LES of oxy-fuel jet flames using the Eulerian Stochastic Fields method with differential diffusion

The Eulerian Stochastic Fields (ESF) Monte Carlo method to solve the transported PDF (TPDF) equation is extended to account for differential diffusion effects by incorporating species individual molecular diffusivities. The method has been applied in Large Eddy simulation (LES) to non-piloted oxy-fuel jet flames at different Reynolds numbers experimentally investigated by Sevault et al. [1]. Due to the high H₂ content in the fuel stream and CO₂ in the oxidizer these flames pose new challenges to combustion modeling as the flame structures are different compared to CH₄/air flames. The simulations show very good agreement with the experiments in terms of mixture fraction conditional mean values for temperature and mayor species on the fuel lean side and the reaction zone, deviations on the fuel rich side are discussed. The trend and location of localized extinction is reproduced well in the simulations, as well as differential diffusion effects in the near field. Additionally, it is shown that a neglect of differential diffusion in the combustion model leads to a lifted flame.     

Allenyl esters as quenching agents for ruthenium olefin metathesis catalysts

In the attempt to synthesize substituted allenyl esters through a metathesis coupling of unsubstituted allenyl esters and alkenes using a variety of ruthenium catalysts, it was discovered that allenyl esters themselves cleanly arrested the activity of the catalysts. Further studies suggests possible utility of allene esters as general quenching agents for metathesis reactions. To explore this idea, several representative olefin metathesis reactions, including ring closing, were successfully terminated by the addition of simple allenyl esters for more convenient purification.     

Size‐Tunable Micron‐Bubbles Based on Fluorous–Fluorous Interactions of Perfluorinated Dendritic Polyglycerols

This paper describes the behavior of various generations of polyglycerol dendrimers that contain a perfluorinated shell. The aggregation in organic solvents is based on supramolecular fluorous–fluorous interactions, which can be described by means of ¹⁹F NMR spectroscopy. In order to study the interaction and aggregation phenomena of dendrimers with perfluorinated shell and perfluoro‐tagged guest molecules we investigated [G3.5]‐dendrimer with a perfluorinated shell in the presence of perfluoro‐tagged disperse red. Noteworthy, the interaction intensities varied in an unexpected manner depending on the equivalents of perfluoro‐tagged guest molecules added to the dendrimers in solution which then formed supramolecular complexes based on fluorous–fluorous interactions. We found that these complexes aggregated around residual air in the solvent to form stable micron‐sized bubbles. Their sizes correlated with the interaction intensities measured for certain dendrimer–guest molecule ratios. Degassing of the solutions led to a quasi phase separation between organic and fluorous phase, whereby the dendrimers formed the fluorous phases. Regassing the sample with air afforded bubbles of the initial size again.     

Probing the out-of-plane distortion of single point defects in atomically thin hexagonal boron nitride at the picometer scale

Crystalline systems often lower their energy by atom displacements from regular high-symmetry lattice sites. We demonstrate that such symmetry lowering distortions can be visualized by ultrahigh resolution transmission electron microscopy even at single point defects. Experimental investigation of structural distortions at the monovacancy defects in suspended bilayers of hexagonal boron nitride (h-BN) accompanied by first-principles calculations reveals a characteristic charge-induced pm symmetry configuration of boron vacancies. This symmetry breaking is caused by interlayer bond reconstruction across the bilayer h-BN at the negatively charged boron vacancy defects and results in local membrane bending at the defect site. This study confirms that boron vacancies are dominantly present in the h-BN membrane.     

First- and second-price sealed-bid auctions applied to push and pull supply contracts

We investigate a newsvendor-type retailer sourcing problem under demand uncertainty who has the option to source from multiple suppliers. The suppliers’ manufacturing costs are private information. A widely used mechanism to find the least costly supplier under asymmetric information is to use a sealed-bid reverse auction. We compare the combinations of different simple auction formats (first- and second-price) and risk sharing supply contracts (push and pull) under full contract compliance, both for risk-neutral and risk-averse retailer and suppliers. We show the superiority of a first-price push auction for a risk-neutral retailer. However, only the pull contracts lead to supply chain coordination. If the retailer is sufficiently risk-averse, the pull is preferred over the push contract. If suppliers are risk-averse, the first-price push auction remains the choice for the retailer. Numerical examples illustrate the allocation of benefits between the retailer and the (winning) supplier for different number of bidders, demand uncertainty, cost uncertainty, and degree of risk-aversion.     

Calabi-Yau 4-folds and toric fibrations

We present a general scheme for identifying fibrations in the framework of toric geometry and provide a large list of weights for Calabi-Yau 4-folds. We find 914 164 weights with degree d ≤ 150 whose maximal Newton polyhedra are reflexive and 525 572 weights with degree d ≤ 4000 that give rise to weighted projective spaces such that the polynomial defining a hypersurface of trivial canonical class is transversal. We compute all Hodge numbers, using Batyrev's formulas (derived by toric methods) for the first and Vafa's formulas (obtained by counting of Ramond ground states in N = 2 LG models) for the latter class, checking their consistency for the 109 308 weights in the overlap. Fibrations of k-folds, including the elliptic case, manifest themselves in the N lattice in the following simple way: The polyhedron corresponding to the fiber is a subpolyhedron of that corresponding to the k-fold, whereas the fan determining the base is a linear projection of the fan corresponding to the k-fold.     

Lithium intercalation into disordered carbon/SiCN composite. Part 2: Raman spectroscopy and <Superscript>7</Superscript>Li MAS NMR investigation of lithium storage sites

Within this work, we analyze the lithium storage sites within carbon/silicon carbonitride (SiCN) composites. Commercial carbons, HD3 (hard carbon) and LD1N and LD2N (soft carbons), of varying porosity are impregnated with polysilazane (HTT 1800) and pyrolysed at 1100 °C. It is found in the first part of this study (Graczyk-Zajac et al. J Solid State Electrochem 19:2763–2769, 2015) that the initial porosity of the carbon phase plays an important role in determining the lithium insertion capacity and rate capability of the composite material. By applying Raman spectroscopy and solid-state ⁷Li MAS NMR on pristine, lithiated, and delithiated samples, we investigate the lithium storage sites within the composite materials. By means of Raman spectroscopy, it has been found that lithium storage in hard carbon-derived composites occurs in a significant extent via adsorption-like process within unorganized carbon, whereas for the soft carbon composites, storage in turbostratic carbon is identified. ⁷Li solid-state NMR confirms these findings revealing that more than 33 % of lithium stored in HD3/SiCN is adsorbed in ionic form at the surface and in pores of the composite, while around 38 % is stored between carbon layers. LD1N and LD2N composites store more than 50 % of lithium in the intercalation-type sites.