Graduation date: 1997

Electron crystallography is an important technique for studying micro- and nano-sized materials. It has two important advantages over X-ray crystallography for structural studies: 1) crystals millions of times smaller than those needed for X-ray diffraction can be studied; 2) it is possible to; focus the electrons to form an image. The local atomic arrangement can be seen directly by high-resolution transmission electron microscopy (HRTEM). The crystallographic structure factor phases, which are lost in recording diffraction patterns, are present in HRTEM images and can be determined experimentally. The main disadvantages of electron crystallography compared to X-ray diffraction are that the data are difficult to collect, often incomplete and suffer from dynamic scattering. New methods need to be developed to overcome these problems. In this work, structure determination of several unique and complex porous materials including zeolites and mesoporous silica is demonstrated. None of the structures of these materials could be solved by X-ray crystallography. New techniques are also developed in order to overcome the disadvantages of electron crystallography. The new techniques include a digital sampling method for collecting precession electron diffraction data and a rotation method for automatic collection of complete 3D electron diffraction data. A number of practical issues concerning data collection and data processing are described and the data quality is analysed. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Submitted.

Increase in consumption of fresh produce over the past decade has resulted in a rise in incidents of foodborne outbreaks due to pathogens. Chemical sanitizers have been extensively used in the industry for decontamination of fresh produce. However, they are ineffective in certain commodities and under certain processing conditions, necessitating the evaluation of alternative technologies. Electron beam irradiated sliced cantaloupe were tested for 21 days of storage for total aerobic bacterial counts, texture, color and sensory parameters as a function of irradiation doses 0, 0.7 and 1.4 kGy and the wash treatments, water and 200 mg/L chlorine applied to the melons before cutting. Melons washed only with water prior to cutting had total aerobic bacterial counts of 4.0, 2.0 and 0.8 log cfu/g on day 0 at irradiation doses of 0, 0.7 and 1.4 kGy respectively. On day 0, melons washed with chlorine prior to cutting had total aerobic bacterial counts of 2.7, and 0.7 log cfu/g at irradiation doses of 0 and 0.7 kGy and below detection limit at 1.4 kGy. Texture measured as compression force was lower only for cantaloupe irradiated at 1.4 kGy. Irradiation did not affect objective color and descriptive attribute flavor and texture sensory attributes of cantaloupe. Irradiation reduced Salmonella Poona by 1.1 log cfu/g at 0.7 kGy and 3.6 log cfu/g at 1.5 kGy. The D-value of S. Poona on irradiated sliced cantaloupe was found to be 0.211 kGy. Among the spoilage organisms, lactic acid bacteria and mold were reduced effectively by irradiation but there was no significant effect on reduction of yeasts. Our results show that electron beam irradiation in combination with chemical sanitizers is effective in decontamination of fresh-cut produce. Electron microscopy images provided valuable information on attachment sites of S. Poona on cantaloupe rind. The ineffectiveness of chemical sanitizers due to possible inaccessibility to pathogens in these attachment sites provides the basis for application of irradiation in decontamination of fresh produce.

