatograph (GC). Preliminary results showed that the synthesized and commercial ZnO catalysts (ZnO-B and ZnO Merck) present photocatalytic activity and performance similar to TiO2 for the rhodamine B degradation. However, the ZnO catalysts presented lower performance when compared with TiO2 for hydrogen production, under the same conditions. It was observed that the highest hydrogen yield occurs for low concentrations of catalyst (0.05 gL1) and high concentrations of ethanol, being less dependent on pH.
177

Estudo computacional do óxido de zinco puro e dopado com metais de transição: bulk, superfícies, interfaces e nanotubos / Computational study of pure zinc oxide and doped with transition metals: bulk, surfaces, interfaces and nanotube

Marana, Naiara Letícia [UNESP] 25 April 2017 (has links)
Submitted by Naiara Letícia Marana null (namarana@fc.unesp.br) on 2017-06-23T18:05:03Z No. of bitstreams: 1 Marana_Naiara_Letícia_Tese.pdf: 4675285 bytes, checksum: acbe2527f22092d1278a0801ad362524 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-06-28T16:26:20Z (GMT) No. of bitstreams: 1 marana_nl_dr_bauru.pdf: 4675285 bytes, checksum: acbe2527f22092d1278a0801ad362524 (MD5) / Made available in DSpace on 2017-06-28T16:26:20Z (GMT). No. of bitstreams: 1 marana_nl_dr_bauru.pdf: 4675285 bytes, checksum: acbe2527f22092d1278a0801ad362524 (MD5) Previous issue date: 2017-04-25 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A química computacional tem se mostrado uma ferramenta muito útil no meio científico e tem sido cada vez mais utilizada na pesquisa de novos materiais. Dentre os muitos sistemas estudados com o auxílio da química computacional, destaca-se o óxido de zinco (ZnO), muito utilizado em diversos dispositivos eletrônicos tais como, sensores, células solares, diodos de emissão de luz UV e diodos a laser. À temperatura e pressão ambientes, a estrutura cristalina mais estável do ZnO é hexagonal do tipo wurtzita, na qual os átomos de zinco estão coordenados a quatro átomos de oxigênio. Devido a coordenação tetraédrica e falta de centro de simetria dessa estrutura, o ZnO apresenta propriedades piezoelétricas podendo ser aplicado em sensores piezoelétricos, por exemplo. Atualmente, existem muitos trabalhos científicos relacionados com o ZnO, porém o número de trabalhos teóricos em relação aos trabalhos experimentais ainda é pequeno. Neste sentido, este projeto teve como objetivo a análise das propriedades do ZnO em três morfologias diferentes, bulk, superfícies e nanotubos, aplicando as principais técnicas de modelagem computacional aplicada ao estado sólido tais como escolha do funcional de densidade e funções de base, otimização da geometria, dopagem por substituição de átomos, cálculo de constantes elásticas e piezoelétricas, simulação de pressão hidrostática aplicada a célula unitária, secção do bulk para gerar superfícies, substituição de átomos para formar interfaces, nanotubos e adsorção de moléculas nos nanotubos. Os cálculos foram realizados aplicando-se a Teoria do Funcional de Densidade, com o auxilio do programa CRYSTAL14, utilizando o funcional híbrido B3LYP, com o conjunto de funções de base all-electron. A metodologia aplicada conserva a periodicidade dos sistemas cristalinos (1D para nanotubos, 2D para superfícies ou 3D para bulk), em que os blocos de construção são compostos por células unitárias e podem ser replicados pelo operador de simetria. As análises topológicas foram realizadas aplicando-se a Teoria Quântica de átomos em Moléculas de Bader. Após a escolha do nível de teoria, as propriedades estruturais, eletrônicas, vibracionais, topológicas e constantes elásticas e piezoelétricas foram analisadas para o bulk. Partindo da estrutura otimizada, os átomos de zinco foram substituídos por Mn2+ e Al3+, simulando sistemas dopados. Paralelamente, foi realizado o estudo do comportamento das constantes elásticas e piezoelétricas em função da variação de pressão hidrostática, que mostrou a resposta piezoelétrica do ZnO aumenta em função da pressão. Após o estudo do bulk, as superfícies (101 ̅0), (112 ̅0) e (0001) foram analisadas e estudadas através de sua energia superficial, propriedades estruturais, eletrônicas e topológicas. A partir da monocamada da superfície (0001), os nanotubos armchair, zigzag e quiral foram gerados e estudados de acordo com sua obtenção, estabilidade e diferentes propriedades. A