Some effects of melt-induced orientation on drawing of polypropylene monofilaments

Morphological changes accompanying the deformation of polypropylene filaments with varying degrees of melt-induced orientation are examined using wide-angle x-ray scattering (WAXS), small-angle x-ray scattering (SAXS), and electron microscopy, and their behavior is compared both to completely unoriented film samples and to very highly oriented, hard elastic filaments. Melt-oriented filaments are shown to deform predominantly by a voiding mechanism at low temperatures (<100°C), and destruction of the lamellas to produce fibrils occurs only after extensive drawing. The bimodal crystal texture of the filaments does not appear to greatly affect the low temperature deformation mechanism. High temperature (>100°C) drawing produces a fibrillar structure containing elongated voids.     

Der Wedderburnsche Hauptsatz für alternative Tripelsysteme und Paare

Ohne Zusammenfassung     

Surface changes during polypropylene photo-oxidation: A study by infrared spectroscopy and electron microscopy

The surface oxidation of polypropylene films which occurs during ultraviolet irradiation in air was found to result in extensive surface restructuring. This restructuring was detected by changes in surface infrared spectra, as measured by attenuated total reflection spectroscopy, and by electron microscopy. The 997 cm^?1/974 cm^?1 absorbance ratio of the film surfaces increased steadily during ultraviolet degradation and was interpreted as an increase in helical ordering which resulted from backbone scission during irradiation. This scission probably also results in the increase in crystallinity detected by density changes. Electron microscopy of direct surface replicas and replicas of material detached from the oxidized film surfaces showed that surface cracking resulted during photo-oxidation, and that this oxidation penetrated selectively into the polymer structure. The replicas of detached, oxidized material showed periodic structures related to the interior morphology of the films. The observed restructuring is believed to be entirely responsible for the decrease in percentage elongation at break which results from photodegradation.     

Absolute and relative entropies from computer simulation with applications to ligand binding

A comparison between two related methods, Schlitter's formula and quasiharmonic analysis, for calculating absolute entropies from the covariance matrix of atomic fluctuations using molecular dynamics (MD) simulations is presented. Calculations for a set of organic compounds in the gas phase are compared to the corresponding statistical thermodynamics results for translational and rotational entropies and to experimental data for vibrational entropies. Encouraging agreement is obtained for translational entropies, but for the rotational contribution, both methods fail to reproduce the theoretically calculated values. Absolute and relative vibrational entropies are found to be better reproduced using quasiharmonic analysis compared to Schlitter's formula. For rotational entropies, we propose a method based on the variances in Euler angles, which gives good agreement with theory. Alternative methods for estimating translational entropies based on principal root mean-square (rms) fluctuations of the center of mass are also presented, and these reproduce theoretically calculated values well. These methodologies are applied to the binding of benzene to T4-lysozyme, where close agreement with the literature is obtained for translational and rotational entropies.     

Light-propagation characteristics of Y-branch defect waveguides in AlGaAs-based air-bridge-type two-dimensional photonic crystal slabs

Y-branch defect waveguides (DWGs) in an AlGaAs-based air-bridge-type two-dimensional (2D) photonic crystal (PC) slab were fabricated, and the resulting optical transmission spectra were measured. Optical beam propagation along the waveguide was successfully observed in vidicon IR images. The measured transmission spectra at the two output ports in the Y-branch DWG were remarkably similar in shape and magnitude. From comparison between the measured and calculated transmission spectra, the observed optical beam was identified as the guided mode based on the Y-branch DWG in the 2D PC slab. The results suggest that the Y-branch DWG used in the experiment has the potential to function as an ultrasmall 3-dB beam splitter with good performance.     

Design,nano-fabrication and analysis of near-infrared 2D photonic crystal air-bridge structures

Selective wet etching is a technique that allows fabrication of freely suspended thin slabs in epitaxial heterostructures. This technique, together with high-aspect ratio dry etching, is used to create two-dimensional (2D) photonic crystals for near-infrared wavelengths in thin suspended AlGaAs membranes. The active photonic crystal areas contain hexagonal arrays of cylindrical holes completely perforating the membrane. For an appropriate selection of the slab thickness and the lattice parameter, dispersion relations for the guided modes are explicitly computed by solving the Maxwell equations in a geometry containing a 2D photonic crystal defined in the core layer of a dielectric waveguide structure. Measurements of the spectral transmittance in air-bridge samples show a narrow 30-dB-deep stop band for TM polarized incident light. The spectral position of the stop band shows a good agreement with theoretical band structure calculations when also the quasi-guided resonant modes outside the light cone are taken into account.     

Enamine Chemistry—XXIV.: Synthesis,thiation, and reduction of lactams

Enamines, 1, prepared from cyclohexanones or cyclopentanones are reacted with acrylamide to give lactams, the condensed 2-piperidones, 2. Ethyl 2-(1-pyrrolidinyl)-2-cyclohexene-1-propanoate, 3, when treated with primary amines, produces the corresponding N-substituted 2-piperidones, 4. Ethyl 2-(1-pyrrolidinyl)-2-cyclohexene-1-ethanoates and ethyl 2-(1-pyrrolidinyl)-2-cyclopentene-1-ethanoate, 5, react with primary amines to give condensed N-substituted 2-pyrrolidones, 6, and non-cyclic imines, 7. The starting enamines, 1, treated with 2-bromo acetamides only afford the N-alkylated compounds 8 (2-pyrrolidino acetamides), and the regioselectivity of this reaction is rationalized in terms of the HSAB-principle. Compound 1 undergoes an exchange reaction (aminolysis) when reacted with primary amines to give the imines 9. Thiation of the lactams 2 and 6 with the Lawesson reagent (LR), affords the corresponding thiolactams, 10. Reduction of the lactams and thiolactams, 2, 6, and 10 by LAH gives the imines, 11, and the enamines, 16. Further reduction of 11 (LAH) affords the saturated amines, 15. The stereochemistry for the formation of 15 is discussed using the torsion angle notation and the principal of least torsional distortion. In a one-pot reaction using LAH-acetic anhydride the lactams, 2, and the thiolactams, 10, are transformed into the enamides, 14. Compound 14 was also obtained from 11 by direct acetylation with acetic anhydride in the presence of triethylamine.     

Enamine chemistry—XVIII: The formation of hexahydrochromane-8a-amines by reductive cyclisation of enamines

Enamines (1) derived from cyclohexanone or cyclopentanone are reacted with electrophilic olefins (ethyl acrylate, ethyl 2-methylacrylate, ethyl 2-butenoate) to give the new enamines, 2. When 2 is reacted with LiAlH₄, reductive cyclisation takes place giving hexahydrochromane-8a-amines of octahydrocyclopentapyrane-7a-amines, 3, in quantitative yields. 3 is hydrolyzed with dilute aqueous hydrochloric acid to hexahydrochromane-8a-ols of octahydrocyclopentapyrane-7a-ols (4) and reacts also with oxalic acid in refluxing dioxane to form the condensed dihydropyranes, 5.