Quantum-scale semiconductors embedded in an electrically-active matrix have the potential to improve photovoltaic (PV) device power conversion efficiencies by allowing the solar spectral absorption and photocarrier transport properties to be tuned through the control of short and long range structure. In the present work, the effects of phase assembly on quantum confinement effects and carrier transport were investigated in CdTe - ZnO nanocomposite thin films for use as a spectrally sensitized n-type heterojunction element. The nanocomposites were deposited via a dual-source, sequential radio-frequency (RF) sputter technique that offers the unique opportunity for in-situ control of the CdTe phase spatial distribution within the ZnO matrix. The manipulation of the spatial distribution of the CdTe nanophase allowed for variation in the electromagnetic coupling interactions between semiconductor domains and accompanying changes in the effective carrier confinement volume and associated spectral absorption properties. Deposition conditions favoring CdTe connectivity had a red shift in absorption energy onset in comparison to phase assemblies with a more isolated CdTe phase. While manipulating the absorption properties is of significant interest, the electronic behavior of the nanocomposite must also be considered. The continuity of both the matrix and the CdTe influenced the mobility pathways for carriers generated within their respective phases. Photoconductivity of the nanocomposite, dependent upon the combined influences of nanostructure-mediated optical absorption and carrier transport path, increased with an increased semiconductor nanoparticle number density along the applied field direction. Mobility of the carriers in the nanocomposite was further mediated by the interface between the ZnO and CdTe nanophases which acts as a source of carrier scattering centers. These effects were influenced by low temperature annealing of the nanocomposite which served to increase the crystallinity of the phases without modification of the as-deposited phase assembly and associated absorption properties. Integration of the nanocomposite as an n-type heterojunction element into a PV device demonstrated the ability to tune device response based on the spectral absorption of the nanocomposite sensitizer film as dictated by the phase assembly. Overall the various phase assemblies studied provided increased opportunity for optimization of the absorption and carrier transport properties of the nanocomposite thin films.

This dissertation focuses on the preparation of new Nafion®/ ex-situ silica nanocomposites membranes and the impact of particle size of spherical silica particles on the nanocomposites' properties. To achieve acceptable power production, fuel cell polymer membranes are required with good proton conductivity, water retention, thermal and mechanical stability. However, to avoid poisoning of fuel cell electrocatalysts with CO or other fuel contaminants, they must be operated at temperatures (>100 °C). At these temperatures, fuel cell membranes dehydrate resulting in dramatic decreases in proton conductivity or complete failure as membranes crack due to volumetric stress from water loss. Even if fuel cell is kept in a humidified chamber, increasing temperature will eventually shut the cell down as Nafion®'s bicontinuous structure "dissolves" into a single poorly conducting phase at temperatures above the polymer's Tg.This research provides systematic studies of effects of silica particle size on properties of silica-Nafion® nanocomposites. Results of this study include new insights into requirements for reproducible particle syntheses, practical methods for avoiding silica particle floatation during Nafion® nanocomposite membranes preparation, and a summary of the influence of particle size and functionalization on Nafion® membrane properties. Stober particle syntheses showed high sensitive to ammonia concentration and we discovered that literature procedures' variability is likely due to researchers failure to actually measure ammonia concentration in their aqueous base (which can be 50% or more off). Homogeneous nanocomposite membranes, as determined by AFM and SEM, were successfully prepared using more viscous dispersions. It was observed that nanocomposites membranes with small particles (<50 nm) showed significant increases in proton conductivity at temperatures above 80 °C. Surface modification of the silica particles improved the proton conductivity at 80 °C. Enhancement on proton conductivity was more pronounced with small modified particles at temperatures < 80 °C but unmodified particles were better than modified particles at temperatures >80 °C. Small, unmodified particles led to enhanced thermal stability of the Nafion® ionic domain, however, surface modification did not result in any thermal stability enhancement. Contrary to the expected, mechanical properties of the Nafion® were degraded by adding the silica particles, especially with smaller particles (<50nm).

No description available.

No description available.

A kaolinite-nylon 6 composite was prepared by a polycondensation reaction from 6-aminohexanoic acid (AHA) intercalated in the kaolinite interlayer space. The basal spacing of kaolinite-AHA was 1.47 nm and the basal spacing of the heated products decreased to 1.16 nm. The signals attributed to nylon 6 were detected in the 13C CP/MAS NMR spectra of the heated products. Formation of nylon 6 in kaolinite was confirmed by appearance of IR band due to amide I and amide II. Sarcosine was intercalated in kaolinite for the first time by guest displacement with methanol from the kaolinite-methanol precursor. The basal spacing of kaolinite-sarcosine was 1.27 nm. This intercalation compound was characterized by NMR, TGA, XRD, and IR. The physical and chemical properties of natural clay sample from Mirandela formation (Portugal) were determined in terms of external skin treatment. The low CEC 4,45meq/100g is consistent with high content of kaolinite in the sample

