The design, analysis, and performance of a small-angle scatterometer are presented. The effects of the diffraction background, geometrical aberrations and system scatter at the small-angles are separated. Graphs are provided that quantify their contribution. The far-field irradiance distributions of weakly truncated and untruncated Gaussian beams are compared. The envelope of diffraction ringing is shown to decrease proportionately with the level of truncation in the pupil. Spherical aberration and defocus are shown to have little effect on the higher-order diffraction rings of Gaussian apertures and as such will have a negligible effect on most scatter measurements. A method is presented for determining the scattered irradiance level for a given BRDF in relation to the peak irradiance of the point spread function. A method of Gaussian apodization is presented and tested that allows the level of diffraction ringing to become a design parameter. Upon sufficient reduction of the diffraction background, the scattered light from the scatterometers' primary mirror is seen to be the limiting component of the small-angle instrument profile. The scatterometer described was able to make a meaningful measurement close enough to the specular direction at 0.6328μm in order to observe the characteristic height and width of the scatter function. This allowed the rms roughness and autocorrelation length of the surface to be determined from the scatter data at this wavelength. The inferred rms roughness agreed well with an independent optical profilometer measurement of the surface. The BRDF of the samples were also measured at 10.6μm. The rms roughness inferred from this scatter data did not agree with the other measurements. The BRDF did not scale in accordance with the scaler diffraction theory of microrough surfaces. The scattering in the visible was dominated by the effects of surface roughness whereas the scattering in the far-infrared was apparently dominated by the effects of contaminants and surface defects. The model for the surface statistics is investigated. A K₀ (modified Bessel function) autocorrelation function is shown to predict the scattered light distribution of these samples much better than the conventional negative-exponential function. Additionally, a sampling theory is developed that addresses the negative-exponentially correlated output of lock-in amplifiers, detectors, and electronic circuits in general. It is shown that the optimum sampling rate is approximately one sample per time constant and at this rate the improvement in SNR is √(N/2) where N is the number of measurements.

The present work analyses the physicochemical phenomena responsible for the microstructure of Pd/SiO2 xerogel catalysts and of metal-free hybrid SiO2 xerogels synthesized by sol-gel process. The samples are synthesized by co-polymerizing tetraethoxysilane (TEOS) with 3-aminopropyltriethoxysilane or 3-(2-aminoethylamino)propyltrimethoxysilane in ethanol, the latter co-reactant possibly forming a complex with palladium. The analysis is conducted by following in situ the formation of the gels' nanostructure by Small-Angle X-ray Scattering (SAXS), by characterizing the microstructure of the final gels by beam-bending, and by analyzing the microstructure of the xerogels after desiccation, most notably by electron tomography. The in situ SAXS analysis shows that the nanometer structure of the gels forms via a reaction-induced phase separation. The microstructure of the hybrid xerogels is hierarchical, as assessed by electron microscopy, nitrogen adsorption and SAXS. Its structure is that of a microcellular foam at large scale, with pores a few hundred nanometers across, supported by elongated filaments, a few ten nanometers wide, each filament being made up by smaller structures, a few nanometers wide. The characteristics of the various structural levels depend on the nature and concentration of the co-reactant used. In the case of xerogel catalysts, electron tomography shows that Pd nanoparticles are regularly dispersed inside the silica, with distances between them comparable to the thickness of the skeleton. On the basis of the time-resolved SAXS and of the characterization of the xerogels, it is argued that a double phase separation process is responsible for the structuring of the gels, with a primary phase separation leading to the microcellular foam morphology, and a secondary phase separation being responsible for the substructure of the filaments. The large scale structure of the gels themselves, before desiccation, is analyzed by beam bending. This enables one to estimate the mechanical properties of the gels as well as the size of their largest pores. The microstructure of aerogels obtained by supercritical drying of the samples is also investigated. The comparison of the characterization data show that the nature and concentration of the co-reactant controls the amount of shrinkage that the gels undergo during desiccation, at the macroscopic scale as well as at the scale of the filaments.

Aus dem Streubild der Kleinwinkelstreuung kann im Allgemeinen, die die Streuvertei-lung erzeugende Struktur nicht eindeutig rekonstruiert werden. Die Ursache dafür wird erörtert und die damit verbundenen Einschränkungen bei der rechnerischen Auswertung der Streukurven an Beispielen veranschaulicht. Dies geschieht an Streukurven, die mit bekannten Größenverteilungen berechnet wurden. Weiterhin wird untersucht, welche Fit- Ansätze sich zur Auswertung der Kleinwinkelstreuexperimente am besten eignen. Als Fit- Ansätze wurden Reihenentwicklungen nach Trigonometrischen- und Polynomfunkti-onen und eine theoretisch motivierte Funktion verwendet. Neben dem entscheidenden Vergleich mit der Streukurve der Ausgangsfunktion werden die Ergebnisse auch den Rechnungen gegenübergestellt, die mit der weit verbreiteten Glatter- Methode erzielt werden.

