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     

The Influence of Variable Convective Velocities on Longitudinal Diffusion

Solutions are presented for the impulsively started uniformstream and simple shear flows past a point source of momentum,which can be interpreted to describe the position and the widthof the front which transmits the knowledge of the singularitythrough a slightly viscous fluid. These understandings are thengeneralized to show that the front always moves with velocityslower than that of a (strictly monotonic) convective velocity,and also that its width always grows faster than with simplediffusion. Finally, a remarkably simple, exact expression is given forvorticity due to a simple shear flow past a point vortex.     

Shape transition from InAs quantum dash to quantum dot on InP(3 1 1)A

We report on the shape transition from InAs quantum dashes to quantum dots (QDs) on lattice-matched GaInAsP on InP(3 1 1)A substrates. InAs quantum dashes develop during chemical-beam epitaxy of 3.2 monolayers InAs, which transform into round InAs QDs by introducing a growth interruption without arsenic flux after InAs deposition. The shape transition is solely attributed to surface properties, i.e., increase of the surface energy and symmetry under arsenic deficient conditions. The round QD shape is maintained during subsequent GaInAsP overgrowth because the reversed shape transition from dot to dash is kinetically hindered by the decreased ad-atom diffusion under arsenic flux.     

Nonlinear optical properties of regioregular main‐chain polyesters

We have prepared new polyesters containing quadratic, nonlinear optical (NLO) active chromophores covalently incorporated into the main chain. In these polymers, the sequence of the chromophore units along the main chain is rigorously head to tail. All the polyesters are processable, both in the melt and in solution. For one polyester, a full second‐order NLO characterization has been performed. An out‐of‐resonance d₃₃ coefficient of 21 pm/V at 1368 nm has been measured. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2719–2725, 2007     

Pressure effects in a plastic columnar discotic triphenylene

The effect of hydrostatic pressure on the structure of a plastic columnar discotic triphenylene has been investigated. The goal was to determine whether pressure can be used to modify electronic properties via changes in structural properties of columnar discotics to any significant extent. The findings are that (i) the intra- and inter-columnar distances are reduced in a nearly isotropic fashion, (ii) that the crystal sizes are reduced and (iii) that a transition takes place from a more highly ordered plastic columnar to a less ordered hexagonal columnar state with increasing pressure. The induced decrease of the molecular distances, amounting to 6% for pressures up to 17 kbar, are clearly too small to induce an appreciable modification of the electronic structure and thus opto-electronic properties.     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Control of a liquid–liquid heat exchanger

 The analytical solutions of equations describing the dynamics of distributed parameter systems are usually complicated in form and derivations and inconvenient to use for simulation and control system design. The liquid–liquid counter flow heat exchanger is an example of these disturbed parameter systems. An analytical solution of the dynamics of a symmetrically operated counter flow heat exchanger in the form of transfer function matrix is investigated in open-loop and close-loop conditions. The resulting non-linear model was linearized using perturbation approach. A feed-forward path controller to counteract at any disturbances in the boundary temperature and a non-interactive controller to decouple the outputs were implemented. Received on 22 February 2001 / Published online: 29 November 2001