This thesis contains two main parts: the first part focusses on an electron diffraction study on unsupported antimony (Sb) clusters, while in the second part the design and development of a time-of-flight mass spectrometer (TOFMS) is discussed. Electron diffraction is an ideal tool to study the structure of clusters entrained in a beam. The main advantage of this technique is the ability to study the clusters in situ and in an interaction-free environment. It is therefore not necessary to remove the particles from the vacuum system which would lead to oxidation. Since the particles do not have to be deposited on a sample for further investigation, there is also no substrate which could influence the cluster structure. An additional advantage is the short exposure to the electron beam, thereby minimising the likelihood of damaging the particles. Sb clusters were produced using an inert-gas aggregation source. To control the cluster properties the source temperature, pressure and type of cooling gas can be adjusted. In the range of source parameters tested, Sb clusters with three different structures were observed: a crystalline structure corresponding to the rhombohedral structure of bulk Sb, an amorphous structure equivalent to the structure of amorphous Sb thin films, and a structure with the same diffraction signature as Sb4 (Sb evaporates mainly as Sb4). This last structure was found to belong to large particles consisting of randomly oriented Sb4 units. In order to study the size distributions and morphologies of the Sb clusters, the clusters were deposited onto substrates and studied under an electron microscope. The crystalline particles showed a wide variety of strongly faceted shapes. Depending on source conditions, the average cluster diameters ranged from 15 to 130 nm. There was a considerable disagreement between these values and the size estimates from the diffraction results with the latter being smaller by an order of magnitude. This might be due to the existence of domains inside the clusters. The amorphous particles were all found to be spherical with mean sizes between 27 and 45 nm. The Sb4 particles showed a liquid-like morphology and tended to coalesce easily. Their sizes ranged from 18 to 35 nm. To obtain an independent method for determining the cluster size, a TOFMS was designed and developed in collaboration with Dr Bernhard Kaiser. However, the TOFMS failed to detect a cluster signal in the original set-up which is most likely due to a defective ioniser and underestimated cluster energies. Further tests were performed in a new vacuum system and mass spectra for palladium clusters were successfully recorded.

Thesis (M.S.)--Youngstown State University, 2008. / Includes bibliographical references (leaves 74-79). Also available via the World Wide Web in PDF format.

Thesis (M.Sc. (Chemistry)) - Rhodes University, 2009.

Includes bibliographical references (p. 46-47). / "Physics Chemsitry" -t.p.

Thesis (PH. D.)--Columbia University, 1941. / Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

This work aimed to evaluate the subsystems of a novel mediated oxycombustion system and determine the expected final conditions of the integrated subsystems. The subsystems included a cerium based oxygen transport membrane, transport membrane coatings to assist in the pickup and release of oxygen, and a molten intermediary oxygen carrier. Various doping levels of yttrium and zirconium were investigated, both as singular dopants and in a co-doped scheme. Regression analysis was performed to quantitatively evaluate how each dopant affected the material properties. Zirconium was not found to have statistically significant effects, although an effect was clearly noted on pure ceria. Functions of the doping level of yttrium were found for relative density, hardness, and the contributing factors of electrical conductivity. Chemical looping combustion experiments were performed to determine viable candidates for oxygen pickup and release coatings. It was discovered that a release coating was not necessary due to the use of a reactive fluid, and iron showed promise as a pickup coating but short of showing statistical significance. The ability of antimony oxide to react with hydrocarbon fuels and be regenerated by oxygen was investigated to determine the reaction rates. It was discovered that a co-doping scheme of yttrium and zirconium at a level of 8.33% (1/12th) each achieved the highest oxygen flux with a value of 3.671x10-7 mol O/s/cm2. All of the subsystems were we analyzed and a complete, theoretical system was described. It is recommended that the shape of the oxygen transport membrane be of a single-closed-end cylinder. This allows the increase of oxygen permeation with a smaller device footprint. It was found that the system would be capable of combusting 6.699 grams of carbon based fuel per minute per square meter of footprint. This equates to a heat rate of 3.6 kilowatts per square meter when utilizing a medium volatile bituminous coal. This value will continue to be improved as further research is conducted into the components of the system.

