Solubility of helium in melts of the metallic glass system Pd-Ni-P and in related systems

Glass melts of the metallic alloy system Pd_10–70Ni_10–70P_14–26 were saturated with helium gas during the melt-spinning process. Some melts with platinum substituted for palladium; manganese, iron or cobalt for nickel; and boron for phosphorus could also be saturated. The helium could be extracted from the glasses and the amount of gas was quantitatively measured with a mass spectrometer. The helium solubilities, obtained between 750 and 1250° C, varied between about 2 and 45 (l He per mol glass) (T/273). These solubilities turned out to be strongly composition-dependent. This fact is discussed in terms of different short-range order structure units which are directly related to the free volume available for the gas solution process.     

Polymer melt elongation—methods,results, and recent developments

For film blowing of polyethylene it has been shown previously that melt elongation is very powerful for polymer characterization. With two types of rheometers, simple (also called “uniaxial”) elongational tests as well as creep tests can be performed homogeneously. In simple elongation, the melts of branched polyethylene show a remarkable strain hardening. With respect to their advantages and disadvantages, these rheometers complement each other. For multiaxial elongations the various modes of deformation can be performed by means of the rotary clamp technique. With the strain rate components ordered such that \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}₁₁ ? \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}₂₂ ≥ \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}₃₃, the ratio m = \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}₂₂/\documentclass{article}\pagestyle{empty}\begin{document}$ \dot \varepsilon $\end{document}₁₁ characterizes the test mode. The Stephenson definition of the elongational viscosities makes use of the linear viscoelastic material equation and proves to be very efficient because the linear shear viscosity (t) (“stressing” viscosity) can act as the reference for the nonlinear behavior in elongation. Results are given for polyisobutylene measured not only in simple, equibiaxial, and planar elongations, but also in new test modes with a change of m during the deformation. This allows one to investigate the consequences of a deformation-induced anisotropy of the rheological behavior.     

A Distributed O(1)-Approximation Algorithm for the Uniform Facility Location Problem

We investigate a metric facility location problem in a distributed setting. In this problem, we assume that each point is a client as well as a potential location for a facility and that the opening costs for the facilities and the demands of the clients are uniform. The goal is to open a subset of the input points as facilities such that the accumulated cost for the whole point set, consisting of the opening costs for the facilities and the connection costs for the clients, is minimized. We present a randomized distributed algorithm that computes in expectation an ${\mathcal {O}}(1)$ -approximate solution to the metric facility location problem described above. Our algorithm works in a synchronous message passing model, where each point is an autonomous computational entity that has its own local memory and that communicates with the other entities by message passing. We assume that each entity knows the distance to all the other entities, but does not know any of the other pairwise distances. Our algorithm uses three rounds of all-to-all communication with message sizes bounded to $\mathcal{O}(\log(n))$ bits, where n is the number of input points. We extend our distributed algorithm to constant powers of metric spaces. For a metric exponent ?≥1, we obtain a randomized ${\mathcal {O}}(1)$ -approximation algorithm that uses three rounds of all-to-all communication with message sizes bounded to $\mathcal{O}(\log(n))$ bits.     

Wiederaufarbeitung von Kernbrennstoffen

Reprocessing of spent nuclear fuels . The present waste disposal concept for nuclear power plant requires the rapid construction of a reprocessing plant in the Federal Republic of Germany, with the location still being uncertain (Bavaria or Lower Saxony). The task of such a plant will consist in recovering usable nuclear fuels and processing them to new fuel elements. Waste materials are prepared for final disposal. The components of the plant are presented with their design data, associated development plans are discussed, and changes with respect to former plans, in particular the maintenance concept, are outlined. The article also reports the present status of the licensing procedure and current planning.     

