On the role of the microporous layer in PEMFC operation

The condition of liquid water breakthrough at the cathode of polymer electrolyte fuel cells (PEMFC) is studied experimentally and data on corresponding water saturation and capillary pressure are provided for gas diffusion layers (GDL) with and without a microporous layer (MPL). The data demonstrate that the GDL saturation at water breakthrough is drastically reduced from ca. 25% to ca. 5% in the presence of MPL. This observation is consistent with considerations of invasion percolation in finite-size lattices and suggests an explanation for the role of MPL in improving PEMFC performance at high current densities.     

Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane–water interface

The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol-capped gold nanoparticles at the hexane–water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). A series of gold colloids were made using nanoparticles ranging in size from 1.60 to 2.85 nm dissolved in hexane for the interfacial tension analysis. Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense monolayer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. (Phys Chem Chem Phys 9:6351–6358, 2007). The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol-capped gold nanoparticles at liquid–liquid interfaces.     

Lateral post-buckling analysis of beams

Summary The nonlinear lateral buckling response of perfect stocky beams in the vicinity of the critical bifurcational state is discussed. Attention is focused on the initial post-buckling response. This depends on the nature of the critical branching point which is explored by using a nonlinear (lateral) bending-curvature relationship. It is found that the plane of loading (associated with the major moment of inertia) looses its stability through a stable symmetric bifurcation point. Hence, the above beams are not sensitive to imperfections, exhibiting post-buckling strength. However, the post-buckling equilibrium path is quite shallow, so that the load-carrying capacity of such beams above the critical state is rather limited. The analysis is supplemented by illustrative examples forI-beams for which the effect of various parameters on the initial postbuckling path is also discussed.

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Analyse des lateralen nachkritischen Knickverhaltens von Balken

Übersicht Das nichtlineare Knickverhalten von perfekten gedrungenen Balken in der Nachbarschaft des kritischen Verzweigungspunktes wird untersucht, wobei sich die Aufmerksamkeit insbesondere auf den Beginn der nachkritischen Phase richtet. Diese hängt vom Charakter des kritischen Verzweigungspunktes ab, der seinerseits mit Hilfe einer nichtlinearen (lateralen) Biegemoment-und Krümmungs-Beziehung analysiert wird. Es zeigt sich, daß die Stabilität in der Belastungsebene-verbunden mit dem maximalen Flächenmoment zweiter Ordnung-über einen stabilen symmetrischen Verzweigungspunkt verlorengeht. Daher sind solche Balken unempfindlch gegenüber Imperfektionen, sie zeigen nachkritische Belastbarkeit. Der nachkritische Gleichgewichtspfad ist jedoch sehr flach, so daß die Tragfähigkeit dieser Balken oberhalb des kritischen Zustandes recht begrenzt ist. Die Untersuchung ist durch illustrative Beispiele für I-Balken untermauert, für welche der Einfluß der verschiedenen Parameter auf den anfänglichen nachkritischen Pfad herausgearbeitet wird.

     

Convective mass transfer across fluid interfaces in straight angular pores

Steady convective mass transfer to or from fluid interfaces in pores of angular cross-section is theoretically investigated. This situation is relevant to a variety of mass transport process in porous media, including the fate of residual non-aqueous phase liquid ganglia and gas bubbles. The model incorporates the essential physics of capillarity and solute mass transfer by convection and diffusion in corner fluid filaments. The geometry of the corner filaments, characterized by the fluid–fluid contact angle, the corner half-angle and the interface meniscus curvature, is accounted for. Boundary conditions of zero surface shear (‘perfect-slip’) and infinite surface shear (‘no-slip’) at the fluid–fluid interface are considered. The governing equations for laminar flow within the corner filament and convective diffusion to or from the fluid–fluid interface are solved using finite-element methods. Flow computations are verified by comparing the dimensionless resistance factor and hydraulic conductance of corner filaments against recent numerical solutions by Patzek and Kristensen (J. Colloid Interface Sci 236, 305–317 2001). Novel results are obtained for the average effluent concentration as a function of flow geometry and pore-scale Peclet number. These results are correlated to a characteristic corner length and local pore-scale Peclet number using empirical equations appropriate for implementation in pore network models. Finally, a previously published “2D-slit” approximation to the problem at hand is checked and found to be in considerable error.     

