Extrusion of pastes with a piston extruder for the determination of the local solid and fluid concentration, the local porosity and saturation and displacement profiles by means of NMR imaging

 Nuclear Magnetic Resonance (NMR) was used to investigate the extrusion behaviour of PTFE pastes in a ram extruder. By means of ¹H-NMR imaging (MRI) it is possible to determine the local proton density and therefore, the local fluid concentration. The ¹⁹F-MRI provides the local solid concentration. Thus the local saturation and the local porosity can be calculated with the information of the local fluid and solid concentration. Furthermore displacement profiles can be derived from NMR images by means of correlation techniques without any preparation or marking of the pastes. Received: 8 May 2000   Accepted: 1 May 2001     

Measurement of the Seperation between Atoms beyond Diffraction Limit

We propose a scheme to obtain the distance of two identical atoms placed inside the standing wave field by monitoring the collective resonance fluorescence spectrum emitted by the two particles. We find three different parameter ranges, depending on the distance of the atoms as compared to the transition wavelength. For large interparticle distances, dipole-dipole coupling is negligible, and the main system evolution arises from the interaction with the standing wave field. In the small-distance limit, the dynamics is dominated by the dipole-dipole interaction. Finally, in the intermediate region, a rich interplay of the various couplings arises, which however is lifted for strong driving laser fields. The present measurement procedure allows us to distinguish the three cases. In each of the cases, we show how to determine the distance of the two particles and their respective positions relative to the nodes of the standing wave field with fractional-wavelength precision.     

Palladium complexes of a chiral P,C-chelating phosphino-(sulfinylmethyl)phosphonium ylide ligand

A new type of phosphino-phosphonium ylide ligand bearing a chiral sulfinyl center affords a P,C-chelated palladium(II) complex with a resolved asymmetric ylidic carbon atom. According to ³¹P NMR analysis of the crude material, the diastereoselectivity of the complexation at room temperature is ca. 7:1. In the crystal state, an X-ray diffraction analysis of one epimer reveals a quasi C₂-symmetric chloro-bridged dinuclear structure, where the (S) configuration of the sulfur atom induces a (S) configuration of the ylidic carbon atom. A in situ Pd(0) catalyst generated from the phosphino-ylide and Pd(PPh₃)₄ promotes allylic substitution of 3-acetoxy-1,3-diphenylpropene by sodium malonate in 70% yield and 5% e.e.     

Wait-and-switch stochastic model of the non-Debye relaxation. Derivation of the Burr survival probability

Stochastic mechanism of relaxation, in which a dipole waits until a favourable condition for reorientation exists, is discussed. Assuming that an imposed direction of a dipole moment may be changed when a migrating defect reaches the dipole, we present a mathematically rigorous scheme relating the local random characteristics of a macroscopic system to its effective relaxation behaviour. We derive a relaxation function (the Burr survival probability) that is characterized by the stretched exponential or the power-law behaviour.     

Unions and Intersections of Families of Lp-Spaces

Let L^Ψ and E^Ψ be the ORLICZ space and the space of finite elements respectively, on a measure space (Ω, Σ, μ), and let T ? (0, ∞). It is proved that if inf {p: p ? T} ? T or sup {p: p ? T} ? T and μ is an infinite atomless measure, then there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cup L^p }\limits_{p\varepsilon T} $\end{document} and moreover, there is no ORLICZ function Ψ such that: \documentclass{article}\pagestyle{empty}\begin{document}$ L^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document} or \documentclass{article}\pagestyle{empty}\begin{document}$ E^\varphi = Lin\mathop { \cap L^p }\limits_{p\varepsilon T} $\end{document}.     

Optimized conditions for hydrocarbon group type analysis of base oils by thin-layer chromatography-flame ionisation detection

The results of research on the optimization of the thin-layer chromatography-flame ionisation detection for the determination of group composition of natural base oils, including separation of the aromatics into subgroups, are presented. Neutral base oils obtained in several steps of refining from vacuum distillation petroleum fractions are the most difficult to analyze by hydrocarbon group type analysis (HGTA) because of the high content of aliphatic fragments in their molecules. Factors affecting the accuracy and precision of the results were identified. The paper presents the analytical procedure, including two different calibration methods, as well as the results of studies on the reproducibility of HGTA of typical base oils of different viscosity classes under the optimized conditions. The same conditions were found suitable for HGTA of other high-boiling petroleum fractions by TLC with flame ionisation detection. The paper also introduces a new procedure for reproducible determination of polar fractions in base oils utilizing solid-phase extraction columns, and presents a corrected procedure for the determination of saturated compounds and aromatics (mono-, bi- and polycyclic) in base oils by column liquid chromatography.     

