Extension of the chain‐end,free‐volume theory for predicting glass temperature as a function of conversion in hyperbranched polymers obtained through one‐pot approaches

Compared with linear polymers, more factors may affect the glass‐transition temperature (T_g) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. T_g's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of T_g to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. T_g's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. T_g values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. T_g values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of T_g versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that T_g increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004     

Fast electrons generation by RF and random fields near the antenna I. One dimensional model and regular fields

Test particle motion and acceleration has been explored in strong radio frequency (RF) fields, for which quasilinear ponderomotive force approximation is not valid. By nonlinear acceleration in spatially varying wave amplitude of RF travelling wave, electrons may be accelerated to time averaged velocities significantly larger than the RF wave phase velocity, and than the boundary plasma thermal velocity, in RF fields of several Volts per centimeter at wave frequency of 7 MHz. It is also demonstrated that even weak spatial gradients, much weaker than those expected in experiments, of the RF wave field amplitude, have significant consequences for the particle motion. Estimates are presented of the total energy transferred from the near antenna RF field to the plasma due to the nonlinear electron acceleration effects.     

Transient binary nucleation from ethanol-hexanol vapour

We study condensation of ethanol-hexanol vapour by numerical solution of kinetic equations. The number of droplets formed in unit volume is computed within self-consistent classical model. It is shown that formation of ethanol-rich droplets prevails at the initial stage of nucleation process, but in the stationary state formation of droplets near the saddle point (on cluster formation energy surface) plays the dominant role. Presented at the 6th Joint Seminar “Development of Materials Science in Research and Education”, Karlštejn, Czech Republic, 17–19 September 1996. This work was supported by Grant No. A1010615 of the Grant Agency of the Academy of Sciences of the Czech Republic.     

Luttinger liquid with asymmetric dispersion

We present an extension of the Tomonaga-Luttinger model in which left and right-moving particles have different Fermi velocities. We derive expressions for one-particle Green's functions, momentum-distributions, density of states, charge compressibility and conductivity as functions of both the velocity difference ε and the strength of the interaction β. This allows us to identify a novel restricted region in the parameter space in which the system keeps the main features of a Luttinger liquid but with an unusual behavior of the density of states and the static charge compressibility κ. In particular κ diverges on the boundary of the restricted region, indicating the occurrence of a phase transition. Received 20 May 2002 / Received in final form 23 August 2002 Published online 19 November 2002     

Spin-trapped hydroxyl free radicals studied at low field by Field-Cycled Dynamic Nuclear Polarization

The technique of Field-Cycled Dynamic Nuclear Polarization (FC-DNP) involves the EPR irradiation of a free radical solution and the subsequent observation of the NMR signal, the experiment being carried out at a range of magnetic field strengths in order to measure the free radical’s EPR spectrum. In this work FC-DNP has been used to study the EPR spectrum of DMPO spin-trapped hydroxyl free radicals at magnetic field strengths between 0.5 mT and 13.0 mT (5–130 Gauss). The low-field EPR spectrum contains six separate EPR lines, in contrast to the well-known X-band spectrum where only four are seen. Knowledge of the spin-adduct’s EPR spectrum will be of use to workers involved in low-field EPR, especially those conducting biological or in-vivo spin-trapping experiments.     

Singular terms of helicity amplitudes at one loop in QCD and the soft limit of the cross sections of multi-parton processes

We describe a general method that enables us to obtain all the singular terms of helicity amplitudes of n-parton processes at one loop. The algorithm uses helicity amplitudes at tree level and simple color algebra. We illustrate the method by calculating the singular part of the one-loop helicity amplitudes of all 2 → 3 parton subprocesses. The results are used to derive the soft gluon limit of the cross sections of all 2 → 4 parton scattering subprocesses which provide a useful initial condition for the angular ordering approximation to coherent multiple soft gluon emission, incorporated in existing Monte Carlo simulation programs.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Erratum: Synthesis and characterization of diorganotin(IV) complexes of Schiff bases with ONO‐type donors and crystal structure of [N‐(2‐hydroxy‐4‐nitrophenyl)‐3‐ethoxysalicylideneiminato]diphenyltin(IV)

The article referenced above was first published online on 30 August 2007 with incorrect pagination; the pagination has now been corrected online and in print. Copyright © 2007 John Wiley & Sons, Ltd.     

Efficiency and effectiveness of Spanish football teams: a three-stage-DEA approach

In this paper, we apply a three-stage-DEA model to the Spanish Professional Football League, which means separating the teams’ economic behaviour into three components: operating efficiency—of the offence and defence—athletic or operating effectiveness, and social effectiveness. The results showed that the technical inefficiency of the defence is greater than that of the offence, both being caused by aspects linked to the poor management of players’ abilities and by the football team’s size. Teams showed a favourable evolution of their offensive and defensive efficiency during the 2004/2005 season and to a lesser extent in the season before. The point system assigned by the professional football league regulations evaluates the teams’ athletic effectiveness, but we detected that the teams with the most experience perform athletically in a more effective manner. Their social effectiveness is strongly related to the level of play in itself and to factors linked to their PFL ranking: participation in international competitions for important football teams; or the struggle of minor football teams to stay in the first division.