High-throughput experimentation in synthetic polymer chemistry: From RAFT and anionic polymerizations to process development

The application of combinatorial and high-throughput approaches in polymer research is described. An overview of the utilized synthesis robots is given, including different parallel synthesizers and a process development robot. In addition, the application of the parallel synthesis robots to reversible addition fragmentation termination (RAFT) radical polymerizations and ionic copolymerizations is overviewed. Moreover, first results concerning the process development of semi-batch free radical polymerizations are described.     

Thermal diffusivity measurements in porous ceramics by photothermal methods

Received: 16 September 1996/Accepted: 6 January 1997     

Photo-induced evolution of copper sheets from cluster molecules and its application to photolithographic copper patterning

UV photoexcitation of (t-butylethynyl copper)₂₄ cluster films induces segregation of the crystals into metallic and organic phases and leads to evolve the metallic sheets sandwiched by organic polymers. The growth of the metallic crystals in the plane of the photo-electromagnetic field is attributed due to plasmon-plasmon interaction among nanoparticles embedded in dielectric polymer matrices. The surface enhanced photochemical reaction of residual cluster molecules on the photon incident direction is expected to take an important role for joining the metal particles to produce a metallic sheet. We can apply this phenomenon for photolithographic copper pattern generation on a flexible base plate.     

Scalar and axial-vector mesons

Almost thirty years ago, Penny G. Estabrooks asked “Where and what are the scalar mesons?” (P. Estabrooks, Phys. Rev. D 19, 2678 (1979)). The first part of her question can now be confidently responded (E. van Beveren et al., Z. Phys. C 30, 615 (1986)). However, with respect to the “What” many puzzles remain unanswered. Scalar and axial-vector mesons form part of a large family of mesons. Consequently, though it is useful to pay them some extra attention, there is no point in discussing them as isolated phenomena. The particularity of structures in the scattering of --basically-- pions and kaons with zero angular momentum is the absence of the centrifugal barrier, which allows us to “see” strong interactions at short distances. Experimentally observed differences and similarities between scalar and axial-vector mesons on the one hand, and other mesons on the other hand, are very instructive for further studies. Nowadays, there exists an abundance of theoretical approaches towards the mesonic spectrum, ranging from confinement models of all kinds, i.e., glueballs, and quark-antiquark, multiquark and hybrid configurations, to models in which only mesonic degrees of freedom are taken into account. Nature seems to come out somewhere in the middle, neither preferring pure bound states, nor effective meson-meson physics with only coupling constants and possibly form factors. As a matter of fact, apart from a few exceptions, like pions and kaons, Nature does not allow us to study mesonic bound states of any kind, which is equivalent to saying that such states do not really exist. Hence, instead of extrapolating from pions and kaons to the remainder of the meson family, it is more democratic to consider pions and kaons mesonic resonances that happen to come out below the lowest threshold for strong decay. Nevertheless, confinement is an important ingredient for understanding the many regularities observed in mesonic spectra. Therefore, excluding quark degrees of freedom is also not the most obvious way of describing mesons in general, and scalars and axial-vectors in particular.     

Resonant Optical Absorption in Semiconductor Quantum Wells

We have calculated the intraband photon absorption coefficients of hot two-dimensional electrons interacting with polar-optical phonon modes in quantum wells. The dependence of the photon absorption coefficients on the photon wavelength λ is obtained both by using the quantum mechanical theory and by the balance-equation theory. It is found that the photon absorption spectrum displays a local resonant maximum, corresponding to LO energy, and the absorption peak vanishes with increasing the electronic temperature.     

