Dortmund, Techn. Univ., Diss., 2008.

Thesis--Oulun yliopisto, 1992. / eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Although markets for alternative batteries, such as Li-ion, are growing, Pb-alloy batteries still dominate the market due to their low cost and good functionality. Even though these Pb-alloy batteries have been around since their discovery in 1859, little research involving advanced characterization techniques, such as synchrotron radiation X-ray diffraction (SR-XRD) and transmission electron diffraction (TEM) have been performed on Pb-alloys and sulfation, a failure mode in lead acid batteries, with regards to thermally- and electrochemically-induced changes at the atomic and microstructural scale. Therefore, there is a need to close this scientific gap between research and the application of Pb-alloy battery material. The main objectives of this research are to examine the process of sulfation and its growth mechanisms as well as to study the effects of minor alloying additions in Pb-alloy material. In the first case, nucleation and growth mechanisms of PbSO4 nano- and micro-particles in various solutions are examined using TEM to potentially reduce or control the buildup of PbSO4 on battery electrodes over time. The time dependency of particle morphology was observed using various reaction conditions. This insight can provide avenues to reduce unwanted buildup of PbSO4 on battery electrodes over time which can extend battery life and performance. This is followed by in situ SR-XRD studies of the grain growth and phase evolution associated with adding minor alloying elements, a varying combination of Sb, As, Ca, Sn, Al, In, Ba, and Bi, in Pb-alloy grid material during isothermal holds and thermal cycling. Additionally, sulfation studies were performed in H2SO4 solutions, and the Pb-alloys underwent cyclic voltammetry. Through this research, knowledge of elemental effects on Pb-alloys and corresponding sulfation effects provide insight into ways to extended the life and increase the efficiency of Pb-alloy batteries.

<p>This Licentiate thesis presents research accomplished at theSection of Atomic and Molecular Physics at the Royal Instituteof Technology in Stockholm using photon induced fluorescencespectroscopy (PIFS) during the last two years.</p><p>The main results presented are summarized:</p><p>- Neutral photodissociation in CO was observed aftersynchrotron photon excitation in the range 19-26 eV bycollecting dispersed fluorescence from excited neutral C atoms.Follow-up ab initio calculations point out CO Rydberg seriesconverging to the CO+ C and D states as precursors.</p><p>- The branching ratio between N2 + (B-X)(v’=1,v’’=2) and (v’=0,v’’=1)transitions in the 20-46 eV energy range reveals strongnon-Franck-Condon effects. Ab initio calculations indicate thatthe autoionization of certain superexcited states areresponsible for some of the structures present in the branchingratio curve, confirming the important role of non-Rydbergdoubly excited resonant states (NRDERS) in de-excitationprocesses above the ionization potential.</p><p>- Photon induced neutral dissociation processes in NO arereported. Neither Rydberg series nor other molecular states inNO known so far can account for the collected data. From abinitio calculations more information regarding the NO precursorstates and the mechanism behind the observed neutraldissociation were obtained.</p><p>- The details of a new experimental set-up for gas phasefluorescence measurements using synchrotron radiation aredescribed. It is able to perform simultaneous measurements ofdispersed and total fluorescence in the visible range. Thefirst results obtained with this set-up are presented,concerning fluorescence after excitation of the N2 molecules inthe N 1s edge.</p><p>These four studies conform the set of papers enclosed in theLicentiate thesis.</p><p>Finally a pre-study to further apply PIFS to speciespreviously excited by microwave discharge is included as futureplans.</p>