The exploration for unconventional energy reserves has rapidly increased over the last five to ten years. Currently, there are a number of companies actively exploring for coalbed methane (CBM) in New Zealand. This study investigates one of these prospects, the subbituminous Huntly coalfield. Coal core was retrieved from the two major seams in the coalfield, the Renown and the Kupakupa. Three coals types were identified (1) bright lustre, non-banded, (2) bright lustre, moderately banded and (3) bright lustre, highly banded. As the degree of banding increases, the average thickness of the vitrain bands increase, the amount of structured vitrinite macerals also increase and the vitrodetrinite content decreases. The Renown seam is predominantly composed of bright non-banded coal while in the Kupakupa seam the more banded coal types are dominant. On average, the Renown seam has both the capacity to hold more gas and has higher gas contents than the stratigraphically lower Kupakupa seam. Additionally, gas content, on average, was found to be highest in intervals of the non-banded coal type and lowest in the highly banded coal type. Cluster analysis found that gas content is associated with hydrogen, volatile matter, calorific value and collodetrinite. As such, gas appears to be preferentially retained/produced in the matrix-dominated material. While not causally linked with gas content, gas holding capacity showed associations with the sporinite, inertodetrinite, funginite and vitrodetrinite; of note, these macerals are highest in the non-banded coal type. Gas holding capacity is thought to be a function of coal texture. Ash yield was found to inversely affect total gas content when ash yield is >10%. Below 10%, it is thought that inorganic elements are organically bound. The small angle scattering analysis indicated that inorganic matter was in the 12.5 Å < r < 125 Å pore size range. The influence of inorganic material was more noticeable in vitrain than matrix samples and is proposed to exist as thin inorganic coatings. Total porosity of the Huntly coal is primarily composed of micropores with macroporosity only contributing a small proportion. In addition, the specific surface area of the coals is also largely contributed by the micropores. Methane holding capacity on a dry, ash-free basis showed positive correlations with both micro- and macroporosity. When methane holding capacity was considered on an ‘as analysed’ basis, correlation was only identified with macroporosity. Possibly gas holding capacity is affected by the presence of moisture blocking access to gas adsorption sites in smaller pores. Considerable variation is present in both gas adsorption and gas desorption results between drill holes, between seams and also within individual seam intersections. Gas adsorption capacity and gas content are used to calculate % saturation for a reservoir, a key assessment parameter. It was found that multiple samples of both gas adsorption capacity and gas content are required to reduce the uncertainty around the calculated % saturation (at least three of each in the current study). Additionally, adsorption isotherm samples need to be collected as fresh as possible to minimize oxidation and moisture loss. Delaying sample analysis was found to result in an overestimation of gas adsorption capacity.

Thesis (Ph.D.) -- McMaster University, 1999. / Includes bibliographical references (p. 112-116). Also available via World Wide Web.

Thesis (Ph.D.) - University of St Andrews, March 2008.

Thesis (Ph. D.)--University of Rhode Island, 2004. / Typescript. Includes bibliographical references (leaves 88-97).

No description available.

Aus dem Streubild der Kleinwinkelstreuung kann im Allgemeinen, die die Streuvertei-lung erzeugende Struktur nicht eindeutig rekonstruiert werden. Die Ursache dafür wird erörtert und die damit verbundenen Einschränkungen bei der rechnerischen Auswertung der Streukurven an Beispielen veranschaulicht. Dies geschieht an Streukurven, die mit bekannten Größenverteilungen berechnet wurden. Weiterhin wird untersucht, welche Fit- Ansätze sich zur Auswertung der Kleinwinkelstreuexperimente am besten eignen. Als Fit- Ansätze wurden Reihenentwicklungen nach Trigonometrischen- und Polynomfunkti-onen und eine theoretisch motivierte Funktion verwendet. Neben dem entscheidenden Vergleich mit der Streukurve der Ausgangsfunktion werden die Ergebnisse auch den Rechnungen gegenübergestellt, die mit der weit verbreiteten Glatter- Methode erzielt werden.

This work is the result of two separate lines of study into the family of frustrated rare-earth pyrochlores with ferromagnetic interactions. The first is an examination of Yb2Ti2O7 and Ho2Ti2O7 through small angle neutron scattering (SANS) techniques. The sensitivity to anisotropic ferromagnetic correlations of SANS makes it an ideal tool to investigate the anomalous scattering of Yb2Ti2O7 , and to take a closer look into the low Q region of the spin ice Ho2Ti2O7 , where long range dipolar effects modify magnetic scattering. We show that in Yb2Ti2O7 the ferromagnetic order observed by other researchers coexists with short range HHH correlations to 0.03 K. We identify a new feature in Yb2Ti2O7 , a medium range (on the order of 100 ̊A) ferromagnetic correlation which appears to correlate well with the systems heat capacity anomaly. In Ho2Ti2O7 , we observe isotropic magnetic scattering in the low Q region that correlates to the system heat capacity anomaly. The second research project involves the system Ho2Sn2−xTixO7 with x=0,0.5,1,1.5,2. We use SQUID magnetometry and inelastic neutron scattering to examine the effects of B-site disorder on the spin ice system. We find some discrepancies with previous generation instrument results for the crystal electric field (CEF) Hamiltonian, and find results consistent with our previously hypothesized picture of the effects of B-site disorder on the CEF levels. We also observe increased spin dynamics in the disordered compounds, which is consistent with recent theory work predicting a transition to a quantum spin liquid phase in disordered non-kramers spin ice compounds. / Thesis / Master of Science (MSc)