Phenomenological πN→ππN amplitude and the modelling of the Olsson–Turner and Chew–Low approaches

The phenomenological amplitude for the reaction πN→ππN fixed by fittings to the experimental data in the energy region 0.300 ≤P _Lab≤ 500 MeV/c is used for modelling the Chew–Low extrapolation and Olsson–Turner threshold approach. It is shown that the uncritical application of the former results in enermous theoretical errors, the extracted values being in fact random numbers. The results of the Olsson–Turner method are characterized by significant systematic errors coming from unknown details of the isobar physics. Received: 10 December 1997     

Peak tailing in electrophoresis due to alteration of the wall charge by adsorbed analytes a: Numerical simulations and asymptotic theory

When analytes containing cationic components, such as proteins, are separated in fused silica capillaries or micro-chips, they adsorb strongly to the negatively charged channel walls. Broadened and highly asymmetric peaks in the detector signal is symptomatic of the presence of such wall interactions. Band broadening is caused by the introduction of shear into the electroosmotic flow which leads to Taylor dispersion. The shearing flow in turn is caused by axial variations in zeta-potential due to adsorbed analytes. In this paper, numerical solutions of the coupled electro-hydrodynamic equations for fluid flow and the advection-diffusion equation for analyte concentration are presented in the limit of thin Debye layers. The simulations reproduce many of the qualitative effects of wall adsorption familiar from observation. Further, the simulation results are compared, and found to agree very well (to within a percent for characteristic values of the parameters) with a recently developed asymptotic theory.     

Granular flows in a rotating drum: the scaling law between velocity and thickness of the flow

The flow of dry granular material in a half-filled rotating drum is studied. The thickness of the flowing zone is measured for several rotation speeds, drum sizes and beads sizes (size ratio between drum and beads ranging from 47 to 7400). Varying the rotation speed, a scaling law linking mean velocity vs. thickness of the flow, v∼h^m, is deduced for each couple (beads, drum). The obtained exponent m is not always equal to 1, the value previously reported for a drum in litterature, but varies with the geometry of the system. For small size ratios, exponents higher than 1 are obtained due to a saturation of the flowing zone thickness. The exponent of the power law decreases with the size ratio, leading to exponents lower than 1 for high size ratios. These exponents imply that the velocity gradient of a dry granular flow in a rotating drum is not constant. More fundamentally, these results show that the flow of a granular material in a rotating drum is very sensible to the geometry, and that the deduction of the “rheology” of a granular medium flowing in such a geometry is not obvious.     

Phenomenology and theory of horizontally oscillated granular mixtures

We overview the physics of a granular mixture subject to horizontal oscillations, recently investigated via experiments and molecular dynamics simulations. First we discuss the rich phenomenology exhibited by this system, which encompasses both segregation and dynamical instabilities. Then we show that the phenomenology can be explained via an effective interaction approach, by which the driven, non-thermal, granular mixture in mapped into a monodispersed thermal system of particles interacting via an effective potential. After determining the effective interaction we discuss its microscopic origin and investigate how it induces the observed phenomenology. Finally, as much as in thermal fluids, from the effective interaction we derive a Cahn-Hilliard dynamics equation, which appears to capture the essential characteristics of the dynamics of the granular mixture.     

Strength and failure of cemented granular matter

Cemented granular materials (CGMs) consist of densely packed solid particles and a pore-filling solid matrix sticking to the particles. We use a sub-particle lattice discretization method to investigate the particle-scale origins of strength and failure properties of CGMs. We show that jamming of the particles leads to highly inhomogeneous stress fields. The stress probability density functions are increasingly wider for a decreasing matrix volume fraction, the stresses being more and more concentrated in the interparticle contact zones with an exponential distribution as in cohesionless granular media. Under uniaxial loading, pronounced asymmetry can occur between tension and compression both in strength and in the initial stiffness as a result of the presence of bare contacts (with no matrix interposed) between the particles. Damage growth is analyzed by considering the evolution of stiffness degradation and the number of broken bonds in the particle phase. A brutal degradation appears in tension as a consequence of brittle fracture in contrast to the more progressive nature of damage growth in compression. We also carry out a detailed parametric study in order to assess the combined influence of the matrix volume fraction and particle-matrix adherence. Three regimes of crack propagation can be distinguished corresponding to no particle damage, particle abrasion and particle fragmentation, respectively. We find that particle damage scales well with the relative toughness of the particle-matrix interface with respect to the particle toughness. This relative toughness is a function of both matrix volume fraction and particle-matrix adherence and it appears therefore to be the unique control parameter governing transition from soft to hard behavior.