adsorção de moléculas de NH3 à parede dos nanotubos armchair e zigzag foi estudada onde foram investigadas as alterações nas propriedades decorrentes da adsorção, mostrando que os nanotubos de ZnO são possíveis de serem aplicados em sensores de gás amônia. Por fim, o estudo de sistemas com interface ZnO/GaN foram estudadas para as superfícies (101 ̅0) e (112 ̅0) e nanotubos armchair e zigzag. Ao final, concluiu-se que os sistemas de interface podem ser aplicados em LEDs, por exemplo, pois o controle de espessura e material pertencente à camada externa da interface leva a diferentes emissões no espectro eletromagnético, indo do UVA ao Verde. Com este estudo, pretendeu-se investigar o máximo das três morfologias do ZnO na fase wurtzita e sugerir algumas possíveis aplicações. / Computational chemistry has proved to be a very useful tool in the scientific field and has been increasingly used in the research of new materials. Among the many systems studied with the aid of computational chemistry, we highlight zinc oxide (ZnO), widely used in many electronic devices such as sensors, solar cells, UV light emitting diodes and laser diodes. At room temperature and pressure, the most stable crystalline structure of ZnO is hexagonal of the wurtzite type, in which the zinc atoms are coordinated to four oxygen atoms. Due to the tetrahedral coordination and lack of center of symmetry of this structure, the ZnO presents piezoelectric properties and can be applied in piezoelectric sensors, for example. Currently, there are many papers related to ZnO, however the number of theoretical articles in relation to the experimental works are still small. In this sense, this project aimed the analysis of ZnO properties in three different morphologies, bulk, surfaces and nanotubes, applying the main techniques of computational modeling to solid state such as the choice of density functional and basic functions, optimization of geometry, doping by atom replacement, calculation of elastic and piezoelectric constants, hydrostatic pressure simulation applied to unit cell, bulk section to generate surfaces, replacement of atoms to form interfaces, nanotubes and adsorption of molecules in nanotubes. The calculations were performed applying the Density Functional Theory, with the help of the CRYSTAL14 program, using the hybrid function B3LYP, with the set of all-electron base functions. The applied methodology preserves the periodicity of the crystalline systems (1D for nanotubes, 2D for surfaces or 3D for bulk), in which the building blocks are composed of unit cells and can be replicated by the symmetry operator. The topological reviews were performed applying the Quantum Theory of atoms in Bader's Molecules. After choosing the level of theory, the structural, electronic, vibrational, topological and elastic and piezoelectric constants were analyzed for bulk. From the optimized structure, the zinc atoms were replaced by Mn2+ and Al3+, simulating doped systems. In parallel, a study of the behavior of the elastic and piezoelectric constants was conducted due to the hydrostatic pressure variation, which showed that the piezoelectric response of ZnO increases according to the pressure. After the bulk study, the surfaces (101 ̅0), (112 ̅0) and (0001) were analyzed and studied through their surface energy, structural, electronic and topological properties. From the surface monolayer (0001), the armchair, zigzag and chiral nanotubes were generated and studied according to their obtainment, stability and different properties. The adsorption of NH3 molecules to the wall of the armchair and zigzag nanotubes was studied and an investigation of the changes in the adsorption properties was carried out, showing that ZnO nanotubes are possible to be applied in ammonia gas sensors. Finally, the study of systems with ZnO/GaN interface was conducted for the surfaces (101 ̅0) and (112 ̅0), and armchair and zigzag nanotubes. At the end, it was concluded that the interface systems can be applied in LEDs, for example, because the control of thickness and material belonging to the outer layer of the interface leads to different emissions in the electromagnetic spectrum, going from UVA to green. This study aimed to investigate the maximum of three ZnO morphologies in the wurtzite phase and to suggest some possible applications. / FAPESP: 2013/19713-7 / FAPESP: 2016/07954-8
178

