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A wide range catalyst screening with noble metal and oxide catalysts for a metal–air battery with an aqueous alkaline electrolyte was carried out. Suitable catalysts reduce overpotentials during the charge and discharge process, and therefore improve the round-trip efficiency of the battery. In this case, the electrodes will be used as optimized cathodes for a future lithium–air battery with an aqueous alkaline electrolyte. Oxide catalysts were synthesized via atmospheric plasma spraying. The screening showed that IrO2, RuO2, La0.6Ca0.4Co3, Mn3O4, and Co3O4 are promising bi-functional catalysts. Considering the high price for the noble metal catalysts further investigations of the oxide catalysts were carried out to analyze their electrochemical behavior at varied temperatures, molarities, and in case of La1−x Ca x CoO3 a varying calcium content. Additionally all catalysts were tested in a longterm test to proof cyclability at varied molarities. Further investigations showed that Co3O4 seems to be the most promising bi-functional catalyst of the tested oxide catalysts. Furthermore, it was shown that a calcium content of x = 0.4 in LCCO has the best performance.
We tested the MOF framework Cu-BTC for natural gas (NG) storage. Adsorption isotherms of C1–C4 alkanes were simulated applying the Grand Canonical ensemble and the Monte Carlo algorithm in a classical molecular mechanics approach. Experimental monocomponent isotherm of the alkanes was used to validate the force field. We performed multicomponent adsorptions calculations for three different quaternary mixtures of C1–C4 alkanes, matching typical NG streams composition, and predicted theoretical storage capacities, efficiency and accumulation of the NG within that composition. Despite being one of the frameworks with greatest storage capacity of methane, we found that Cu-BTC presented great sensitivity to the variation of the heavier alkanes in NG composition. When we increase the percentage of butane from 0.1% to 0.7% in the mixture, the mass of components retained in the discharge pressure (1 bar) increases from 35 to 60%. We also perform siting and interaction energy investigations and compare the NG storage performance of the Cu-BTC with that of activated carbons. To our knowledge, this is the first study regarding the efficiency of the NG storage in Cu-BTC.
Private households constitute a considerable share of Europe's electricity consumption. The current electricity distribution system treats them as effectively passive individual units. In the future, however, users of the electricity grid will be involved more actively in the grid operation and can become part of intelligent networked collaborations. They can then contribute the demand and supply flexibility that they dispose of and, as a result, help to better integrate renewable energy in-feed into the distribution grids.
A laser-operated, angle-tunable transducer was employed to excite selectively elastic waves guided along the apex of a solid wedge. The propagation of wedge waves at anisotropic monocrystalline silicon edges with different symmetry properties was studied by optical detection. The reduced symmetry in crystals, as compared to isotropic media, causes a number of new features, such as the existence of supersonic leaky wedge waves, tilted spatial pulse profiles, and other peculiarities of their localization. Experimental and theoretical results are presented for three different types of symmetry configurations: the wedge symmetric about its midplane, the wedge symmetric about the plane normal to its apex line, and the wedge symmetric about one of its faces. The experiments include accurate measurements of the phase velocity and the wave field distribution, providing information on localization and coupling of wedge waves with other waves. Theoretically, the wedge waves were treated by the Laguerre function method, extended to modes that are not localized at the tip of the wedge. This approach allowed an accurate description of the observed localized and leaky wedge waves in anisotropic wedges.
Packed beds serve as thermal energy storages (TES) and heat exchangers (HEX) in different technological applications. In this paper, a general heterogeneous model of heat transfer in packed beds is developed. It is implemented by lumped element formulation in object-oriented modeling language Modelica and is successful validated with data sets taken from two different experiments reported in literature.
The main advantages of the introduced model are the general, theory-based approach and the lumped element formulation in Modelica. The first point mentioned above should allow to simulate a packed bed TES/HEX without the necessity applying measured data for model calibration or to apply specific heat transfer correlations with restricted application. The second point establishes the possibility to integrate the TES/HEX model within plant models of larger scale without increasing the simulation time drastically.
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.
Energy management in distribution grids is one of the key challenges that needs to be overcome to increase the share of fluctuating renewable energies. Current control systems for energy management mainly demonstrate centralized- or decentralized-hierarchical control structures. Very few systems manifest a fully decentralized multiagent-based control structure. Multiagent-based control systems promise to be an advantageous approach for the future distributed energy supply system because no central control entity is necessary, which eases parameterization in case of grid topology changes, and the agents are more stable against failures and changes of control topologies. Research is necessary to prove these benefits. In this study, we introduce a design of a multiagent-based voltage control system for low-voltage grids. In detail we introduce cooperative decision-making processes and software solutions that allow the agents to perceive and control their environment, the agent-discovery and localization in different types of communication networks, agent-to-agent communication, and the integration of the multiagent system in existing grid-control infrastructures. Furthermore, the study proposes how different existing technologies can be combined into an applicable multiagent-based voltage control system: the Java/OSGi-based OpenMUC framework allows a generic field–device interaction; peer-to-peer discovery and session establishment functionalities are combined with the agent communication defined by the Foundation for Intelligent Physical Agents (FIPA). The ripple control-signal technology is applied as a fallback communication between the agent and a central grid-control center.
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.
Turbinen aus der Tragetasche
(2014)
Am Karlsruher Institut für Technologie wurde der Prototyp eines Kleinwindkraftwerks zur autarken Stromversorgung entwickelt. Das "Energypack" genannte System besteht aus einem 1,10 m langen PVC-Gehäuse mit dreieckigem Querschnitt, Generator, Seilen sowie Funkgerät und kostet ab 50 Euro. Mit dem Energypack kann ein Dynamo mit 2,5 W angetrieben werden. An der Dualen Hochschule BW Heidenheim wurde das System "Anemotec" entworfen, das anstelle von Windflügeln über ein schraubenähnliches Gewinde verfügt. Der Rotor und die Windführung bestehen aus glasfaserverstärkten Werkstoffen. Die erzeugte Leistung liegt bei 365 W, die Stromgestehungskosten liegen bei 23 Cent pro kWh. Die von der Hochschule Offenburg entwickelte Windturbine "Windzip" arbeitet mit einem H-Rotor und besteht aus neun leicht gekrümmten Blechen, die wie Planeten in unterschiedlichem Abstand und in unterschiedlicher Höhe um einen vertikalen Stab kreisen. Bei einer Windgeschwindigkeit von 10 Meter pro Sekunde wurde damit eine Leistung von 40 W erzeugt.
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.
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.
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.
Impedance of the Surface Double Layer of LSCF/CGO Composite Cathodes: An Elementary Kinetic Model
(2014)
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.
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).
Ansatzpunkte zur Verknüpfung von Wertmanagement und Wertemanagement aus Sicht der Führungspraxis
(2014)