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81.
Theoretical models of the interfacial tension coefficient in polymer blends, v12, were evaluated. A new working relation was derived that makes it possible to compute v12 from the chemical structure of two polymers. The calculations involve determination of the dispersive, polar and hydrogen-bonding parts of the solubility parameter from the tabulated group and bond contributions. The computed values of v12 for 46 blends were found to follow the experimental ones with a reasonable scatter of ± 36%. Next, the experimental methods of v12-measurements were critically examined. Although many have been developed for low viscosity Newtonian fluids, most are irrelevant to industrial polymeric systems. For the present studies two were selected. Values of v12 were measured using the so-called “capillary breakup method,” and a newly developed method based on the retraction rate of deformed drop. 相似文献
82.
Joanna Korec Karol A. Stasiewicz Katarzyna Garbat Leszek R. Jaroszewicz 《Molecules (Basel, Switzerland)》2021,26(24)
This paper is a continuation of previous work and shows the enhancement of the surface plasmon resonance effect in a tapered optical fiber device. The study investigated liquid crystal cells containing a tapered optical fiber covered with a silver nanolayer, surrounded by a low refractive index liquid crystal in terms of the properties of light propagation in the taper structure. Silver films with a thickness of d = 10 nm were deposited on the tapered waist area. Measurements were performed at room temperature; liquid crystal steering voltage U from 0 to 200 V, with and without any amplitude modulation with a frequency of f = 5 Hz, and the wavelength λ ranged from 550 to 1200 nm. A significant influence of the initial arrangement of liquid crystals molecules on light propagation was observed. Three types of liquid crystal cells—orthogonal, parallel, and twist—were considered. During the measurements, resonant peaks were obtained—the position of which can also be controlled by the type of liquid crystal cells and the steering voltage. Based on the obtained results, the best parameters, such as highest peak’s width reduction, and the highest SNR value were received for twisted cells. In addition, the present work was compared with the previous work and showed the possibility of improving properties of the manufactured probes, and consequently, the surface plasmon resonance effect. In the presented paper, the novelty is mainly focused on the used materials as well as suitable changes in applied technological parameters. In contrast to gold, silver is characterized by different optic and dielectric properties, e.g., refractive index, extension coefficient, and permittivity, which results in changes in the light propagation and the SPR wavelengths. 相似文献
83.
In this paper we prove the existence of solutions for a hyperbolic hemivariationalinequality of the form u″ + Bu + ∂j (u) ∋ f where B is a linear elliptic operator and ∂j is the Clarke subdifferential of a locally Lipschitz function j. Our result is based on the parabolic regularization method. 相似文献
84.
Dariusz Bieliński Leszek Pysklo Jan Dul Ludomir Ślusarski Grażyna Janowska Grażyna Lewandowicz 《Macromolecular Symposia》2003,194(1):233-240
Characterization of the surface layer of starch powder, originated from potato or maize, was carried out applying various experimental techniques: Fourier-transformed infrared internal reflection spectroscopy (FTIR-IRS), inverse gas chromatography (IGC) and scanning electron microscopy (SEM). The main kinds of starch were studied as potential fillers for rubber and results discussed in terms of factors requiring modification to improve starch miscibility and activity towards rubber. Starch of high amylopectine content shows surface enrichment with amylose what makes crystallinity of the surface layer higher than in bulk of the material. Particles of the both kinds of starch have very smooth surface (morphological index, Im = 0.995), highly resistant to its geometrical development. Dispersive component of the surface energy of starch was found to be similar to that of low energy polymers (γsd = 32.5 mJ/m2 at 23°C) and its surface to be of electron-donor character. 相似文献
85.
Wout De Nolf Jakub Jaroszewicz Roberto Terzano Ole Christian Lind Brit Salbu Bart Vekemans Koen Janssens Gerald Falkenberg 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(8):775
The performance of a combined microbeam X-ray fluorescence/X-ray powder diffraction (XRF/XRPD) measurement station at Hamburger Synchrotronstrahlungslabor (HASYLAB) Beamline L is discussed in comparison to that at European Synchrotron Radiation Facility (ESRF) ID18F/ID22. The angular resolution in the X-ray diffractograms is documented when different combinations of X-ray source, optics and X-ray diffraction detectors are employed. Typical angular resolution values in the range 0.3–0.5° are obtained at the bending magnet source when a ‘pink’ beam form of excitation is employed. A similar setup at European Synchrotron Radiation Facility beamlines ID18F and ID22 allows to reach angular resolution values of 0.1–0.15°. In order to document the possibilities and limitations for speciation of metals in environmental materials by means of Hamburger Synchrotronstrahlungslabor Beamline L X-ray fluorescence/X-ray powder diffraction setup, two case studies are discussed, one involved in the identification of the crystal phases in which heavy metals such as chromium, iron, barium and lead are present in polluted soils of an industrial site (Val Basento, Italy) and another involved in the speciation of uranium in depleted uranium particles (Ceja Mountains, Kosovo). In the former case, the angular resolution is sufficient to allow identification of most crystalline phases present while in the latter case, it is necessary to dispose of an angular resolution of ca. 0.2° to distinguish between different forms of oxidized uranium. 相似文献
86.
