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We present a two dimensional (2D) planar chromatographic separation of estrogenic active compounds on RP-18 (Merck, 1.05559) and silica gel (Merck, 1.05721) phase. A mixture of 13 substances was separated using a solvent mix consisting of methanol–acetonitrile–water (2 + 2 + 1, v/v/v) on RP-18 phase in the first direction and cyclohexane–butylacetate–methanol (8 + 6 + 1, v/v/v) in the second direction on silica gel plate. Both developments were carried out over a distance of 70 mm. We used the grafted method to combine both plates in a 2D-separation. This 2D-separation method can be used to quantify 17α-ethinylestradiol (EE2) in an effect-directed analysis using the yeast strain Saccharomyces cerevisiae BJ3505. The test strain (according to McDonnell) contains the estrogen receptor. Its activation by estrogen active compounds is measured by inducting the reporter gene lacZ that encodes the enzyme ß-galactosidase. This enzyme activity is determined on plate by using the fluorescent substrate MUG (4-methylumbelliferyl ß-D-galactopyranoside).
Lithium–sulfur (Li/S) cells are promising candidates for a next generation of safe and cost-effective high energy density batteries for mobile and stationary applications. At present, most Li/S cells still suffer from relatively poor cyclability, capacity loss under moderate current densities and self-discharge. Furthermore, the underlying chemical mechanisms of the general discharge/charge behavior as well as Li/S-specific phenomena like the polysulfide shuttle are not yet fully understood. Here we present a thermodynamically consistent, fully reversible continuum model of a Li/S cell with simplified four-step electrochemistry, including a simple description of the polysulfide shuttle effect. The model is parameterized using experimental discharge curves obtained from literature and reproduces behavior at various current densities with fairly high accuracy. While being instructively simple, the presented model can still reproduce distinct macroscopic Li/S-cell features caused by the shuttle effect, e.g., seemingly infinite charging at low charge current densities, and suboptimal coulombic efficiency. The irreversible transport of active material from the cathode to the anode results in a voltage drop and capacity loss during cycling, which can also be observed experimentally.
The characteristic features and applications of linear and nonlinear guided elastic waves propagating along surfaces (2D) and wedges (1D) are discussed. Laser-based excitation, detection, or contact-free analysis of these guided waves with pump–probe methods are reviewed. Determination of material parameters by broadband surface acoustic waves (SAWs) and other applications in nondestructive evaluation (NDE) are considered. The realization of nonlinear SAWs in the form of solitary waves and as shock waves, used for the determination of the fracture strength, is described. The unique properties of dispersion-free wedge waves (WWs) propagating along homogeneous wedges and of dispersive wedge waves observed in the presence of wedge modifications such as tip truncation or coatings are outlined. Theoretical and experimental results on nonlinear wedge waves in isotropic and anisotropic solids are presented.
Pure component sorption isotherms of n-butane, isobutane, 1-butene and isobutene on the metal–organic framework (MOF) 3∞[Cu4(μ4-O)(μ2-OH)2(Me2trz-pba)4] at various temperatures between 283 K and 343 K and pressures up to 300 kPa are presented. The isotherms show a stepwise pore filling which is typical for structurally flexible materials with broad adsorption–desorption hysteresis loops. Gate opening pressures in their endemic characteristic depend on the used hydrocarbon gases. From all investigated gases only the isotherms of 1-butene present a second step at a relative pressure above p/p0 = 0.55. As a consequence, only 1-butene can fully open the framework resulting in a pore volume of 0.54 cm3 g−1. This result is in good agreement with the value of 0.59 cm3 g−1 calculated based on single crystal structure data. The isosteric heat of adsorption was calculated from the experimental isotherms for all C4-isomers. At low loadings the isosteric heat is in a narrow region between 41 and 49 kJ mol−1. Moreover, in situ XRD measurements at different relative hydrocarbon pressures were performed at 298 K for the C4-isomers. The differences in the pressure-depending powder diffraction patterns indicate phase transitions as a result of adsorption. Similar diffraction patterns were observed for all C4-hydrocarbons, except 1-butene, where the second step at higher relative pressure (p/p0 > 0.55) is accompanied by an additional phase transition. This powder pattern resembles that of the as-synthesized MOF material containing solvent molecules in the pore system. The resulting structural changes of the material during guest and pressure induced external stimuli are evidenced by the new coupled XRD adsorption equipment.
