Glass transitions and mixed phases in block SBS

Differential scanning calorimetry (DSC) does not allow for easy determination of the glass‐transition temperature (T_g) of the polystyrene (PS) block in styrene–butadiene–styrene (SBS) block copolymers. Modulated DSC (MDSC), which deconvolutes the standard DSC signal into reversing and nonreversing signals, was used to determine the (T_g) of both the polybutadiene (PB) and PS blocks in SBS. The T_g of the PB block was sharp, at ?92 °C, but that for the PS blocks was extremely broad, from ?60 to 125 °C with a maximum at 68 °C because of blending with PB. PS blocks were found only to exist in a mixed PS–PB phase. This concurred with the results from dynamic mechanical analysis. Annealing did not allow for a segregation of the PS blocks into a pure phase, but allowed for the segregation of the mixed phase into two mixed phases, one that was PB‐rich and the other that was PS‐rich. It is concluded that three phases coexist in SBS: PB, PB‐rich, and PS‐rich phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 276–279, 2005     

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     

Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

QUALITATIVE AND QUANTITATIVE ANALYSIS OF STOCHASTIC PROCESSES BASED ON MEASURED DATA, II: APPLICATIONS TO EXPERIMENTAL DATA

Analysis of stochastic processes governed by the Langevin equation is discussed. The analysis is based on a general method for non-parametric estimation of deterministic and random terms of the Langevin equation directly from given data. Separate estimation of the terms corresponds to the decomposition of process dynamics into deterministic and random components. Part I of the paper presented several possibilities for qualitative and quantitative analysis of process dynamics based on such decomposition. In Part II, some of these analysis possibilities are applied to experimental datasets from metal cutting and laser-beam welding.     

Needle Variations and Almost Lower Semicontinuous Differential Inclusions

It is shown that the construction of needle variations can be carried out for almost lower semicontinuous differential inclusions rather than for the case of ordinary single-valued continuously differentiable vector fields usually considered in the literature. The construction leads to needle variations whose flows are in general set-valued but still have good differentiability properties. The variations are constructed by using single-valued selections that are not necessarily continuous with respect to the state variable, but have instead a much weaker 'integral continuity' property, somewhat more general that the 'directional continuity' considered in previous work by A. Cambini and S. Querci, A. Pucci, and A. Bressan. The existence of many such selections is proved by slightly adapting an argument due to Bressan, extending it from the lower semicontinuous to the almost lower semicontinuous case, and strengthening it to yield not only directional continuity at all points but also full continuity at a specified point.     

Galactic model of element formation

A cosmological model is presented that produces He, C, O, D, Li, Be, and B in their observed abundances without a Big Bang. The elements are produced during the 1.5-Gy formation period of a galaxy, with C, O, and other heavy elements produced by stars of M>12 M₃ , He by stars of 6 M_s<M<12 M_s, and D, Li, Be, and B by cosmic-ray reactions in a nearly pure H plasma halo. Thus, the model shows that the major elements used in astrophysical studies can be produced during galactic formation by exactly the same processes known to function today at much lower rates     

Self-broadening in the millimeter-wave spectrum of ozone

Self broadened widths of seven lines of ozone between 75 and 120 GHz have been measured at room temperature. The variation with temperature of the self-broadening parameter for three of these lines has been studied in the range 245–292°K.