Optical Properties of Wurtzite Semiconductors Studied Using Cathodoluminescence Imaging and Spectroscopy

January 2013 (has links)
abstract: The work contained in this dissertation is focused on the optical properties of direct band gap semiconductors which crystallize in a wurtzite structure: more specifically, the III-nitrides and ZnO. By using cathodoluminescence spectroscopy, many of their properties have been investigated, including band gaps, defect energy levels, carrier lifetimes, strain states, exciton binding energies, and effects of electron irradiation on luminescence. Part of this work is focused on p-type Mg-doped GaN and InGaN. These materials are extremely important for the fabrication of visible light emitting diodes and diode lasers and their complex nature is currently not entirely understood. The luminescence of Mg-doped GaN films has been correlated with electrical and structural measurements in order to understand the behavior of hydrogen in the material. Deeply-bound excitons emitting near 3.37 and 3.42 eV are observed in films with a significant hydrogen concentration during cathodoluminescence at liquid helium temperatures. These radiative transitions are unstable during electron irradiation. Our observations suggest a hydrogen-related nature, as opposed to a previous assignment of stacking fault luminescence. The intensity of the 3.37 eV transition can be correlated with the electrical activation of the Mg acceptors. Next, the acceptor energy level of Mg in InGaN is shown to decrease significantly with an increase in the indium composition. This also corresponds to a decrease in the resistivity of these films. In addition, the hole concentration in multiple quantum well light emitting diode structures is much more uniform in the active region when Mg-doped InGaN (instead of Mg-doped GaN) is used. These results will help improve the efficiency of light emitting diodes, especially in the green/yellow color range. Also, the improved hole transport may prove to be important for the development of photovoltaic devices. Cathodoluminescence studies have also been performed on nanoindented ZnO crystals. Bulk, single crystal ZnO was indented using a sub-micron spherical diamond tip on various surface orientations. The resistance to deformation (the "hardness") of each surface orientation was measured, with the c-plane being the most resistive. This is due to the orientation of the easy glide planes, the c-planes, being positioned perpendicularly to the applied load. The a-plane oriented crystal is the least resistive to deformation. Cathodoluminescence imaging allows for the correlation of the luminescence with the regions located near the indentation. Sub-nanometer shifts in the band edge emission have been assigned to residual strain the crystals. The a- and m-plane oriented crystals show two-fold symmetry with regions of compressive and tensile strain located parallel and perpendicular to the ±c-directions, respectively. The c-plane oriented crystal shows six-fold symmetry with regions of tensile strain extending along the six equivalent a-directions. / Dissertation/Thesis / Ph.D. Physics 2013
179

Fabrication et analyse de nanomatériaux à bases d'oxydes par des techniques de diffusion de rayonnement / Fabrication and analysis of nanomaterials bases oxides by scattering technics

