Cold‐drawn induced microstructure in PVC‐bentonite nanocomposites

The mechanical properties and cold drawn‐induced micro and nanostructure of polyvinyl chloride (PVC)‐bentonite nanocomposites have been investigated. Molded sheets with 5 wt% concentration of bentonite and two processing additives were melt extruded and two‐roll‐milled processed. The flame retardant additive promoted polymer intercalation whereas a pigment dispersant promoted clay exfoliation, the polymer matrix showed isotropic orientation. The intercalated nanocomposite exhibited nanoplates oriented with their planes parallel to the molded sheet surface and the Young's modulus and yield stress were significantly enhanced relative to neat PVC. The strain at fracture (～144%) was slightly reduced relative to the matrix (～167%). Cold drawing induced molecular chain orientation along the tensile axis and preserved the orientation of the intercalated nanoclays. The fracture mechanism, as investigated via scanning electron microscopy (SEM) revealed plastic fracture mechanism (similar to neat PVC). On the other hand, the exfoliated nanocomposite did not show any improvement in mechanical properties but rather a significant decay of strain at fracture (～44%). The fractured region, as examined by SEM, exhibited microvoid morphology. Analysis of the fractured region showed PVC macromolecules oriented along the tensile axis but no preferred orientation of the nanoclays. The limited strain at fracture found for this material appears to be associated with the initially randomly oriented nanoclays being unable to orient under the tensile deformation. The nanoclays would act as stress concentrators leading to rapid material's failure due to loss of adhesion with the polymer matrix. The results suggest that exfoliated nanoclays could play a detrimental role when the nanocomposite is subjected to large deformations at temperatures well within the glassy regime. Copyright © 2009 John Wiley & Sons, Ltd.     

Critical slowing down in optical bistability

The role of critical slowing down in optical bistability is discussed, taking fully into account the non-linear effects. In particular, we show that the critical slowing down may lead to interesting novel applications, such as compact optical delay lines and electric field to time converters.     

Quantum mechanical masterequation and Fokker-Planck equation for the damped harmonic oscillator

For the statistical operator of the damped harmonic oscillator a Masterequation is given in operator form describing both inelastic and elastic, purely phase destroying processes. By expressing the statistical operator in the diagonal representation with respect toGlauber's coherent states the Masterequation is transformed into a Fokker-Planck equation forGlauber's quasiprobability distribution function. The general solution of this Fokker-Planck equation is calculated. It is shown how the solution of a Masterequation can be used for calculating correlation functions and expressions are given for the amplitude and intensity correlation functions which are in complete formal agreement with the corresponding classical formulae.     

Polycyclic aromatic hydrocarbons by ring-closing metathesis

A strategy for the synthesis of polycyclic aromatic hydrocarbons (PAHs) by the ring-closing olefin metathesis (RCM) of pendant olefins on a phenylene backbone has been developed. RCM of 2,4',6',2' '-tetravinyl-[1,1';3',1' ']terphenyl and 2,2',5',2' '-tetravinyl-[1,1';4',1']terphenyl affords in high yield the isomeric [a,j] and [a,h] dibenzanthracenes, respectively. In contrast with other intramolecular annulation methods, such as Friedel-Crafts acylations, this reaction is completely regioselective. Since RCM is reversible and PAHs are often thermodynamic sinks, this strategy is an effective and general method for the preparation of PAHs. Density functional theory calculations support these results. Carbon disulfide is a suitable solvent for these reactions.     

Synthesis and multidisciplinary characterization of polyelectrolyte multilayer-coated nanogold with improved stability toward aggregation

An interesting nanodrug delivery system is polyelectrolyte multilayer-coated nanogold. For better understanding of the binding of polycations or the counter-indicative deposition of polyanions on the citrate-stabilized gold nanoparticles, we used a surface-enhanced Raman spectroscopy to characterize the orientation of the polyions towards the gold surface. It was found that poly-allylamine replaces citrate molecules while the polyanion, poly-styrene sulfonate, intercalates in the citrate shell. One of the major obstacles for polyelectrolyte-coated nanogold is its tendency to agglomerate in the presence of high ion concentration as present, e.g., in blood. A novel encapsulation protocol for polyelectrolyte multilayer coating of gold nanoparticles was developed to successfully overcome this drawback. Moreover, electrostatic functionalization of the polyelectrolyte shell with a model target molecule for cancer, folic acid, induced a significant increase in the particle uptake in folate-receptor over-expressing breast cancer cell lines, VP 229 and MDA MB 231, compared to non-targeted particles or cells (non-activated macrophages) not expressing the folate receptor.     

Magnetocaloric properties of as-quenched Ni50.4Mn34.9In14.7 ferromagnetic shape memory alloy ribbons

The temperature dependences of magnetic entropy change and refrigerant capacity have been calculated for a maximum field change of Δ H=30 kOe in as-quenched ribbons of the ferromagnetic shape memory alloy Ni_50.4Mn_34.9In_14.7 around the structural reverse martensitic transformation and magnetic transition of austenite. The ribbons crystallize into a single-phase austenite with the L2₁-type crystal structure and Curie point of 284 K. At 262 K austenite starts its transformation into a 10-layered structurally modulated monoclinic martensite. The first- and second-order character of the structural and magnetic transitions was confirmed by the Arrott plot method. Despite the superior absolute value of the maximum magnetic entropy change obtained in the temperature interval where the reverse martensitic transformation occurs (|\varDelta S_M^max|=7.2 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=7.2\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}) with respect to that obtained around the ferromagnetic transition of austenite (|\varDelta S_M^max|=2.6 J kg^-1 K^-1)(|\varDelta S_{\mathrm{M}}^{\max}|=2.6\mbox{ J}\,\mbox{kg}^{-1}\,\mbox{K}^{-1}), the large average hysteretic losses due to the effect of the magnetic field on the phase transformation as well as the narrow thermal dependence of the magnetic entropy change make the temperature interval around the ferromagnetic transition of austenite of a higher effective refrigerant capacity (RC^magn_eff=95J kg^-1\mathrm{RC}^{\mathrm{magn}}_{\mathrm{eff}}=95\mbox{J}\,\mbox{kg}^{-1} versus RC^struct_eff=60J kg^-1)\mathrm{RC}^{\mathrm{struct}}_{\mathrm{eff}}=60\mbox{J}\,\mbox{kg}^{-1}).     

The self-consistent pendulum picture of the free electron laser revised

We reconsider the one-particle dynamics of a Free Electron Laser, adopting the so-called universal scaling. By a fully hamiltonian treatment of the electron and radiation field variables, we show that the electron phase-plane is never that of a pendulum. Actually, besides an elliptic and a hyperbolic pendulum-like fixed point, an extra elliptic point is present at the same phase value as the hyperbolic one, for large values of the detuning parameter δ. On decreasing δ, these two points collapse, which implies a dramatic change in the electron orbit topology, at a value of the detuning parameter which coincides with the instability threshold for exponential gain in the many-electron system.