Reflections on Ernest Roy Davidson: the UW years 1962–1984

In the following research acetylation as an unexplored factor in the anomeric effect in carbohydrate chemistry has been examined. Crystallographic data for methyl glycosides and their acetates have been compared and discussed. Some of the methyl glycosides form hydrogen bonding with the participation of acetal oxygen atoms. This seems to have the most significant influence on the structural diagnostic parameters for anomeric effect.

Abbreviations: Me-α-Glc: methyl α-D-glucopyranoside; Me-β-Glc: methyl β-D-glucopyranoside; Me-α-Gal: methyl α-D-galactopyranoside; Me-β-Gal: methyl β-D-galactopyranoside; Me-α-Man: methyl α-D-mannopyranoside; Me-β-Man: methyl β-D-mannopyranoside; Ac-Me-α-Glc: methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside; Ac-Me-β-Glc: methyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside; Ac-Me-α-Gal: methyl 2,3,4,6-tetra-O-acetyl-α-D-galactopyranoside; Ac-Me-β-Gal: methyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside; Ac-Me-α-Man: methyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranoside; Ac-Me-β-Man: methyl 2,3,4,6-tetra-O-acetyl-β-D-mannopyranoside; GIPAW (Gauge Including Projector Augmented Waves) calculations: a DFT based method used for calculating nuclear magnetic resonance parameters; CP/MAS NMR: cross-polarisation (CP) magic angle spinning (MAS) NMR spectroscopy; δ_ss: chemical shift in ¹³C CP/MAS NMR spectrum; δ_t: theoretical chemical shift: as derived from GIPAW DFT; dis: distorted multiplet in ¹H NMR spectrum.     

Semipolar (11\bar 2\bar 2) ZnO thin films grown on LaAlO3‐buffered LSAT (112) single crystals by pulsed laser deposition

Semipolar (11\bar 2 \bar 2) ZnO was successfully grown on (112) LaAlO₃/(LaAlO₃)_0.29(Sr₂AlTaO₆)_0.35 substrate by pulsed laser deposition. The epitaxial relationship is [11\bar 23]_{\rm ZnO} // [11\bar 1]_{\rm LAO/LSAT} with the polar axis of [000\bar 1]_{\rm ZnO} pointing to the surface. For ZnO films with thickness of 1.6 μm, the threading dislocation density is ～1 × 10⁹ cm^–2, and the density of basal stacking faults is below 1 × 10⁴ cm^–1. The (11\bar 2 \bar 2) ZnO exhibits strong D⁰X emissions with a FWHM of 9 meV and very few green–yellow emissions in the low‐temperature (10 K) and room‐temperature photoluminescence spectra, respectively.

     

Simple model for blistering mechanism

A simple model for blistering mechanism is proposed for energies higher than 20 keV. The model assumes that through the nucleation of smaller bubbles, a critical bubble radius is reached. The planar stress results of Jeffery for a semi-infinite plate with a circular hole subject to a uniform inner normal pressure are roughly taken as valid for the three-dimensional case. Under this assumption, the thickness of the blister's cover and critical ion dose for blister formation are calculated from the knowledge of the mean projected range of ions and blister diameter taken from experimental results. The resulting values are in agreement with the experimental values reported. The model can qualitatively explain breakage at the top of the dome-shaped blisters observed in molybdenum at 1100 K.     

Interatomic potentials in transition metals

The different roles played by the valence s and d electrons in determining the bulk properties of pure transition metals is described. In the light of this the expected behaviour of the inert gas-metal and metal-metal interatomic potentials is discussed.     

Laser Light and X-Ray Diffraction Studies of Oriented Isotactic Polypropylene (iPP) Prepared by Temperature Slope Crystallization

Isotactic polypropylene (iPP) film was melt-crystallized in a temperature gradient. The iPP film showed well oriented α- and β-crystalline textures along the gradient. The crystalline structure, phase transition boundary and lamellar twisting were examined by X-ray diffraction and laser light diffraction (LLD). On the α-β boundary, LLD shows a sharp streak perpendicular to the boundary, where the a-axis of the β-crystal is oriented perpendicular to the temperature gradient. Apart from the boundary, the a-axis of the β-crystal becomes parallel to the gradient. The β-crystal shows lamellar twisting with a pitch of 200 μm at room temperature. When heated the β-crystal, the lamellar distance of 295Å at room temperature decreases to 285Å at 80–100°C and then increases to more than 300Å above 120°C. During the heating, the value of the twist period increases from 200 to 210 μm at 90–100°C, and then to above 224 μm at 140°C. The increase of the twist period is related to the increasing crystalline thickness of the β-lamellae.     