This thesis describes the effect of pressure on crystal structures that are in some way unusual. The aim was to investigate whether pressure could be used to force these ‘structural oddities’ to conform to more conventional behaviour. In many cases pressure-induced phase transitions were observed, and the driving forces of these are considered. L-serine monohydrate crystallises with layers of hydrogen bonded serine molecules. Layers are linked together by H-bonds from the donor atoms of water molecules. The orientation of the water molecules between the layers is uncommon for other layered hydrates in the CSD. A single crystal of serine hydrate undergoes a pressure-induced phase transition at 5 GPa, which is characterised by a rotation of the water molecules to an orientation which is more frequently observed. PIXEL calculations show that the transition is driven by the PV term in the equation G = U - TS + PV. An attempt to reproduce the transition in another layered hydrate with a similar topology was partially successful in the compression of S-4-sulfo-L-phenylalanine monohydrate, which undergoes a similar phase transition at 1 GPa. Methyl 2-(9H-carbazol-9-yl)benzoate crystallises unusually with eight molecules in the asymmetric unit (Z’ = 8). Compression of a single crystal results in a phase transition at ca. 5 GPa to give a Z’ = 2 polymorph. The PV term is an important contributor to the driving force of the transition. The geometries of the molecules in phase-II are significantly less stable than in phase-I, and as pressure is released on phase-II the need to adopt a more stable molecular conformation eventually outweighs the PV advantage. The Z’ = 8 structure is eventually re-established at 4.6 GPa. This work illustrates how low Z’ polymorphs of the same structure are not always the thermodynamically more stable forms. When recrystallised in situ from a 4:1 by volume solution of methanol and ethanol, a new polymorph of salicylamide is obtained at 0.2 GPa. The ambient pressure phase appears in the CSD to contain a number of abnormally short H…H contacts. We find this model to be incorrect, and have re-determined the structure to find no short H…H contacts. PIXEL and DFT calculations indicate that the high-pressure polymorph is favoured over the ambient phase by the PV term, the zero point energy and entropy. Low completeness that often occurs as a result of shading from the high-pressure cell was improved by the inclusion of multiple crystals within the sample chamber. Bianthrone changes colour from yellow to green on grinding, though this does not occur when subjected to hydrostatic pressure to 6.5 GPa. There is, however, a subtle colour change from bright yellow to dark orange as pressure is applied, and it is likely that this is caused by changes in the - stacking distances. This work highlights how a system can react differently to hydrostatic and non-hydrostatic conditions.

Colloidal quantum dots (QDs) are promising candidates for the next generation of solar cells due to their tunable band gaps, solution processability and the potential for multiple exciton generation. However their stability and the reduction of surface defects are big challenges and effective surface passivation is needed. Passivations via organic ligands have been shown to be imperfect and hinder the charge transfer in devices. Three different QD systems, chosen as exemplars of different approaches to surface passivation, have been investigated with synchrotron-radiation (SR) depth- profiling X-ray photoelectron spectroscopy (XPS). With this technique the chemical composition of the top few nanometres of a sample can be studied with depth. The study of CdTe QDs with and without a chloride treatment revealed the presence of stoichiometric particles prior to, and the likely coexistence of Cl atoms and organic ligands on the surfaces of the QDs after the treatment. The chloride treatment led to a better surface passivation of the QDs resulting in photoluminescence quantum yields of up to 97.2%. Shell thickness estimations using a core/shell/shell model were performed of the chloride treated sample and XPS highlighted the complexity of the structure of the sample. CdTe QDs passivated by a thick CdSe shell were investigated. Indications for an improvement of the stability of the QDs against oxidation were found. The Se:Te ratio was equivalent to a CdSe shell of 0.3-0.4 nm which was significantly smaller than intended, indicating that the butylamine ligand exchange and/or the washing of the sample reduced the thickness of the CdSe shell drastically. The third system studied was PbS QDs that were passivated with a thin CdS shell. XPS of the thoroughly washed QDs confirmed the presence of Cd in an amount equivalent to a 0.13-0.18 nm thick shell. This is thicker than the 0.05 nm shell expected from absorption spectroscopy. A study of ageing of the PbS/CdS QDs revealed that oxidation took place on the surface of the QDs. It was found that sulfur oxidised in stages leading to highly oxidised SO4^2- components. Upon long-term ageing Pb oxidised more rapidly than S, and either some Pb and/or Cd migration or some decomposition of the QDs occurred. The PbS/CdS nanoparticles were more stable than a comparable PbS colloidal quantum dot sample from the literature. The study of the PbS/CdS QDs prior to and after the second wash- ing cycle after a mercaptopropionic acid (MPA) ligand exchange revealed, amongst other things, the removal of MPA and a reduction of the Cd:Pb ratio indicating that (parts of) the QDs decomposed through the ligand exchange or the washing. In addition to the results of the nanoparticles studied some limitations of the study of colloidal QDs with SR depth-profiling XPS are discussed.

