Rapid optical screening technology for direct methanol fuel cell (DMFC) anode and related electrocatalysts

We describe here the development of an optical high-throughput screening method for direct methanol fuel cell catalysts based on the fluorescence of protonated quinine generated during electro-oxidation of methanol. The design of the working electrode allows the parallel quantification of the fluorescence development for up to 60 materials. For the preparation of the working electrode a coating routine has been developed, which allows the use of sol–gel derived materials. Due to the required stability of the electrode catalysts towards the acidic polymer membrane, a fast optical pre-screening method for acid stable materials has been developed. The electrochemical high-throughput system has been validated with Pt-Ru catalysts. Automation of data acquisition and data processing led to a fast and reliable high-throughput screening setup.     

Heterogeneously doped polyethylene glycol as nano-composite soft matter electrolyte

We have applied the concept of heterogeneous doping [1] to prepare and examine composite electrolytes, consisting of silica particles, low molecular weight polyethylene glycol solvents and lithium perchlorate salt. These “soggy sand” electrolytes combine high ionic conductivities (on the order of mS cm⁻¹) and high Li transference numbers (typically 60–80%) with improved mechanical properties. They were characterized using differential scanning calorimetry, dc-polarization and ac-impedance spectroscopy, zeta potential measurements and viscosimetry. Oxide, size and concentration as well as solvent molecular weight were varied to better understand the influence of ceramic oxide fillers on the ion conduction in these systems. As regarding the filler content, we observe that both conductivity and transference number of Li⁺ start increasing already at low volume fractions of oxide particles, reach a maximum and subsequently decrease to low values. The percolating network is – after initial partial coarsening – found to be stable within the time periods of the measurements.     

Synthesis and Characterization of Segmented Block Copolymers Based on Hydroxyl‐Terminated Liquid Natural Rubber and α,ω‐Diisocyanato Telechelics

Summary: Segmented block copolymers, consisting of non‐polar soft segments from hydroxyl‐terminated liquid natural rubber (HTNR) and polar hard segments from α,ω‐diisocyanato telechelics obtained by “criss‐cross”‐cycloaddition, have been synthesized. The block copolymer formation took place under relatively mild reaction conditions at 80 °C in dichloroethane in the presence of dibutyltin dilaurate as a catalyst. The resulting block copolymers were characterized by spectroscopic techniques (¹H NMR, FTIR, UV‐vis spectroscopy) as well as GPC for molar mass determination. The block copolymers were compression molded in a hot stage press, and the resulting samples were characterized by DSC and stress‐strain measurement. The solubility and phase morphology of the materials have also been studied.

Segmented block copolymer from HTNR and α,ω‐diisocyanato telechelics     

Improvement of Aglycone π-Stacking Yields Nanomolar to Sub-nanomolar FimH Antagonists

Antimicrobial resistance has become a serious concern for the treatment of urinary tract infections. In this context, an anti-adhesive approach targeting FimH, a bacterial lectin enabling the attachment of E. coli to host cells, has attracted considerable interest. FimH can adopt a low/medium-affinity state in the absence and a high-affinity state in the presence of shear forces. Until recently, mostly the high-affinity state has been investigated, despite the fact that a therapeutic antagonist should bind predominantly to the low-affinity state. In this communication, we demonstrate that fluorination of biphenyl α-d -mannosides leads to compounds with perfect π–π stacking interactions with the tyrosine gate of FimH, yielding low nanomolar to sub-nanomolar K_D values for the low- and high-affinity states, respectively. The face-to-face alignment of the perfluorinated biphenyl group of FimH ligands and Tyr48 was confirmed by crystal structures as well as ¹H,¹⁵N-HSQC NMR analysis. Finally, fluorination improves pharmacokinetic parameters predictive for oral availability.     

A new method for determining dynamic grain structure evolution during hot aluminum extrusion

In this paper, a new method for analyzing the microstructure evolution of aluminum during deformation at elevated temperatures by extrusion is presented, which is entirely separated from secondary restoration effects viz. static recrystallization and grain growth. In order to observe the development of grains and their orientation under severe plastic deformation, a small-scale forward extrusion setup was designed which allows quenching the extrusion butt together with the die and the container immediately after extrusion to preserve the grain structure evolved during the deformation. The forming path and the forming history of a selected material point were calculated by numerical simulation. The evolution of the microstructure along the forming path was analyzed using electron backscatter diffraction. A database for the development of physically based phenomenological models for predicting and simulating the evolution of microstructure during the hot deformation of EN AW-6082 alloy is provided.     