Le monde des détecteurs infrarouge a été révolutionné, depuis le milieu des années 2000, par l'apparition de nouvelles structures photodétectrices dont les performances surclassent celles des photodiodes. Ces photodétecteurs ont permis le développement d'une nouvelle génération de caméras plus compactes, plus fiables et moins gourmandes en énergie. Cette thèse avait pour objectif l'étude de ces nouvelles structures photodétectrices haute performance à base d'antimoniures pour la détection du moyen infrarouge entre 3-5µm.Les performances d'un photodétecteur dépendent directement de la qualité des matériaux utilisés pour la fabrication de celui-ci. Aussi, le matériau retenu pour faire office de couche d'absorption a donc dans un premier temps été finement caractérisé. Les mesures de durée de vie (DDV) des porteurs minoritaires dans le matériau se sont révélées être les plus pertinentes pour juger de la qualité des échantillons, et il est reporté une mesure de (DDV) à l'état de l'art pour une température de 80K. Le second volet de cette thèse portait sur le dimensionnement d'une structure photodétectrice à l'aide du logiciel de simulations numériques SILVACO. Une structure optimisée a été proposée puis a été fabriquée par épitaxie à jets moléculaires. A partir de celle-ci, des composants ont été réalisés en salle blanche par un procédé technologique standard. Le courant d'obscurité mesuré se situait une décade plus bas que le photocourant typique ce qui s'est avéré très encourageant pour le développement futur d'une filière basée sur ce type de structures. La dernière partie de ce manuscrit propose une piste pour faire varier la longueur d'onde de coupure de la nouvelle structure photodétectrive grâce à l'utilisation d'une couche absorbante à base de superréseaux antimoniures. / Since the middle of the 2000's, new infrared photodetectors have been proposed that demonstrate better performances than photodiodes. This type of new detectors allowed the development of the compactness, reliability and energy consumption of the next generation of infrared cameras. The aim of this thesis is to study these new high performance photodetectors based on antimony semiconductors dedicated to the 3-5µm mid-infrared domain.Photodetectors performance strongly depends on the quality of its absorption material that has been characterized by diffenrent techniques. Lifetime measurements were identified as the most relevant criterion the evaluation of material quality. A state-of-the-art lifetime value has been reported at a temperature of 80K. Then, an optimized design of the photodetector has been determined using the TCAD SILVACO software. The photodetector structure has been grown by molecular beam epitaxy and devices were made by a standard fabrication process in clean room. The measured dark current was a decade lower than the typical photocurrent : this confirmed the potential of this new structure to be used as a high performance mid-infrared photodetector. Finaly, we demonstrate that the cut-off wavelength of the detector can be tuned using antimony-based superlattices.