Controlled destruction of residual crosslinker in a silicone elastomer for drug delivery

In drug delivery systems that use silicone elastomers as a diffusion matrix for the active drug, it is common to crosslink the material by the hydrosilylation reaction. In this platinum‐catalyzed reaction, vinyl groups on a polymer add to the methyl siloxane hydride (MHS) groups on a low molecular mass crosslinker. With an excess of crosslinker, a fast curing is achieved and a fully crosslinked material is formed. Unreacted MHS groups were shown to remain in the elastomer after curing because of the excess crosslinker. In this work, a simple procedure was developed to eliminate the unreacted MHS groups from the final product. We found that storage of the product at +40°C and 75% relative humidity for a few weeks will effectively destroy the residual MHS groups in the elastomer. The effects of varying levels of humidity, oxygen, and temperature on this postcuring procedure were studied. The amount of MHS groups was measured with NMR and IR spectroscopy. We also found that the hardness of the material increased by approximately 25% as a consequence of this postcuring treatment. This increase is probably due to a secondary crosslinking reaction between MHS and silanol groups. Heat treatment at higher temperatures led to an even further increase in the hardness and compression modulus. Because no MHS groups remained in the elastomer when this heat treatment was started, it is apparent that another secondary crosslinking reaction is occurring, probably silanol condensation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2254–2264, 2002     

High-pressure fluidized bed coating utilizing supercritical carbon dioxide

Various particles with sizes between 100 and 200 μm were encapsulated with waxes commonly used in technical coating applications. For this, a homogeneous mixture of molten paraffin and supercritical carbon dioxide was prepared in an autoclave and injected into the high-pressure fluidized bed through a nozzle from the bottom. Due to the different conditions in the mixing autoclave and the fluidized bed, the paraffin precipitated in the vicinity of the nozzle and adhered to the solid particles. A complete, thin, uniform, and solvent-free coating was produced. The use of two paraffins with different alkane compositions resulted in dissimilar spreads on glass beads due to their different glass transition temperatures. A smaller pressure drop across the nozzle led to more uniform and even coatings. Glass beads, ceramic spheres, potassium chloride, and lactose showed similar coating results, whereas different morphologies were observed with a plastic material, characterized by a rougher surface and a lower surface energy. The high quality of the coating was confirmed by standard dissolution tests with coated potassium chloride crystals and lactose agglomerates.     

Piezo- and pyroelectricity in polymer blends of poly(vinylidene fluoride)/poly(methyl methacrylate)

Compatible polymer blends of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) can be used as suitable model systems for investigating the relationship between the physico-chemical structure of polymers and their piezo- and pyroelectric activity. The structure of PVDF/PMMA blends can be varied over a very wide range which can lead to a strong influence on the piezo- and pyroelectric activity and the corresponding coefficients d₃₁ and g₃. The values of d₃₁ and g₃ were found to vary over nearly five decades whereas the normalized coefficients $\text{d}{}_{31}\text{P}$ and $\text{g}{}_3\text{P}$ remain largely unaffected. This emphasizes the importance of the molecular processes causing the macroscopic polarization P during the poling procedure. For a given polarization P and a given temperature T the properties of the polymer matrix, however, are far less important for the values obtained for d₃₁ and g₃. The experimental results were compared with theoretical predictions based on models which were recently developed by Tashiro et al., Broadhurst et al. and by Mopsik et al.. Considering the appropriate scope of each model a good agreement between theory and experiment is observed and general contradictions have not been found.     

The significance of defect chemistry for the rate of gas–solid reactions: three examples

Three examples are revisited in which the reaction rate could be reliably correlated with point defect chemistry highlighting the role of point defects as acid–base active centers. In the case of dehydrohalogenation of tertiary butyl chloride, AgCl becomes increasingly active as heterogeneous catalyst, if AgCl is homogeneously or heterogeneously doped. By such a procedure the silver vacancy concentration is adequately increased. The oxygen incorporation into SrTiO₃ offers an example in which the surface mechanism in terms of adsorbed species, oxygen vacancies and electronic centers has been elucidated. Appropriate surface coatings give rise to significant catalytic effects. Increasing iron (acceptor) doping not only changes the point defect chemistry but also the nature of the rate determining step. Lastly, the electrocatalytic function of Sr-doped LaMnO₃ is considered as regards oxygen reduction reaction and O²⁻ incorporation into Y-doped ZrO₂ in the context of solid oxide fuel cells. Again the defect chemistry is of prime importance for the reaction rate.