Blends of poly(butylene terephthalate) and a polyarylate before and after transesterification

Blends of poly(butylene terephthalate) (PBT) and a copolyester of bisphenol-A with 50% terephthalate-50% isophthalate (PAr), before and after transesterification, have been studied by thermal and dynamic mechanical tests to determine crystallinity and phase behavior. Blends without transesterification, as prepared by solution precipitation, show a single T_g, indicating amorphous miscibility of PBT and PAr. A melting-point depression for PBT crystals is not observed; this means that PBT crystallizes excluding PAr and the entropy of melting is small. The highest fractional crystallinity for PBT is obtained at 20-35% of PAr. Transesterified blends were obtained by holding the physical blends at 250°C for up to 16 h. The transesterified systems show higher T_g's than the corresponding physical blends and also show a marked melting-point depression and lesser PBT crystallinity at the corresponding increased PAr content.     

Trapping efficiencies of various collection solvents after supercritical fluid extraction

A polarity test mix consisting of acetophenone, N, N-dimethylaniline, naphthalene, decanoic acid, 2-naphthol, and n-tetracosane was spiked onto sand, and extracted with supercritical carbon dioxide, to evaluate the collection efficiency of various solvents and solvent mixtures. Nine single collection solvent systems and four mixed collection solvent systems were studied. When one-component collection solvents were employed, quantitative (above 90%) recovery of all analytes was not possible. With mixed collection solvents, recoveries of 90% or better with all analytes studied were possible.     

Reproducibility in capillary supercritical fluid chromatography: Comparison of injection techniques

An analysis of the precision obtained using commercially available microvalve injectors is reported for three modes of injection: conventional split; timed-split; and direct. Results from this study show that good precision (< 3% RSD for external standard and < 1% RSD for internal standard methods) can be obtained with capillary supercritical fluid chromatography (SFC). However, particular attention must be paid to the type of valve used, the orientation of the column relative to the valve, the mode of interfacing or connecting the column to the valve, and the type of pressure or density programming used for the analysis as all of these factors will affect the reproducibility.     

Solid-state extrusion of chain-extended polyethylene

Billets of chain-extended polyethylene were prepared from Alathon 7050 (M_w 59,000, M_n 19,000) in an Instron capillary rheometer by crystallization at a constant pressure of 460 MPa, at a series of teimperatures from 198 to 221°C corresponding to varying degrees of undercooling. This gives chain-extended morphologies with a range of crystallinites and lamellar thicknesses. The billets were then solid-state extruded at 100°C through a conical die with 20° entrance angle up to an extrusion draw ration 23.4. Thermal behavior was studied with differential scanning calorimetry. The orientation function measured by wide-angle x-ray diffraction showed higher orientation function measured by wide-angle x-ray diffraction showed higher orientation at equivalent draw ratio when the initial billets were crystallized at lower temperatures. Drawing efficiency, defined as the ratio of molecular draw ratio (from shrinkage) to extrusion draw ratio correspondingly increases, reaching a maximum of 0.71 in our solid-state extrusion. These studies show that highly chain-extended polyethylene, i.e., with few chain entanglements, draws poorly. Drawability was improved by increasing chain entanglements by lowering the crystallization temperature. Electron micrographs of fracture surface replicas of extrudates revealed the coexistence of undeformed, tilted, partially drawn lamellae and fibrillar structure consistent with the cahange of morphologies in Peterlin's model of plastic deformation.     

The acceleratory degradation of solids according to non-steady-state kinetics

The acceleratory degradation of solids represents an area of research where extreme care must be exercised to obtain reproducible data. Different preparations of the same substance often show great variation in degradation patterns. Many kinetic equations have been developed to describe the kinetics of acceleratory degradations. Most of them are empirical and apply only to certain phases of a degradation. The non-steady-state kinetics which were developed to describe the zip degradation of poly(vinyl chloride) will be shown to describe effectively the unusual degradation behavior of inorganic solids that follow an acceleratory pattern.     

Determination of structure of weak scatterers from holographic images

For a weak scatterer a three dimensional Fourier transform of the image formed by a generalized hologram is shown to yield directly the Fourier transform of the scattering potential evaluated on the Ewald sphere. The entire scattering potential can be approximately determined if the object is illuminated from all directions in a series of experiments and if the scattering potential is essentially bandlimited to within a sphere of radius 4π/λ.     

The nonlinear graviton: Superposition of plane waves

The nonlinear graviton construction of Penrose is given explicitly for the nonlinear superposition of a finite number of plane waves with arbitrary propagation directions, phase, and amplitude profiles. These are realized as generalizedH-spaces for which the asymptotic data are distributional and have singular support on a finite number of null generators ofI ⁺.     

Method of calibrating gel permeation chromatography with whole polymers

Column systems for gel permeation chromatography are usually calibrated by eluting a series of sharp polymer fractions of known molecular weights and by correlating their elution volumes with molecular size or weight. A different method for calibration is proposed in which only one polymer sample, with a broad, well-characterized molecular weight distribution, is used. The cumulative distribution and the integrated, normalized GPC chromatogram are successively superimposed, and molecular weights and corresponding elution volumes are correlated. It is found that calibration curves obtained in this manner show a definite curvature. A possible explanation and correction for this behavior is given, based on the concentration dependence of elution volumes.     

QCD asymptotics and kinematic thresholds in deep inelastic scattering

The Nachtmann moments of deep inelastic scattering structure functions are required by kinematics to contain a so far neglected threshold factor which is dependent on both n and q². Its presence significantly affects the “moment analysis” in the usual QCD phenomenology and it resolves the difficulties connected with improper threshold behavior of the “ξ-scaling” analysis of structure functions.