Control policies for single-stage production systems with perishable inventory and customer impatience

We consider problems of inventory and admission control for make-to-stock production systems with perishable inventory and impatient customers. Customers may balk upon arrival (refuse to place orders) and renege while waiting (withdraw delayed orders) during stockouts. Item lifetimes and customer patience times are random variables with general distributions. Processing, setup, and customer inter-arrival times are however assumed to be exponential random variables. In particular, the paper studies two models. In the first model, the system suspends its production when its stock reaches a safety level and can resume later without incurring any setup delay or cost. In the second model, the system incurs setup delays and setup costs; during stockouts, all arriving customers are informed about anticipated delays and either balk or place their orders but cannot withdraw them later. Using results from the queueing literature, we derive expressions for the system steady-state probabilities and performance measures, such as profit from sales and costs of inventory, setups, and delays in filling customer orders. We use these expressions to find optimal inventory and admission policies, and investigate the impact of product lifetimes and customer patience times on system performance.     

Dispersion Characteristics of Arbitrary Periodic Structures with Rectangular Grooves

The dispersion characteristics of a circular cylindrical waveguide with periodic surface corrugations consisting of rectangular grooves with smoothing are examined using the Space Harmonic Method (SHM). The whole structure is divided into two regions, one describing the propagation volume and one inside the grooves. In the first region, the Floquet theorem is applicable and the field distribution is expressed as a summation of spatial Bloch components, whereas in the second one an appropriate Fourier expansion of standing waves is used. Applying the boundary conditions an infinite system of equations is obtained, which is solved numerically by truncation. Several cases are considered, including the limiting cases of a sinusoidal and a rectangular corrugation profile, to check the accuracy of the method proposed as well as its dependence on the corrugation profile. Numerical results are presented only for transverse magnetic modes, although the formalism can be easily extended to include all kinds of waves that can in principle propagate in such a structure.     

molSimplify: A toolkit for automating discovery in inorganic chemistry

We present an automated, open source toolkit for the first‐principles screening and discovery of new inorganic molecules and intermolecular complexes. Challenges remain in the automatic generation of candidate inorganic molecule structures due to the high variability in coordination and bonding, which we overcome through a divide‐and‐conquer tactic that flexibly combines force‐field preoptimization of organic fragments with alignment to first‐principles‐trained metal‐ligand distances. Exploration of chemical space is enabled through random generation of ligands and intermolecular complexes from large chemical databases. We validate the generated structures with the root mean squared (RMS) gradients evaluated from density functional theory (DFT), which are around 0.02 Ha/au across a large 150 molecule test set. Comparison of molSimplify results to full optimization with the universal force field reveals that RMS DFT gradients are improved by 40%. Seamless generation of input files, preparation and execution of electronic structure calculations, and post‐processing for each generated structure aids interpretation of underlying chemical and energetic trends. © 2016 Wiley Periodicals, Inc.     

Distributed caching over heterogeneous mobile networks

Sharing content over a mobile network through opportunistic contacts has recently received considerable attention. In proposed scenarios, users store content they download in a local cache and share it with other users they meet, e.g., via Bluetooth or WiFi. The storage capacity of mobile devices is typically limited; therefore, identifying which content a user should store in her cache is a fundamental problem in the operation of any such content distribution system. In this work we propose Psephos, a novel mechanism for determining the caching policy of each mobile user. Psephos is fully distributed: users compute their own policies individually, in the absence of a central authority. Moreover, it is designed for a heterogeneous environment, in which demand for content, access to resources, and mobility characteristics may vary across different users. Most importantly, the caching policies computed by our mechanism are optimal: we show that Psephos maximizes the system’s social welfare. To the best of our knowledge, our work is the first to address caching with heterogeneity in a fully distributed manner.