Phase-transformation-induced microstructures, including twin domains, anti-phase domains and inversion domains have been analyzed using the scanning and transmission electron microscopy for BaTiO3, BaCeO3 and CaTiO3 of the perovskite structure. Differential etching rate was taken to identify the ferroelectric domains in tetragonal (t-) BaTiO3. Space group Pbnm (No. 62) usually adopted for the orthorhombic crystals by materials scientists is assumed throughout this research to avoid confusion of the plane and direction indices. Traditional contrast analysis was adopted for determining dislocation Burgers vectors (b) and fault vectors (R) in deformed and phase-transformed perovskites, synthetic ceramics (BaTiO3, BaCeO3 and CaTiO3) as well as natural minerals (CaTiO3), polycrystalline (BaTiO3, BaCeO3 and CaTiO3) as well as single crystal (CaTiO3). Atomic images for the structures of twin boundaries and anti-phase boundaries were taken by high resolution technique and image contrast enhancement was performed using fast Fourier transform. Failure of Friedel¡¦s law is adopted for determining if the crystal belongs to non-centrosymmetric point groups. Whether the twins are £_-, £\- or £k-type (i.e. anti-phase domain boundaries) is analysed from the contrast of extreme fringe patterns. Tilting experiments were performed on selected area diffraction patterns containing un-split row of reflections to ensure that the twin boundaries are the reflection or rotation type. Transformation twinning in all perovskites studied here follows the prediction by the relation of point group symmetries between the high- and low-symmetry phases, assuming continuous, diffusionless, second-order transitions that obey the restrictions imposed by the Landau theory of phase transition. Although such predictions of transformation-induced twinning are only permitted when crystallographic group-subgroup relationship exists and structural coherence retains between the high- and low-symmetry phases, experimental observations for r (rhombohedral) ¡÷ o-BaCeO3 and t ¡÷ o in CaTiO3 that are not related by group-subgroup, c (cubic) ¡÷ t (tetragonal) in CaTiO3 and and c (cubic) ¡÷ t (tetragonal) in BaTiO3 that are related by group-subgroup, are all consistent with the predictions from loss of point group symmetry elements and change of unit cell volume. In order that the Landau theory is conformed, however, an intermediate phase of either the lowest common supergroup (cubic Pm m) or highest common subgroup (monoclinic C2/c), with phase transition experiencing multistage pathways suggested by Christy and assumption of non-disruption conditions proposed by Guymont, was identified to bridge between two structures, such as rhombohedral and orthorhombic that are not group-subgroup related. Both the 90o and 180o ferroelectric twin domains in t-BaTiO3 are the reflection type and have been identified in pressureless-sintered ceramics. Further, fault vectors (R = £`<110]) for such domain boundaries were determined, boundary planes of {110) for the former, {100) and {220) for the latter deduced accordingly. The polar c-direction between adjacent domains was determined by differential etching rate across domain boundaries, convergent beam electron diffraction was also adopted for identification and confirmation of the c-axis for two types of domains in t-BaTiO3. Plastic deformation resulting from the thermodynamic driving force for sintering (?p) intensified by a multiplication factor £p) was evidenced microstructurally from analysing dislocations in pressureless-sintered BaTiO3 where a Frank-Read source was observed. Slip systems are activated for the effective stress acting on the slip plane along the slip direction has exceeded the critical value of resolved shear stress (£nCRSS) and yielding occurs. It has contributed to densification, i.e. the overall system shrinkage of a green powder compact, although if such contribution is at all significant requires studies of sintering kinetics to ascertain. Dislocation dissociation into the scallop-shaped half partials according to the following reactions is determined from analysing corresponding Burgers vectors. [010] + [001] ¡÷ [011] [001] + [10 ] ¡÷ [100] [001] + [110] ¡÷ [111] Both transformation twins lying in {110) and {112) and anti-phase domain boundaries with R = 1/2<111> are detected in o-BaCeO3. For orthorhombic (o-) BaCeO3, fault vectors of the latter R = 1/2<111> determined by contrast analysis was confirmed by high-resolution imaging, but on the contrary, fault vectors the former R = £`<110] and £`<021], respectively, could not be determined from such images. Utilizing the technique of large-angle convergent beam electron diffraction, such fault vectors and dislocation Burgers vectors determined by traditional contrast analysis have been confirmed. Both twinning and dislocations were observed in hot-pressed CaTiO3 prepared in a multi-anvil apparatus. Such twins are deformation twins since hot-pressing was conducted in the orthorhombic stable phase field at 1000oC under 8 GPa. Since fault vectors R = £`<110] determined for {112) and {110) twins are different from the transformation-induced twins in o-CaTiO3, R = £`<021] determined for the {112) twinning in natural perovskite may serve as a diagnostic feature for the deformation twins. Plastic deformation in hot-pressured sample was contributed by both slip and twinning. Slip occurred via slip systems with dislocations of b = [110] gliding in (110) is therefore {110}o <1 0>o (equivalent to {100}pc <001>pc, where pc for pseudo-cubic) often found in perovskites deformed at high temperatures. Another set of dislocations with b = [001] in screw orientation was also determined. APB with R = 1/2<111> detected in natural minerals suggests that the phase transition sequence in CaTiO3 is better described by: (c) ¡÷ t (I4/mcm) ¡÷ o (Pbnm) and such APB are generated from loss of the lattice point at I-centre (1/2,1/2,1/2) in the absence of a second orthorhombic Cmcm between t-I4/mcm and o-Pbnm reported before from neutron and X-ray powder diffraction studies.