A new inrush detection method for transformer differential protection

Contents The long-used restraining principle, based on the detection of 2nd harmonics in the currents, can not always satisfactorily meet the demand of blocking the transformer differential protection for all three phases, because the line currents are not the direct image of the core saturation. The differential protection may become inadequate. A transformer can however be switched on for all cases, without the false or fail-safe tripping, when the harmonic restraint is derived from the magnetic field strength of the core.If a delta-connected winding is present, the magnetic field strengths can not be easily recognized in the line currents, because their zero-sequence component is distorted. A new method is presented, which can estimate the fundamental and the 2nd harmonic of this zero-sequence component. The components of the magnetic field strength can therefore be determined in currents only, whose ratio is known to be characteristic for the core saturation.The proposed method was implemented on an industrial protection system based on a microprocessor and was tested on data obtained from computer-simulation and a model transformer in a laboratory. It turned out that the proposed method performed well on all cases.

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Eine neue Methode der Einschalterkennung für den Transformator-Differentialschutz

Übersicht Die üblicherweise benützte Blockierung beim Einschalten eines Transformators beruht auf der Bewertung der zweiten Harmonischen in den Strömen. Dieses Prinzip kann nicht immer den Transformatorvergleichsschutz in allen drei Phasen blockieren. Dagegen kann ein Transformator in allen Fällen ohne Fehlauslösung eingeschaltet werden, wenn die Blockierung aus der Harmonischen der magnetischen Feldstärke des Kerns abgeleitet wird.Eine neue Methode wird vorgestellt, wie die Homopolarkomponente der Grundschwingung und der zweiten Harmonischen näherungsweise berechnet werden kann. Die benötigten Anteile der Feldstärken können damit aus den Differenzströmen ermittelt werden.Das vorgeschlagene Verfahren wurde auf einer industriell gefertigten Schutzkarte implementiert. Die Überprüfung des Verfahrens erfolgte mit Berechnungsverfahren und durch Messungen im Labor.

     

Selective Oxidation of Propene with Air to Propylene Oxide,a Case Study of Autoxidation Versus Catalytic Oxidation with AMM-Catalysts

The formation of propylene oxide from propene by direct oxidation with air has been studied with a series of new microporous amorphous catalysts containing isolated active sites. Although the materials showed good activities as heterogeneous oxidation catalysts, the formation of acroleine dominated in the gas phase. Oxidation selectivities of the various catalysts are reported. Significant PO-formation was only observed under reaction conditions involving pressures larger 5 bar. Promoting effects of solvents or additives like acetaldehyde could be excluded. Best results were observed in continuous gas phase flow experiments. All catalysts studied proved detrimental to the PO-yield and control experiments pointed to catalyst free autoxidation conditions. A factorial design followed by an optimization of the reaction conditions provided PO-selectivities of 60 % at propene conversion of 11.4 % (T = 290 °C; pressure = 25 bar; propene content = 75 %; total feed = 39.5 ml/min) at continuous reaction conditions. By passivating the inner reactor surfaces with gold, a PO-selectivity of 62.8 % at a propene conversion of 15.1 % could be obtained, indicating, that autoxidation of propene may become a serious contender in the search for improved production processes. This work is a case study of attempted catalyzed selective oxidation with air illustrating potential pitfalls and misleading interpretations.     

SiC ceramic micropatterns from polycarbosilanes

Micropatterned SiC ceramics were fabricated from polycarbosilanes applying a softlithographic replication technique. A polydimethylsiloxane mould replicated from a photolithographic microstructured silicon wafer was used as master structure. The polydimethylsiloxane mould was coated with a solution containing a mixture of two different polycarbosilanes in n-octane. After treatment at 200–400 °C the cross-linked polycarbosilane films were debonded and pyrolysed at 900 °C in nitrogen and subsequently crystallised at temperatures up to 1500 °C in argon. The cross-linking and thermal degradation behaviour of the polycarbosilanes was investigated by Fourier-transform infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. X-ray diffractrometry showed the expected development of a nanocrystalline β-SiC (3 nm) as the main phase with increasing temperature. However, traces of α-SiO₂ derived from the polycarbosilane precursors were also detected by X-ray analysis. Removal of the α-SiO₂ dioxide with hydrofluoric acid in the pyrolysed samples and subsequent increased the crystallite size to 7 nm. The Young's modulus determined by nanoindentation was increased from 3 GPa after cross-linking to 110 GPa after crystallisation. Scanning electron microscopy revealed, that the initial micropatterns were fully retained in the pyrolysed and crystallised SiC ceramics. The micropatterned cross-linked and crystallised β-SiC based substrates exhibited light scattering characteristics, which qualify them as promising candidates for diffractive optical elements in microoptical applications.