Made available in DSpace on 2014-11-10T11:09:59Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-02-26Bitstream added on 2014-11-10T11:57:26Z : No. of bitstreams: 1 000774025.pdf: 1860898 bytes, checksum: 99874674d86c18d175258f3683c34a04 (MD5) / Foram desenvolvidos métodos de determinação de Sb e Pb por espectrometria de absorção atômica com fonte contínua e alta resolução empregando amostragem direta de sólidos. A determinação direta de Sb e Pb foi possível com calibração em meio aquoso utilizando 5 μg de Pd e 2,5 μg de Mg em presença de 0,05% (m/v) de Triton-X como modificador químico. Para o Sb, as temperaturas de pirólise e de atomização foram 1600 °C e 2200 °C respectivamente. O método apresentou massa característica de 1,0 ng e limite de detecção de 0,6 ng. Para o Pb, as temperaturas de pirólise e de atomização foram 1400 °C e 2000 °C respectivamente. A massa característica foi de 5,2 pg e o limite de detecção 4,9 pg. Os desvios padrões relativos do Sb e Pb foram de 2,8% e 4% respectivamente. Estudos de homogeneidade e massa mínima sugeriram boa precisão e exatidão dos métodos na determinação de Sb e Pb em embalagens PET, quando massas entre 0,3 e 0,4 mg para Sb e 0,5 a 0,8 mg para Pb foram utilizadas. Quatro amostras de embalagens PET de diferentes cores foram analisadas pelo método proposto, as concentrações variaram 176,7 a 250,1 mg kg-1 para Sb e de 26,5 a 81,7 pg mg-1 para Pb. Os resultados comparativos obtidos para Sb e Pb empregando HR-CS FAAS e ICP–MS respectivamente, foram concordantes ao nível de 95% de confiança, exceto para o Sb na amostra de PET incolor. O método mostrou-se viável para quantificação dos analitos propostos podendo ser utilizado para controle de qualidade dos PETs, especialmente os que armazenam produtos alimentares. / Methods development were proposed for the determination of Sb and Pb in polyethylene terephthalate (PET) package by high-resolution continuum source atomic absorption spectrometry using direct solid sampling approach. Direct analysis using aqueous standards calibration was possible by using a proper heating program of atomizer and 5 μg Pd and 2.5 μg Mg as modifier in presence of 0.05% (m/v) Triton X-100. With regards to Sb, the pyrolysis and atomization temperatures were 1600°C and 2200°C, respectively. Calibration curves in the 0 – 100 ng range with linear correlation coefficient better than 0.9997 were obtained. The characteristic mass and limit of detection (LOD) were 1.0 ng Sb and 0.6 ng Sb, respectively. The relative standard deviation was 2.8%. For Pb, the of pyrolysis and atomization temperatures were 1400°C and 2000°C, respectively. Calibration in the 0 - 160 pg working range was obtained (R=0.9998) and the relative standard deviations were  4%. The characteristic mass was 5.2 pg Pb and the LOD was 4.9 pg Pb. Studies on homogeneity and minimal mass showed that acceptable precision and accuracy for Sb and Pb may be acquired if masses in the 0.3 - 0.4 mg and 0.5 - 0.8 mg were respectively weighted. PET samples at different colors were analyzed by the proposed method based on direct soid sampling. The concentrations varied from 176.7 to 250.1 mg kg-1 Sb and 26.5 to 80.9 pg mg-1 Pb. These results were in agrement with those obtained by high-resolution continuum source flame atomic absorption spectrometry (for Sb) and inductively coupled plasma mass spectrometry (for Pb) at 95% confidence level (except for the colorless PET).

This work hereby presents the synthesis, spectroscopic and photophysical properties of newly synthesized lead (PbPc) and antimony (SbPc) phthalocyanines. The complexes are either unsubstituted or substituted at the peripheral and non-peripheral positions with phenoxy, 4-t-butylphenoxy and 4-benzyloxyphenoxy groups. The photophysical properties of these complexes were studied in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform as solvents. The fluorescence spectra for PbPc complexes were different to that of the excitation spectra due to demetallation upon excitation. On the other hand, the excitation spectra of oxidized antimony (Sb(V)Pc) derivatives were found to be similar to absorption spectra. High triplet quantum yields for PbPc and SbPc complexes ranging from 0.70 to 0.86, low triplet lifetimes (20–60 μs in DMSO, while they were <10 μs in the rest of the solvents) and low fluorescence quantum yields were observed and is attributed to the presence of heavy atoms (Pb and Sb ions). The nonlinear optical properties of PbPc complexes were studied in dimethylsulfoxide. The optical limiting threshold intensity (Ilim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.8 W/cm2. The photodegradation studies of the PbPc and SbPc complexes synthesized showed that then are stable.

The purpose of this investigation was to study head-transport phenomena in a single crystal of antimony at liquid helium temperatures. In particular, the longitudinal and transverse components of the thermal resistivity tensor were measured as a function of magnetic field up to eighteen kilogauss.