This paper presents new measurements of a bronze cast from the right hand of the famous Italian violin virtuoso Nicolò Paganini (1782-1840). These are compared to anthropometric standard values. In addition, detailed dorsal and palmar views of the cast are shown. With a middle finger length of 75 mm, the palm width is 60 mm and the hand length 152 mm, which is significantly below the 5% percentile of today's standard values. Also the finger length index (0.55), the ratio of finger length to palm length (0.98) and the ratio of finger length to palm width (1.25) are significantly above normal limits. Hence, Paganini had abnormal hand measurements with a very small palm and relatively "long" fingers. This remarkable constellation, among others, could have been advantageous for his amazing skills as a violinist.
Aqueous lithium–oxygen batteries are promising candidates for electric energy storage. In this paper we present and discuss a multiphase continuum model of an aqueous lithium–oxygen single cell including reactions and transport in a porous gas diffusion electrode (GDE). The model is parameterized using in-house half-cell experiments and available literature data on aqueous electrolytes. We validate our transport model with cyclic voltammetry and electrochemical impedance spectroscopy measurements over a wide range of temperatures (25, 40, 55 °C) and electrolyte concentrations (0.1–2 M). We observe very good agreement between simulations and measurements during oxygen reduction conditions. A sensitivity analysis of the validated model demonstrates the influence of the porous structure on GDE performance and gives directions for the future development of electrodes.
In 35 deutschen und 7 europäischen Büro- und Verwaltungsgebäuden wurden auf Basis von Monitoringkampagnen über mehrere Betriebsjahre Raum- und Außentemperaturwerte in zeitlich hoher Auflösung erfasst und der thermische Raumkomfort im Sommer standardisiert nach der Komfortnorm DIN EN 15251:2007-08 detailliert ausgewertet. Ergänzt wird die Auswertung um Kurzzeitmesskampagnen über zwei sehr warme Wochen im Sommer in unsanierten bzw. teilsanierten Bürogebäuden, errichtet im Zeitraum von 1960 bis 1975. Die untersuchten Gebäude mit ihrem jeweiligen Kühlkonzept lassen sich in sechs Kategorien einteilen: ohne Kühlung, passive, luftgeführte und wassergeführte Kühlung sowie Mixed-mode-Kühlung und Vollklimatisierung. Im Quervergleich aller Gebäude werden die Kühlkonzepte gleichermaßen nach dem thermischen Raumkomfort und thermischen Kühlenergiebezug bewertet. Detaillierte Komfortuntersuchungen nach der Europäischen Komfortnorm DIN EN 15251:2007-08 geben Hinweise auf die Wirksamkeit der eingesetzten Kühltechnologien in den jeweiligen Klimazonen. Daraus lassen sich Handlungsempfehlungen für die Planungspraxis und den Gebäudebetrieb ableiten.
This paper reports on the evolution of cracks in the cylinder heads of a large V8 Diesel engine during cyclic engine tests. The observations are compared with the predictions of a lifetime model for combined thermo-mechanical (TMF) and high cycle fatigue (HCF) loading, which is based on a fracture mechanics analysis of microcrack growth in viscoplastic solids and assumes that the crack advance per cycle is proportional to the cyclic crack tip opening displacement. Since the material of the cylinder heads, the cast iron EN-GJV450, exhibits the typical features of cast iron, namely pressure dependence of the yield stress, dilatancy and tension-compression asymmetry, the Gurson model is applied and combined with the viscoplastic Chaboche model. This constitutive model together with the lifetime model is implemented into a finite element code as a user defined material routine. Published model parameters for the considered cast iron are used to carry out the simulation of the engine test. This simulation comprises a CFD analysis to determine the heat transfer coefficients, a thermal analysis of the load cycle and the mechanical analysis. The thermal analysis reproduces the temperatures at various measuring points sufficiently accurately. Finally, the mechanical analysis predicts the location and orientation of the cracks in the valve bridges correctly in all cases. However, the lifetime predictions are rather conservative compared to the tests (by a factor of 1 to 5 in lifetime). This is discussed and explained by the fact that the cracks were detected in the tests only when they had already spread over a substantial fraction of the valve bridge width. To describe this situation a long-crack analysis would be necessary, which is not yet included in the applied lifetime model.