Transport of gases in aromatic polyesters: Correlation with WAXD studies

Polymer packing density can be conveniently measured by either density-based measurements (direct or estimated free volume) or wide-angle X-ray diffraction (WAXD) spectra. Previously reported diffusivity and permeability values for various polyarylates and polyimides are examined on the basis of the packing density measured by these different techniques. It is shown that in these rigid glassy polymers, the mean intersegmental distance, the d-spacing, obtained from WAXD provides a better measure of the effect of polymer packing on diffusivity than either direct density measurements or estimated free volumes. It has been possible to correlate previously reported diffusivity and sorption data for various polyarylates and polycarbonate on the basis of the WAXD investigation, using the d-spacing and the amorphous peak width, respectively. The effect of polyarylate structure on d-spacing has been studied. A series of polyarylates have been synthesized with different substituents on the bridge carbon. In this series the d-spacing remains constant while the carbonyl group density and the glass transition temperatures are varied. However, small substituents on the aromatic ring cause significant changes in the d-spacing. These results can be used to tailor polyarylates with desired intersegmental distances and chain flexibility.     

Scanning LLL x-ray interferometry

A new formalism is presented for the theory of scanning LLL x-ray interferometry, which takes account also of the amount of x-ray absorption and of crystal yawing. It is based on the Takagi approach to the dynamical theory of x-ray diffraction and uses, to a great extent, the formalism of quantum mechanics, in order to reduce the algebraic complexity of the Ewald-von Laue approach. The formalism presented here is an easy-to-handle tool for the study of x-ray propagation in multicrystal systems and for the investigation into deviations of the travelling-fringe period from the spacing of diffracting planes, as it explains how interference features change when moving in paramater space.     

A model of the kinetics of macrocyclic BPA carbonate formation

Cyclic oligocarbonates are synthesized by two-phase interfacial reactions of aryl bischloroformates in the presence of an amine phase transfer catalyst and an alkali: nClOCOArOCOCl + 4nNaOH → (OArOCO)_n + 2nNaCl + nNa₂CO₃ + 2nH₂O. The organocarbonate product may be a macrocyclic oligomer or a linear chain polymer. A qualitative mechanism for this behavior has been proposed by Brunelle, Boden, and co-workers. Four steps are identifiable: activation of the aryl bischloroformate by the amine catalyst, hydrolysis of a portion of this intermediate at the aqueous/organic phase interface, oligomerization between activated and hydrolyzed moieties also at the interface, and chain terminating carbamate formation that leads to polymer. An important modification is made within the framework of the Brunelle and Boden mechanism. While the intramolecular cyclization reaction is formally second-order overall, it behaves as a first-order process. The kinetic constants for both this pseudo-first-order cyclization step and the corresponding second-order linearization step are simply related. It is speculated that the above relationship can be generalized for a whole class of pseudo-first- and second-order rate constants for similar macrocyclic reactions.     

Analysis of atmospheric particular matter and water using atomic emission spectrometry with inductively-coupled plasma and two-jet plasmatron

Summary A method for the atomic emission spectrometric analysis of air and water with inductively coupled and two-jet direct current plasmas has been developed. The method has been applied to the determination of impurity contents with good accuracy and sensitivity.     

Determination of ammonia and nitric acid using a diffusion denuder method

Summary A diffusion denuder technique, using annular denuders, has been introduced in our laboratory. The characteristics of different coatings for the enrichment of both ammonia and nitric acid have been determined in a laboratory study applying test atmospheres. The results, partly differing substantially from theoretical predictions, are presented here. The method has been applied for the determination of trace amounts of ammonia and nitric acid at various sites in the upper Rhine region.     

Pit your wits against young minds!

This column is a place for those bits of contagious mathematics that travel from person to person in the community, because they are so elegant, suprising, or appealing that one has an urge to pass them on. Contributions are most welcome.     

Intercalated smectic-A structures in a new class of laterally branched substances

X-ray, DSC and optical studies of a new class of substances with aromatic rings in the lateral branches are reported. The thermal behaviour of the substances is discussed. The X-ray measurements lead to a structural model of the SA phases consisting of layer structures with intercalating molecules.     

Raman spectroscopy of carbon fibres

Investigations of coated carbon fibres are reported using Raman spectroscopy. Relationships between different process parameters (for example precursor concentration, reactor temperature and various precursors) and the resulting types of carbon fibres are discussed.