On the Durrmeyer-type modification of some discrete approximation operators

In [10], for continuous functionsf from the domain of certain discrete operatorsL _n the inequalities are proved concerning the modulus of continuity ofL _nf. Here we present analogues of the results obtained for the Durrmeyer-type modification $\tilde L_n $ ofL _n. Moreover, we give the estimates of the rate of convergence of $\tilde L_n f$ in Hölder-type norms     

Balancing domain decomposition for problems with large jumps in coefficients

The Balancing Domain Decomposition algorithm uses in each iteration solution of local problems on the subdomains coupled with a coarse problem that is used to propagate the error globally and to guarantee that the possibly singular local problems are consistent. The abstract theory introduced recently by the first-named author is used to develop condition number bounds for conforming linear elements in two and three dimensions. The bounds are independent of arbitrary coefficient jumps between subdomains and of the number of subdomains, and grow only as the squared logarithm of the mesh size . Computational experiments for two- and three-dimensional problems confirm the theory.

     

Computer controlled spreading resistance system for measurement of carrier concentration profiles of silicon structures

A new computer controlled equipment for carrier concentration profile determination of silicon structures by a spreading resistance technique is presented. The required data and plots can easily be obtained by means of a new software package, which has been specially developed for this purpose. Measurements have been performed on different structures in order to verify the suitability of both the measuring system and the software package. The reproducibility has been found to be within 5% for the investigated structures.     

Kinetics and mechanism of the phenolysis of asymmetric diaryl carbonates

The reactions 4-methylphenyl 4-nitrophenyl carbonate (MPNPC), 4-chlorophenyl 4-nitrophenyl carbonate (CIPNPC), 4-methylphenyl 2,4-dinitrophenyl carbonate (MPDNPC), and 4-chlorophenyl 2,4-dinitrophenyl carbonate (CIPDNPC) with a homogeneous series of phenoxide anions are subjected to a kinetic investigation in aqueous solution (25.0 degrees C, ionic strength 0.2 M (KCI)). Under an excess of phenoxide with respect to the substrate, all of these reactions obey pseudo-first-order kinetics and are first order in phenoxide. The Br?nsted-type plots for the nucleophilic rate constants (k(N)) are linear, with slopes beta = 0.48 (MPNPC), 0.67 (ClPNPC), 0.41 (MPDNPC), and 0.32 (ClPDNPC). The magnitude of these slopes and the absence of a curvature in the Br?nsted plot at pK(a) = 7.1 for the CIPNPC reactions are consistent with concerted mechanisms (one step). The carbonates MPDNPC and ClPDNPC are more reactive than MPNPC and CIPNPC, respectively, toward phenoxide nucleophiles. This can be explained by the presence of a second nitro group in the nucleofuge of the dinitro derivatives, which (i) leaves their carbonyl carbon more positively charged, making them better electrophiles, and (ii) makes 2,4-dinitrophenoxide a better leaving group than 4-nitrophenoxide. The 4-chloro derivatives are more reactive than the corresponding 4-methyl derivatives. This should be due to the greater electron withdrawal of 4-chloro than 4-methyl, which makes the former carbonyl more electrophilic. Comparison of the concerted phenolysis of MPNPC with the stepwise reactions of secondary alicyclic amines with the same substrate indicates that substitution of a secondary alicyclic amine group in a zwitterionic tetrahedral intermediate by a phenoxy group greatly destabilizes the intermediate. An equation is deduced for log k(N) in terms of the basicity of the nucleophile, the nonleaving moiety, and the leaving group. This equation shows that for these reactions, the sensitivity of log k(N) to the basicity of the nonleaving moiety (beta(nlg) = -0.27) is very similar to that of the nucleofuge (beta(lg) = -0.25).