This thesis presents interdisciplinary, collaborative research in the field of synchrotron microbeam radiation therapy (MRT). Synchrotron MRT is an experimental radiotherapy technique under consideration for clinical use, following demonstration of efficacy in tumour-bearing rodent models with remarkable sparing of normal tissue. A high flux, X-ray beam from a synchrotron is segmented into micro-planar arrays of narrow beams, typically 25 μm wide and with peak-to-peak separations of 200 μm. The radiobiological effect of MRT and the underlying cellular mechanisms are poorly understood. The ratio between dose in the ‘peaks’of the microbeams to the dose in the ‘valleys’, between the microbeams, has strong biological significance. However, there are difficulties in accurately measuring the dose distribution for MRT. The aim of this thesis is to address elements of both the dosimetric and radiobiological gaps that exist in the field of synchrotron MRT. A method of film dosimetry and microdensitometry was adapted in order to measure the peak-to-valley dose ratios for synchrotron MRT. Two types of radiochromic film were irradiated in a phantom and also flush against a microbeam collimator on beamline BL28B2 at the SPring-8 synchrotron. The HD-810 and EBT varieties of radiochromic film were used to record peak dose and valley dose respectively. In other experiments, a dose build-up effect was investigated and the half value layer of the beam with and without the microbeam collimator was measured to investigate the effect of the collimator on the beam quality. The valley dose obtained for films placed flush against the collimator was approximately 0.25% of the peak dose. Within the water phantom, the valley dose had increased to between 0.7–1.8% of the peak dose, depending on the depth in the phantom. We also demonstrated, experimentally and by Monte Carlo simulation, that the dose is not maximal on the surface and that there is a dose build-up effect. The microbeam collimator did not make an appreciable difference to the beam quality. The measured values of peak-to-valley dose ratio were higher than those predicted by previously published Monte Carlo simulation papers. For the radiobiological studies, planar (560 Gy) or cross-planar (2 x 280 Gy or 2 x 560 Gy) irradiations were delivered to mice inoculated with mammary tumours in their leg, on beamline BL28B2 at the SPring-8 synchrotron. Immunohistochemical staining for DNA double strand breaks, proliferation and apoptosis was performed on irradiated tissue sections. The MRT response was compared to conventional radiotherapy at 11, 22 or 44 Gy. The results of the study provides the first evidence for a differential tissue response at a cellular level between normal and tumour tissues following synchrotron MRT. Within 24 hours of MRT to tumour, obvious cell migration had occurred into and out of irradiated zones. MRT-irradiated tumours showed significantly less proliferative capacity by 24 hours post-irradiation (P = 0.002). Median survival times for EMT-6.5 and 67NR tumour-bearing mice following MRT (2 x 560 Gy) and conventional radiotherapy (22 Gy) increased significantly compared to unirradiated controls (P < 0.0005). However, there was markedly less normal tissue damage from MRT than from conventional radiotherapy. MRT-treated normal skin mounts a more coordinated repair response than tumours. Cell-cell communication of death signals from directly irradiated, migrating cells, may explain why tumours are less resistant to high dose MRT than normal tissue.