87.
Leszek Plaskota Grzegorz W. Wasilkowski 《Journal of Fixed Point Theory and Applications》2009,6(2):227-248
This is an overview of recent results on complexity and optimality of adaptive algorithms for integrating and approximating
scalar piecewise r-smooth functions with unknown singular points. We provide adaptive algorithms that use at most n function samples and have the worst case errors proportional to n−r for functions with at most one unknown singularity. This is a tremendous improvement over nonadaptive algorithms whose worst case errors are at best proportional to n−1 for integration and n−1/p for the Lp approximation problem. For functions with multiple singular points the adaptive algorithms cease to dominate the nonadaptive
ones in the worst case setting. Fortunately, they regain their superiority in the asymptotic setting. Indeed, they yield convergence of order n−r for piecewise r-smooth functions with an arbitrary (unknown but finite) number of singularities. None of these results hold for the L∞ approximation. However, they hold for the Skorohodmetric, which we argue to be more appropriate than L∞ for dealing with discontinuous functions. Numerical test results and possible extensions are also discussed. 相似文献
88.
The axial coordination of central Mg(2+) ion in chlorophylls is of great structural and functional importance for virtually all photosynthetic chlorophyll proteins; however, little thermodynamic data are available on the ligand binding to these pigments. In the present study, spectral deconvolution of the bacteriochlorophyll Q(X) band serves to determine the ligand binding equilibria and relationships between thermodynamic parameters of ligand binding, ligand properties, and steric interactions occurring within the pigment. On the basis of the temperature effects on coordination, DeltaH degrees, DeltaS degrees, and DeltaG degrees of binding various types of ligands (acetone, dimethylformamide, imidazole, and pyridine) to diastereoisomeric bacteriochlorophylls were derived from respective van't Hoff's plots. At ambient temperatures, only ligation by imidazole and pyridine occurs spontaneously while DeltaG degrees becomes positive for ligation by acetone and dimethylformamide, due to a relatively large entropic effect, which is dominating when the energetic effects of ligation are small. It reflects, in quantitative terms, the control of the equatorial coordination of the Mg(2+) ion via the axial coordination: a "hard" free Mg(2+) ion is made into a softer center through the coordination of tetrapyrrole. Pigment structural features have comparable effects on the energetic and entropic contributions to the difference of ligation free energy between the diastereoisomers of bacteriochlorophyll. DeltaS degrees and DeltaH degrees values are consistently lower for the S epimer, most likely due to the steric crowding between bulky substituents. The two epimers show a 5 J.mol(-1).K(-1) difference in DeltaS degrees values, regardless of the ligand type, while the difference in DeltaH degrees amounts to 1.7 kJ.mol(-1), depending on the ligand. Such steric control of ligation would relate to the partial diastereoselectivity of chlorophyll self-assembly and, in particular, the very high diastereoselectivity of the ligation of chlorophylls in photosynthetic proteins. 相似文献
89.
Sliwińska-Bartkowiak M Ratajczak B Golibrocki L Banaszak M 《The Journal of chemical physics》2006,124(14):144516
We report the experimental and simulation studies for the system of nitrobenzene-cyclododecane, showing an apparent critical point, which lies in their metastable, experimentally inaccessible state, below their melting point, affecting physical and chemical properties of this system in the stable liquid phase. The nonlinear dielectric effect (NDE) was measured in the mixture of nitrobenzene with cyclododecane. The mixture has been found to show an apparent critical point which lies below the melting point, manifested as anomalous NDE behavior in the vicinity of the critical concentrations in the stable liquid phase. The melting temperature of this system was estimated using the differential scanning calorimetry method. For such a system, we also performed Monte Carlo (MC) simulations that aimed to analyze the kinds of phase transitions observed and the conditions of their occurrence in Lennard-Jones mixture. The enthalpy, configurational energy, and radial distribution function have been estimated by the MC simulation method in the N-P-T system. Immiscibility conditions according to the approach by Schoen and Hoheisel [Mol. Phys. 57, 65 (1986)] are also discussed. 相似文献
90.
Krzysztof Staliński Zofia Urbańczyk-Lipkowska Leszek Rupnicki 《Journal of organometallic chemistry》2006,691(11):2394-2402
A series of tri- and tetraorganotin compounds containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand and tert-butyl, methyl and/or phenyl groups on the tin has been synthesized. All the novel compounds have been characterized, especially by means of the multinuclear NMR investigation, the results of which are discussed. The tin halides, as pairs of diastereoisomers in solution, crystallize in the form of one diastereoisomer. The single-crystal X-ray analysis of tin iodide 10a revealed pseudo-equatorial position of the tert-butyl group opposite to the isopropyl group. In the corresponding diastereomeric tin hydrides values of 1J(1H-117/119Sn) differ significantly, suggesting a different pseudo-axial/equatorial position of the hydrogen atom. 相似文献