Thesis (M. Phil.)--University of Hong Kong, 2002. / Includes bibliographical references (leaf 99).

In this thesis we discuss quantum Hall effects in bilayer graphene and other novel two-dimensional electron systems, focusing on the interplay between nontrivial Fermi surface topology and electron-electron interactions. In the first chapter I will give a brief introduction to some aspects of the quantum Hall effects. The second chapter discusses the physics in bilayer graphene in the absence of external magnetic fields. The first half discusses the band gap opening and trigonal warping effects in its bandstructure, and the second half focuses on the insulating ground state that results from electron-electron interactions. The third chapter discusses the single-particle Landau level structure in bilayer graphene. We will see that when both the band gap and trigonal warping effects are present, the highest Landau level in the valence band is three-fold degenerate at small magnetic fields. As the field increases, the three fold degeneracy is lifted and the Landau level structure gradually reduces to that in the absence of trigonal warping effects. At the end of the chapter we will demonstrate a formalism to map the momentum distribution of the single-particle Landau level structure. Such a mapping will give valuable information about the single-particle bandstructure. The fourth chapter deals with electron-electron interactions in the integer quantum Hall regime, where there is no fractional filling of the orbital degrees of freedom. In such a regime, the effect of electron-electron interactions often leads to spontaneous ordering of the internal degrees of freedom, such as spin, layer and valley. The first part of the chapter will establish the general formalism of Hartree-Fock theory in the quantum Hall regime, and then a specific theory for gapped bilayer graphene with trigonal warping effects is constructed. The resulting ground states are analyzed in the last part of the chapter. / text

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published_or_final_version / Physics / Master / Master of Philosophy

Electron crystallography has evolved as a powerful method for structural characterization of a wide range of materials. It has two significant advantages over other methods for structure determination, e.g. X-ray diffraction. Electrons interact much more strongly with matter compared to X-rays and they can be focused by electromagnetic lenses to form images with atomic resolution. These advantages make electron crystallography a unique tool for characterization of crystalline materials suffering from small crystal size and complex or disordered structures.      Zeolites are a class of microporous materials with significance in several applications. They often possess complex and disordered structures, which demand large efforts in the structure determination.      Over the last years, two new electron crystallographic methods have been developed; the rotation electron diffraction (RED) and the structure projection reconstruction from a through-focus series of high resolution transmission electron microscopy (HRTEM) images. In this thesis, they will be applied for structure determination of four new zeolite structures, including EMM-25 and EMM-23 with two ordered structures, and ITQ-39 and ITQ-38 with disordered structures. Each of the structure solutions have different challenges to overcome. The high silica borosilicate EMM-25 was solved by the RED method. The aluminosilicate EMM-23 was solved by a combination of HRTEM and RED. The structure solution of two materials with disordered structures, ITQ-39 and ITQ-38, will be described. For materials containing disorders, structure projection images are of utmost importance.      Furthermore, the mesoporosity inside hierarchically porous ZSM-5 crystals was studied by a combination of focused ion beam (FIB) and HRTEM imaging. The last part of this thesis explores STEM imaging for use in structure determination from 3D reconstruction. / <p>At the time of the doctoral defence the following papers were unpublished and had a status as follows: Papers 4 and 5: Manuscipts; Paper 10: Manuscript</p>

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