Random Copolymers of 1,5-Dioxepan-2-one

ABSTRACT

Copolymers of 1,5-dioxepan-2-one (DXO) and e-caprolactone (?-CL), δ-valerolactone (δ-VL) or L-lactide (LLA) have been synthesized and characterized. High molecular weight copolymers were obtained using stannous-2-ethyl hexanoate as catalyst in bulk. Reactivity ratios for the copolymerization of DXO and δ-VL were determined at 110°C as r_VL=0.5 and r_DXO=2.3. At high conversion, depolymerization of δ-VL occurred, resulting in lower molecular weight and variations in the copolymer composition.

Physical properties, such as crystallinity and melting temperature of the DXO-copolymers proved to be strongly dependent on the choice of comonomer and on the molar composition of the copolymers. DXO appears to be incorporated into the poly-?-caprolactone (PCL) crystals and to some extent into the poly-δ-valerolactone (PVL) crystals, resulting in a more gradual decrease in crystallinity with increasing amount of DXO.     

Novel SiGe island coarsening kinetics: ostwald ripening and elastic interactions

Real-time light scattering measurements of coherent island coarsening during SiGe/Si heteroepitaxy reveal unusual kinetics. In particular, the mean island volume increases superlinearly with time, while the areal density of islands decreases at a faster-than-linear rate. Neither observation is consistent with standard considerations of Ostwald ripening. Modification of the standard theory to incorporate the effect of elastic interactions in the growing island array reproduces the observed behavior.     

Reaction of Cu and Cl2 stimulated by synchrotron radiation

Light-induced reactions of poly-Cu with Cl₂ and the formation of CuCl _x films were studied in the spectral range of 105–400 nm by using synchrotron radiation. The efficiencies of the reactions with Cl₂ pressures between 10^–5 and 10^–2 mbar were determined from the height distributions of spatial structures in the CuCl _x films. The heights typically range from 10 to 10⁴ nm. An efficiency of about 10⁷ CuCl _x molecules per dissociated Cl₂ molecule is observed at high Cl₂ exposures. At low Cl₂ pressures CuCl _x formes anisotropically in the irradiated area. The efficiency is determined by light-induced surface processes supporting the build up of CuCl _x in the long wavelength range and competing processes at short wavelengths which reduce the efficiency.     

Dynamic observations of interface motion during the oxidation of silicon

We describe real time observations of the behaviour of the silicon-oxide interface during oxidation in situ in an ultrahigh vacuum transmission electron microscope. We have formed clean, flat Si(111) surfaces by heating under UHV and allowed oxidation or oxygen etching to proceed in the microscope. We have examined the kinetics of both the oxidation and etching reactions using an imaging technique based on the use of forbidden reflections in silicon. We find that oxidation to form SiO₂ occurs by the reaction of discrete monolayers with no flow of surface steps. This is in dramatic contrast to oxygen etching, during which the volatile oxide SiO evaporates preferentially from step edges.     

Sub-nanometer Au monolayer-protected clusters exhibiting molecule-like electronic behavior: quantitative high-angle annular dark-field scanning transmission electron microscopy and electrochemical characterization of clusters with precise atomic stoichiometry

The synthesis and characterization of the clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) are described. These mixed-ligand, sub-nanometer clusters, prepared via exchange of dodecanethiol onto phosphine-halide gold clusters, show enhanced stability relative to the parent. The characterization of these clusters features the precise determination of the number of gold atoms in the cluster cores using high-angle annular dark-field scanning transmission electron microscopy, allowing the assignment of 13 gold atoms (+/-3 atoms) to the composition of both cluster molecules. Electrochemical and optical measurements reveal discrete molecular orbital levels and apparent energy gaps of 1.6-1.7 eV for the two cluster molecules. The electrochemical measurements further indicate that the Au13[PPh3]4[S(CH2)11CH3]2Cl2 cluster undergoes an overall two-electron reduction. The electrochemical and spectroscopic properties of the two Au13 cluster molecules are compared with those of a secondary synthetic product, which proved to be larger Au thiolate-derivatized monolayer-protected clusters with an average core of Au180. The latter shows behavior fully consistent with the adoption of metallic-like properties.     

Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.     

A high-temperature structure for Ta2O5 with modulations by TiO2 substitution

Solid solutions in the series (1−x)Ta₂O₅−xTiO₂ with x=0.0-0.1 were prepared by high-temperature ceramic processing methods, and the crystal structure was determined at room temperature by transmission electron microscopy, electron diffraction and high-resolution lattice imaging. A structural model is proposed for the oxygen-deficient tantalum oxide (Ta₂O₅) phase with high TiO₂ doping level (x=0.08). The model is based on edge sharing of an oxygen octahedron-hexagonal bi-pyramid-octahedron molecular building block unit that repeats four times per unit cell. Electron diffraction reveals a monoclinic distortion from a pseudo-tetragonal model structure that is modulated primarily along 〈110〉. The modulation length varies with increasing TiO₂ content. Furthermore, by quantitative HREM analysis and matching of lattice images by simulation, it is shown that the modulation is associated with small ionic displacements in specific lattice planes that coincide with Ta ions in the model structure coordinated by oxygen hexagonal bi-pyramids. Based on this evidence, it is suggested that the modulation comes from a replacement of Ta with Ti ions, and the loss of inversion symmetry in the modulated structure is related to the dielectric properties of the material.     

Real meromorphic functions and linear differential polynomials

We determine all real meromorphic functions f in the plane such that f has finitely many zeros, the poles of f have bounded multiplicities, and f and F have finitely many non-real zeros, where F is a linear differential polynomial given by F = f (k) +Σk-1j=0ajf(j) , in which k≥2 and the coefficients aj are real numbers with a0≠0.     

Detection of lateral composition modulation by magnetoexciton spectroscopy

An experimental signature for detecting spontaneous lateral composition modulation in a (InAs) (GaAs) short period superlattice on a InP substrate based on magnetoexciton spectroscopy is described. We find by aligning the magnetic field in three crystallographic directions, one parallel to and the other two perpendicular to the composition modulation direction, that the magnetoexciton shifts are anisotropic and are a good indicator for the presence of composition modulation.