The change of the superstructure of semicrystalline polymers during deformation: results from small-angle scattering with synchrotron radiation

The change of the superstructure of different polyethylenes during uniaxial deformation is investigated. The method used is small-angle scattering with synchrotron radiation. For branched polyethylene (Lupolen 1840D) the whole deformation range is analyzed. Beginning with superstructure of the lamellar cluster type, the superstructure partly disappears on a time scale of a few minutes and the fibrillar structure is built up. The degree of destruction and rebuilding depends on the drawing temperature. For very high molecular weight polyethylene (GUR) a reversible change of the superstructure at higher deformation ratios and at different temperatures is observed. The superstructure of (ethylene—hexene) copolymers (TIPELIN) at high draw ratios depends on the drawing temperature and is almost independent of the side group content. Interfibrillar microcracks parallel to the draw direction are produced in samples with a low side group content for draw ratios λ ≥ 1.5.     

The many facets of linear programming

We examine the history of linear programming from computational, geometric, and complexity points of view, looking at simplex, ellipsoid, interior-point, and other methods. Received: June 22, 2000 / Accepted: April 4, 2001?Published online October 2, 2001     

Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Cores and retracts

Theretracts (idempotent, isotone self-maps) of an ordered set are naturally ordered as functions. In this note we characterize the possible ways that one retract can cover another one. This gives some insight into the structure of the ordered set of retracts and leads to a natural generalization of the core of an ordered set.Supported by NSERC Operating Grant 41702.     

π π andK¯K channel coupling

We investigate the origin of the attraction in theK¯K channel around the threshold by introducing an additional channel to theππ andK¯K channels in a separable potential formalism assuming, in general, no direct interaction in theK¯K channel. To reproduce the features of the data, we find that the threshold of the additional channel is much above thef ₀(975) meson position. We show that this three-channel problem can be reduced to an effective two-channel problem where thef ₀(975) behaves as if it were aK¯K molecule bound by the coupling to the exotic channel. This picture is also supported by the fact that a single pole only, in the complexK¯K momentum plane, is associated to thef ₀(975) meson. Various physical observables, like the decay branching ratio and theK¯K scattering length, are then discussed in an effective two-channel framework.     

Coboundaries of irreducible markov operators onC(K)

LetK be a compact Hausdorff space, and letT be an irreducible Markov operator onC(K). We show that ifgεC(K) satisfies sup _N ‖Σ _j ^=0N T ^j g‖<∞, then (and only then) there existsfεC(K) with (I − T)f=g. Generalizing the result to irreducible Markov operator representations of certain semi-groups, we obtain that bounded cocycles are (continuous) coboundaries. For minimal semi-group actions inC(K), no restriction on the semi-group is needed.