Polymorphism in alternating polyketones studied by x-ray diffraction and calorimetry

Differential scanning calorimetry and high temperature x-ray diffraction were used to study the perfectly alternating copolymer of ethene and carbon monoxide (polyketone; POKC2). It was found that oriented POK-C2 fibers show a crystalline phase transition at a temperature between 110–125°C with a 10% change in crystalline density. At this temperature, the crystal structure reported recently (POK-α) is transformed to a crystal structure that was reported in the past for room temperature imperfectly alternating polyketone. The latter structure will be designated as POK-β. The influence of chain defects on the crystal structure was studied by synthesizing terpolymers (POK-C2/C3), in which small amounts of propylene-CO units are incorporated into the polymer backbone. The resulting terpolymers differ from the copolymer by the presence of methyl groups randomly distributed along the polyketone backbone chain. Evidence is presented that indicates that the methyl groups are built into the crystal lattice as defects. With more than 5 mole-% propene the terpolymer fibers crystallize exclusively in the β-modification. Below this level the α/β ratio (at room temperature) increases with decreasing amounts of propene. Both as-synthesized and as-spun POK-C2 were found to consist of both POK-α and POK-β; the α/β ratio depends on the method of preparation. Because the drawn POK-C2 fibers studied here consist exclusively of POK-α, the process of spinning and drawing leads to the transformation of unoriented β-rich material into oriented POK-α. © 1995 John Wiley & Sons, Inc.     

Chaotic Maps, Control Parameter, and Liapunov Exponent

We describe a one-dimensional chaotic map wherethe Liapunov exponent is a smooth function of a controlparameter.     

Fixed mesh approximation of ordinary differential equations with impulses

When trains of impulse controls are present on the right-hand side of a system of ordinary differential equations, the solution is no longer smooth and contains jumps which can accumulate at several points in the time interval. In technological and physical systems the sum of the absolute value of all the impulses is finite and hence the total variation of the solution is finite. So the solution at best belongs to the space BV of vector functions with bounded variation. Unless variable node methods are used, the loss of smoothness of the solution would a priori make higher-order methods over a fixed mesh inactractive. Indeed in general the order of -convergence is and the nodal rate is . However in the linear case -convergence rate remains but the nodal rate can go up to by using one-step or multistep scheme with a nodal rate up to when the solution belongs to . Proofs are given of error estimates and several numerical experiments confirm the optimality of the estimates. Received March 15, 1996 / Revised version received January 3, 1997     

Pricing and distributed QoS control for elastic network traffic

We study a processor-sharing model in which users choose between a high- and a low-priority service, based on their utility functions and prices charged by the service provider. The latter aims at revenue maximization. The model is motivated by file transmissions in data networks with distributed congestion control.     

Weighted Sobolev embedding with unbounded and decaying radial potentials

We prove embedding results of weighted W1,p(RN) spaces of radially symmetric functions. The results then are used to obtain ground and bound state solutions of quasilinear equations with unbounded or decaying radial potentials.     

The generator coordinate approximation for molecules: A review

The generator coordinate approximation is a non-adiabatic theory of molecular systems. Its fundamental outlines were developed during the 1970's. A further analysis and first applications were published during the 1980's. In this paper, we review the present status of the theory.     

Kinetics and mechanisms of chlorine transfer from chloramine to amines in aqueous medium

The kinetics and the equilibrium constant of the chlorine transfer reaction between monochloramine NH₂Cl and the amines: C₂H₅NH₂, (CH₃)₂CHNH₂, (CH₃)₂NH, and (C₂H₅)₂NH are investigated by spectrophotometry in aqueous medium at 25°C, in the pH range from 8 to 13 and for an ionic strength equal to 1.03 ± 0.05M. For a concentration of total ammonia equal to 1M, the observed rate constant is pH independent below 8 and above 12.8 and reaches a maximum located between the pK_as of NH₄⁺ and RR'NH₂⁺. From these results and those obtained earlier for NH₂Cl and CH₃NH₂, the reaction is shown to involve an interaction between neutral molecules NH₂Cl and RR'NH, subject to general acid catalysis. The ability of an interaction corresponding to a specific catalysis and involving NH₃Cl⁺ and RR'NH rather than NH₂Cl and RR'NH₂⁺ is also discussed. The activation parameters are given for each reaction.     

Algebraic cycles and topology of real Enriques surfaces

For a real Enriques surface Y we prove that every homology class in H₁(Y (R), Z/2) can be represented by a real algebraic curve if and only if all connected components of Y(R) are orientable. Furthermore, we give a characterization of real Enriques surfaces which are Galois-Maximal and/or Z-Galois-Maximal and we determine the Brauer group of any real Enriques surface Y.