Fall, Safall 06 May 2011 (has links)
Ce travail de thèse porte sur l’étude d’oxydes (ZnO et SiO2) fabriqués par voie sol-gel. Dans un premier temps, nous avons étudié la cinétique de croissance des nanoparticules de ZnO en milieu aqueux. L’étude in-situ de la croissance d’oxyde de zinc par la technique de croissance en milieu aqueux (ACG) a été réalisée grâce à la radiation synchrotron de l’ESRF sur la ligne ID10B. Nous avons réalisé la diffraction de rayons X en incidence rasante sur un substrat plongé dans une solution constituée de nitrate de zinc hexahydraté [Zn(NO3)2,6H2O], d’hexamethylenetetramine (HMT) (C6H12N4) et de l’eau dé-ionisée comme solvant. Nous avons réussi à mettre en évidence l’existence de nanoparticules de ZnO dans la solution et suivre la cinétique de formation. La deuxième partie de ce travail est consacrée à l’étude des films minces de silice mésoporeux structurés par un tensioactif connu sous l’acronyme Brij58. Nous avons commencépar établir le diagramme de phase du Brij58 par la diffusion centrale des rayons X (SAXS), complété par l’établissement d’un diagramme d’état solide-liquide par la rhéologie. Grâce à ce diagramme de phase nous avons pu fabriquer des films minces de silice. L’étude de la structuration des films a été réalisée par la diffusion des rayons X en incidence rasante (GISAXS) et la réflectivité des rayons X. Nous avons finalisé ce travail par l’utilisation des films mésoporeux comme matrice hôte à deux fluides : l’eau et le CO2, et par l’insertion de nanocristaux de ZnO dans les pores de la matrice mésoporeuse. / This thesis presents the study of oxides (ZnO and SiO2) synthesized by sol-gel method. Firstly, we study the kinectics growth of ZnO nanoparticles in aqueous medium. The aqueous chemical growth of ZnO was done at the ESRF (ID10 beamline) for using the synchrotron radiation (22 Kev). The in-situ monitoring by synchrotron radiation on a substrate placed in solution made up from zinc nitrate hexahydrate [Zn(NO3)2,6H2O, 98%, Acros Organics] and hexamethylenetetramine (HMT, C6H12N4, 99%, Acros Organics) precursors dissolved in equimolar concentration in deionized water (MilliQ, 18.2Mo), allowed us to highlight the presence of ZnO nanoparticles in solution and permit to follow the kinetics of the formation of zinc oxide. In the second part, we have synthesized and analysed mesoporous silica thin films templated by a non-ionic surfactant, the Brij58. This work required to establish the binary phase diagramm Water/Brij58 by Small Angle X-rays Scattering (SAXS) at room temperature. The SAXS study is complemented by the determination of the liquid-solid transition of binary system Water/Brij58 by rheolgy. The study of well structured films was carried out by Grazing Incidence Small Angle X-rays Scattering (GISAXS) and by X-rays reflectivity. Lastly, our aim was then to combine the synthesis of porous thin film with the inclusion of zinc oxide nanocrystals in the pores. We completed this work by using these films as porous host matrix for two fluids, water and CO2.
180

Plastic UV radiation protection operating by Stokes emission

Li, Rui January 2013 (has links)
A range of inorganic nanoparticles/nanophosphors that act as ultraviolet radiation absorbers were characterised and assessed in this thesis. Iron doped lithium aluminate phosphor was synthesised using a solid state reaction and also by flame spray pyrolysis. The phosphors prepared by different synthesis methods were characterised to identify their crystal structures and morphologies. Downconverting photoluminescent properties of the phosphors both as pure powders and embedded in polypropylene by co-rotating twin screw extrusion are reported. Zinc oxide nanoparticles made by flame spray pyrolysis were also investigated. They were incorporated into polymers by means of three different approaches including co-rotating twin screw extrusion, spin coating and solvent casting. The resulted composite films were explored to understand the distribution of the zinc oxide nanoparticles. The transmittance and ultraviolet absorption of the nanocomposites were studied and are reported herein. Another set of nanophosphors studied were zinc rich luminescent zinc oxides. They were prepared from the zinc oxide nanoparticles by firing them in a reducing atmosphere. The as-prepared nanophosphors manifested good downconverting photoluminescent properties and maintained their functions when embedded into polystyrene by solvent casting. In this thesis a new route of synthesising aluminium doped zinc oxide nanoparticles was also established. This new approach was based on a series of unexpected results within some trials that were attempting to coat a layer of alumina on the zinc oxide nanoparticles. The concentration of the Al3+ in the final product could be adjusted by tailoring the amount of the Al3+ in the reactants during the synthesis procedures. It was also possible to coat various zinc oxide nanostructures with the aluminium doped zinc oxide.

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