Effect of Temperature and Comonomer Content on Thermal Behavior and Crystallization Property of the Propylene–Ethylene Random Copolymers

The effects of ethylene units content and crystallization temperature on the conformations, and the thermal and crystallization behavior were investigated by a combination of Fourier transform infrared (FTIR) spectroscopy, wide angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). The characterization of FTIR spectroscopy proves that the longer helical conformation sequences of the propylene–ethylene random (PER) samples decrease, whereas the shorter helical conformation sequences increase with the increase in ethylene units content. The increase of the shorter helical conformation sequences is favorable for the formation of the γ-phase in the crystals. A group of broad endothermic peaks can be seen clearly in the DSC curves of PER copolymers, which may be associated with the melting of mixtures of the α- and γ-forms in the crystals. The melting point, crystallization temperature, and crystallinity degree of the PER copolymers decrease with the increase in ethylene units contents. Three typical melting peaks of the PER copolymers crystallized isothermally between 80°C and 130°C were observed. The two higher melting peaks result from melting of the α- and γ-phase in the crystals, whereas the materials crystallized on quenching give the lowest peak. The WAXD results confirm that the PER copolymers crystallize from the melt, as mixtures of α and γ forms, in a wide temperature range. The critical number ζ_lim of the crystallizable units for the α-form increases with the increase in crystallization temperature for PER copolymers, which is favorable for the formation of the γ phases. The amount of γ-form increases with the increase in crystallization temperature at the expense of its α component, then reaches a maximum value at the crystallization temperature of 115°C, and finally decreases with further increase in the crystallization temperature.     

Effects of molecular geometry on liquid crystalline phase behaviour: isotropic-nematic transition

The effects of range and geometry of a simple attractive square-well on the phase diagram of hard ellipsoids and hard spherocylinders is systematically studied using a simple van der Waals type theory. The orientational single particle distribution function is approximated using the Onsager trial function. The quantitative errors introduced by this are thought to be considerably smaller than the use of the van der Waals approximation, which has been shown to give qualitatively correct phase diagrams for similar models. The phase diagrams obtained for hard ellipsoids and hard spherocylinders of aspect ratios ranging between 3 and 10 with a variety of square-well attractions are found to fall into three general types. The first type shows liquid-vapour coexistence and an isotropic-nematic transition, which meet at a liquid-vapour-nematic triple point. The second type shows a marked widening of the isotropic-nematic biphasic region which pre-empts the liquid-vapour coexistence. The final phase diagram shows a strong destabilization of the nematic phase with respect to the isotropic, which results in a shift of the phase transition to higher densities and pressures as the temperature is lowered.     

Neutron diffraction experiments in diamond and sapphire anvil cells

Diamond anvil cells (DAC) provide the highest static pressures ≥1?Mbar. Because of the low intensity of neutron sources, for a long time it was thought impossible to use DAC or other anvil cells in neutron experiments. We describe pressure cells with diamond and sapphire anvils and neutron instrumentation allowing neutron diffraction experiments to be carried out under pressures as high as 50?GPa, temperatures down to 0.1?K, and applied magnetic fields up to 7.5?T.     

High pressure X-ray diffraction study on BaWO4-II

BaWO₄-II has been synthesized at 5 GPa and 610°C. Its high pressure behavior was studied by in situ synchrotron X-ray diffraction measurements at room temperature up to 17 GPa. BaWO₄-II retains its monoclinic structure. Bulk and axial moduli determined by fitting a third-order Birch–Murnaghan equation of state to lattice parameters are: K ₀=86.2±1.9 GPa, K ₀(a)=56.0±0.9 GPa, K ₀(b)=85.3±2.4 GPa, and K ₀(c)=146.1±3.2 GPa with a fixed K′=4. Analysis of axial compressible modulus shows that the a-axis is 2.61 times more compressible than the c-axis and 1.71 times more compressible than the b-axis. The beta angle decreases smoothly between room pressure and 17 GPa from 93.78° to 90.90°.     

Structure refinement of sub-cubic-mm volume sample at high pressures by pulsed neutron powder diffraction: application to brucite in an opposed anvil cell

Neutron powder diffraction measurements of 0.9 mm³ of mixture of deuterated brucite and pressure medium were conducted at pressures to 2.8 GPa, using an opposed anvil cell and a medium-resolution diffractometer at Japan Proton Accelerator Research Complex pulsed neutron source. Spurious-free diffraction patterns were successfully obtained and refined to provide all structural parameters including Debye–Waller factors. Tilting of hydroxyl dipoles of brucite toward one of the three nearest-neighbor oxygen anions was confirmed to be substantial at pressure as low as 1.5 GPa. By this application, technical feasibility to analyze such a small sample has been newly established, which would be useful to extend the applications of neutron diffraction at high pressures.