Investigation into the ROMP copolymerization of peptide‐ and PEG‐functionalized norbornene derivatives

The ring‐opening metathesis polymerizations (ROMP), using RuCl₂ (PCy₃)₂CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007     

Lein?l, Lein?lfirniss und Oelfarben

Ohne Zusammenfassung     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

Effect of short glass fiber on structure and viscoelastic behavior of olefinic polymers synthesized with metallocene catalyst

Several composites were prepared on the basis of an ethylene homopolymer and different copolymers of ethylene and 1‐hexene, synthesized with a metallocene catalyst, as matrices and a content of a 5 wt % of short glass fiber. The effect of the fiber incorporation on the structure and mechanical and viscoelastic behaviors was analyzed for the different samples. The glass fibers induced a slightly higher crystallinity, and the crystallite morphology significantly changed (long spacings and crystal orientation). The incorporation of fibers did not reinforce the different matrices under study at this low content; consequently, the mechanical parameters, such as Young's modulus, yielding stress, and microhardness, were lower in the composites as compared with those values found in the neat polyolefins. The location and apparent activation energies of distinct relaxation processes are also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1244–1255, 2003     

Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003     

Morphological instability induced by the interaction of a particle with a solid-liquid interface

Motivated by recent experimental findings, we investigate the possible occurrence and characteristics of quasicrystalline order in two-dimensional mixtures of point dipoles with two sorts of dipole moments. Despite the fact that the dipolar interaction potential does not exhibit an intrinsic length scale and cannot be tuned a priori to support the formation of quasicrystalline order, we find that configurations with long-range quasicrystallinity yield minima in the potential energy surface of the many particle system. These configurations emanate from an ideal or perturbed ideal decoration of a binary tiling by steepest descent relaxation. Ground state energy calculations of alternative ordered states and parallel tempering Monte-Carlo simulations reveal that the quasicrystalline configurations do not correspond to a thermodynamically stable state. On the other hand, steepest descent relaxations and conventional Monte-Carlo simulations suggest that they are rather robust against fluctuations. Local quasicrystalline order in the disordered equilibrium states can be strong.Received: 15 September 2004, Published online: 26 November 2004PACS: 61.44.Br Quasicrystals - 75.50.Kj Amorphous and quasicrystalline magnetic materials - 82.70.Dd Colloids     

Mechanisms of n‐butanol formation in butyl acrylate latexes

The mechanisms involved in the formation of n‐butanol during the synthesis of butyl acrylate containing latices were investigated. The experimental results showed that neither the hydrolysis of butyl acrylate nor of the ester bond in the butyl acrylate segments of the polymer played a major role in the formation of n‐butanol, which was mainly generated from the polymer backbone, by transfer reactions to polymer chain followed by cyclization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5838–5846, 2007     

Arsenic determination in marine sediment using ultrasound for sample preparation.

This work deals with As determination in marine sediment using ultrasound for sample preparation. It is shown that As can be quantitatively extracted from marine sediment using 20% (v/v) HCl and sonication. The slurry is centrifuged and the analyte is determined in the supernatant by hydride generation atomic absorption spectrometry (HG AAS). A flow injection (FI) system is employed for hydride generation, with 0.5% (m/v) NaBH(4) used as reducdant and a 20% (v/v) HCl used as sample carrier. The limit of quantification is 1.6 microg g(-1) of As, which is based on 800 microl of sample solution and 0.200 g of sample mass in a volume of 50 mL. Certified and non certified marine sediment samples were analyzed; the results were in accordance with the certified or reference values. Speciation analysis by HPLC-ICP-MS showed that As(V) is the only detectable As species present in the supernatant of the centrifuged sample.     

Study of the dynamic structure factor of strong glasses

The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm⁻¹. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q² dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.     

Closed-form solutions for a rectangular layer with central crack under anti-plane shear stress

We consider the problem of determining the stress distributionin a finite rectangular elastic layer containing a Griffithcrack which is opened by internal shear stress acting alongthe length of the crack. The mode III crack is assumed to belocated in the middle plane of the rectangular layer. The followingtwo problems are considered: (A) the central crack is perpendicularto the two fixed lateral surfaces and parallel to the othertwo stress-free surfaces; (B) all the lateral surfaces of therectangular layer are clamped and the central crack is parallelto the two lateral surfaces. By using Fourier transformations,we reduce the solution of each problem to the solution of dualintegral equations with sine kernels and a weight function whichare solved exactly. Finally, we derive closed-form expressionsfor the stress intensity factor at the tip of the crack andthe numerical values for the stress intensity factor at theedges of the cracks are presented in the form of tables.