Dry matter, crude protein and starch degradation characteristics of one corn (Pioneer 39P78) and four barley grain varieties (CDC Bold, CDC Dolly, Harrington and Valier) were evaluated in two in situ nylon bag trials. Trial 1 compared ground and rolled treatments of Harrington barley and Pioneer 39P78 corn, whereas Trial 2 evaluated ground and rolled treatments of the four barley varieties. Rumen degradability characteristics were compared with analytical results from thermal- and synchrotron-source FTIRM. Infrared absorbance spectra were collected from corn and four barley varieties using thermal-source FTIRM on the mid-IR beamline at the Canadian Light Source, Ltd. (Saskatoon, SK). Synchrotron-source FTIRM spectral data was collected for corn, Harrington barley and Valier barley on the U2B mid-IR beamline at NSLS-BNL (Upton, NY). CHO:Amide I peak area ratios were compared to the in situ rumen degradation results to determine if FTIRM spectral data could be related to the rate and extent of rumen degradation, and if thermal- and synchrotron-source FTIRM yielded different results. A grain x processing method interaction (P<0.01) was observed in both in situ trials where grinding produced a greater increase in the rate and extent of rumen degradation for Harrington barley than it did for corn (Trial 1) along with a greater increase in the rate and extent of rumen degradation for CDC Bold and CDC Dolly than for Harrington and Valier (Trial 2). Among barley varieties, increasing rate and extent of rumen degradation (CDC Bold>CDC Dolly>Harrington>Valier) corresponded to increasing starch:protein ratio as estimated by chemical analysis. This relationship was reversed for corn and Harrington barley where corn had a higher starch:protein ratio yet slower rumen degradation kinetics. For both thermal- and synchrotron-source FTIRM, CHO:amide I peak area ratios were greater (P<0.05) for corn than for Harrington barley. Comparison of CHO:amide I peak area ratios of barley varieties measured with thermal-source FTIR showed that varieties with higher (P<0.05) CHO:Amide I peak area ratios generally had higher rate and extent of rumen degradation. This indicates that starch:protein ratio estimated with FTIRM may be an indicator of rumen degradability characteristics when comparing varieties of the same grain, but not for different species of grains.

The overarching goal of this project was to improve breast cancer screening protocols first by collecting small angle x-ray scattering (SAXS) images from breast biopsy tissue, and second, by applying pattern recognition techniques as a semi-automatic screen. Wavelet based features were generated from the SAXS image data. The features were supplied to a classifier, which sorted the images into distinct groups, such as normal and tumor. <p>The main problem in the project was to find a set of features that provided sufficient separation for classification into groups of normal and tumor. In the original SAXS patterns, information useful for classification was obscured. The wavelet maps allowed new scale-based information to be uncovered from each SAXS pattern. The new information was subsequently used to define features that allowed for classification. Several calculations were tested to extract useful features from the wavelet decomposition maps. The wavelet map average intensity feature was selected as the most promising feature. The wavelet map intensity feature was improved by using pre-processing to remove the high central intensities from the SAXS patterns, and by using different wavelet bases for the wavelet decomposition. <p>The investigation undertaken for this project showed very promising results. A classification rate of 100% was achieved for distinguishing between normal samples and tumor samples. The system also showed promising results when tested on unrelated MRI data. In the future, the semi-automatic pattern recognition tool developed for this project could be automated. With a larger set of data for training and testing, the tool could be improved upon and used to assist radiologists in the detection and classification of breast lesions.

The overarching goal of this project was to improve breast cancer screening protocols first by collecting small angle x-ray scattering (SAXS) images from breast biopsy tissue, and second, by applying pattern recognition techniques as a semi-automatic screen. Wavelet based features were generated from the SAXS image data. The features were supplied to a classifier, which sorted the images into distinct groups, such as normal and tumor. <p>The main problem in the project was to find a set of features that provided sufficient separation for classification into groups of normal and tumor. In the original SAXS patterns, information useful for classification was obscured. The wavelet maps allowed new scale-based information to be uncovered from each SAXS pattern. The new information was subsequently used to define features that allowed for classification. Several calculations were tested to extract useful features from the wavelet decomposition maps. The wavelet map average intensity feature was selected as the most promising feature. The wavelet map intensity feature was improved by using pre-processing to remove the high central intensities from the SAXS patterns, and by using different wavelet bases for the wavelet decomposition. <p>The investigation undertaken for this project showed very promising results. A classification rate of 100% was achieved for distinguishing between normal samples and tumor samples. The system also showed promising results when tested on unrelated MRI data. In the future, the semi-automatic pattern recognition tool developed for this project could be automated. With a larger set of data for training and testing, the tool could be improved upon and used to assist radiologists in the detection and classification of breast lesions.