Vertically aligned nanocomposite (VAN) oxide thin films are unique nanostructures with two-phase self-assembled, heteroepitaxially grown on single-crystal substrates. Both phases tend to grow vertically and simultaneously on a given substrate with lattice matching in the system. The nanostructured thin film system could form different in-plane morphologies including nano-checkerboard, nanopillar in matrix and nanomaze structures. The VAN thin films with tunable vertical lattice strain and novel microstructures provide fascinating approaches to achieve enhanced functionalities. In this dissertation, the microstructure and vertical strain effect on low-field magnetoresistance (LFMR) have been investigated in heteroepitaxial La0.7Sr0.3MnO3 (LSMO):CeO2 and LSMO:ZnO VAN thin films with a vertical strain of 0.13 % and 0.5 %, respectively. We demonstrate that LFMR can be tuned by column width and vertical strain in these VAN systems, i.e., smaller column width and larger vertical strain could result in a larger LFMR in the vertical nanocomposite heteroepitaxial thin films. The physical mechanism of enhanced LFMR in LSMO-based VAN has been explored. Single-phase LSMO and LSMO-based VANs have been grown on different substrates with different secondary phase compositions. Substrate effect in single-phase LSMO films shows that LFMR tends to increase with grain misorientation factor because the cross-section of electron conduction paths reduces as grain misorientation factor increases. (LSMO)1-x:(ZnO)x VAN heteroepitaxial films without large angle grain boundary (GB) have been used to study the pure phase boundary (PB) effect on the LFMR. It shows that increased PBs tends to reduce the cross-section of the conducting path and thus favor the spin-dependent tunneling in nanomaze structures with ferromagnetic/insulating/ferromagnetic vertical sandwiches. Tilted aligned LSMO nanostructured films with artificial GBs have been designed to investigate pure GBs influence on LFMR. The results indicate that decoupling of neighboring ferromagnetic (FM) domains by artificial GBs is necessary to achieve enhanced LFMR properties; and the strength of the GBs can be controlled by post-annealing to tune the LFMR effect. The VAN heteroepitaxial films display excellent microstructure compatibility and strain tuning. Perovskite oxides can be combined with many other oxide materials to form VAN architectures. The microstructure and lattice strain in the unique heteroepitaxial VANs can be used to engineer and tune the existing/new functionalities.

The confinement of magnetic nanoparticles (Prussian blue analogues (PBAs) has been achieved using mesostructured silica as a matrix. The PBAs have the general formula AxMy[M'(CN)n]z, where A is an alkali metal cation; M: CoII, NiII, SmIII; and M': CoII. The two reactions were run in parallel and led to a mesostructured silica matrix that contains nanoparticles of PBA homogeneously distributed within the silica framework. As initially reported for the synthesis of Co3[Fe(CN)6]2 magnetic nanoparticles, in the research conducted for this thesis, this synthesis has been extended to other compounds and to lanthanides such as Sm and has also included the study of the influence of different parameters (pH, concentration). As these nanocomposites are potentially good candidates for the preparation of bimetallic nanoparticles and oxides through controlled thermal treatment, the second goal of the research was to employ an adapted thermal treatment in order to prepare metal and metal oxide nanoparticles from PBA, directly embedded in the silica matrix. To this end, the influence of the thermal treatment (temperature, time, atmosphere) on the nature and structure of the resulting materials was investigated, with a focus on the potential use of the combustion of the organic templates as in-situ reducing agents. For some compounds, the preparation of bimetallic nanoparticles was successful. This method was tentatively applied to the preparation of specific Sm:Co bimetallic compounds, are well known as one of the best permanent magnets currently available.

This study was undertaken to prepare polystyrene (PS)/montmorillonite (MMT) nanocomposites by different methods, including melt intercalation, in-situ polymerization and masterbatch methods. The in-situ polymerization method consisted of dispersing the styrene monomer into the galleries of MMT followed by subsequent polymerization. The PS/MMT nanocomposites formed by melt intercalation method were prepared on a twin-screw extruder. The masterbatch method was in fact a two-step process. As the first step, a high clay content composite of polystyrene (masterbatch) was prepared by in-situ polymerization, and then the prepared masterbatch was diluted to desired compositions with commercial polystyrene in a twin-screw extruder.The structural, thermal and mechanical properties of the nanocomposites were examined. X-Ray diffraction (XRD) analysis showed that the d-spacing of the in-situ formed nanocomposites containing 0.73 and 1.6 wt. %organoclay increased from 32.9 &amp / #506 / to 36.3 and 36.8 &amp / #506 / respectively, indicating intercalation while the dspacing of the other prepared materials remained nearly unchanged compared to pure organoclay. At low clay content, (&lt / 1 wt.%), in-situ formed nanocomposites showed the best improvement in mechanical properties including tensile, flexural, impact strength and Young&rsquo / s modulus. In all the three methods, the addition of organoclay increased the Young&rsquo / s modulus compared to neat resin, but the maximum improvement was 88.5 %, obtained at 0.73 wt. % organoclay in the in-situ formed material. In-situ polymerization method did not prove to be efficient at high clay loadings in terms of mechanical properties. At high clay loadings, the effects of the three methods on promoting mechanical properties were not significantly different from each other. The glass transition temperature increased from 105.5 oC in the pure polystyrene to 108.4 oC in the in-situ formed nanocomposite at 0.73 wt % organoclay due to the restricted mobility of the polymer chains within the organoclay layers.

Title: Stability of plasma polymers under various conditions. Author: Jindřich Matoušek Department/Institute: Department of Macromolecular Physics/Charles University in Prague Supervisor of the doctoral thesis: prof. RNDr. Hynek Biederman, DrSc., Department of Macromolecular Physics Abstract: The depositions of plasma polymer thin films were carried out using plasma polymerization depostition. The working gas mixture consisted of argon and monomer vapours. The source monomers used were n-hexane and terthiophene. The depositions of nanocomposite thin films Sn/pp n-hexane by means of magnetron sputtering in a working gas mixture of argon and n-hexane were done. The resulting thin films were characterized by XPS, FTIR, AFM, SEM, TEM, optical microscope and elipsometry. The influence of deposition parameters on the resulting thin film propertires was studied. The ageing of the thin films in humidity and distilled water was studied. The current-voltage characteristics of selected thin films were measured. Keywords: plasma polymer, nanocomposite, ageing.

L'auteur n'a pas fourni de résumé de moins de 4000 caractères en français / L'auteur n'a pas fourni de résumé de moins de 4000 caractères en anglais