Facile synthesis of potassium tetrathiooxalate – The “true” monomer for the preparation of electron-conductive poly(nickel-ethylenetetrathiolate)

Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[K_x(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K₂[3]). Heating of K₂[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K₄[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K₂[4]), the product of the decarbonylation of K₂[3]. Preliminary experiments reveal that the involvement of K₂[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications.     

A moment method for splashing and evaporation processes of polydisperse sprays

A new moment method for the modelling of polydisperse sprays is proposed that simultaneously takes into account the dispersion in droplet size and droplet velocity. For the derivation of this Eulerian method the kinetic spray equation is used which constitutes a partial differential equation for the probability density function of droplets. To reduce the complex kinetic spray equation to a form that can be managed with the available numerical procedures, moment transforms with respect to the droplet velocity and the droplet size are conducted. The resulting moment equations are closed by choosing an approximate probability density function which applies to polydisperse sprays. The method is successfully tested for configurations in which a polydisperse spray is either splashed, evaporated or effected by a Stokes drag force. The tests are organised in such a way that crossing of two spray distributions is always included. The new method is able to capture the polydisperse nature of sprays as well as the bi-(or multi-) modal character of the droplet velocity distribution function, for example, when droplets cross each other.     

Material-based process-chain optimization in metal forming

The characteristics of a manufacturing product are influenced by a variety of different factors, such as the material properties of the base product. The prediction of properties that give optimal results in metal forming applications is a complex task but of high interest for the manufacturer. To realize such a prediction scheme, the process chain is split up into individual process steps and for each of them an inverse modeling is required. The specific aim of this work is to present an approach for the inverse problem formulation of a process step and to solve it using methods of machine learning. Moreover, the challenges that often arise due to the ill-posed nature of inverse problems will be discussed. The main focus is on the crystallographic texture of metals, which strongly affects the deformation behavior during a process step and highly influences the characteristics of the final product. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A canonical module characterization of Serre’s (R1)

In this short note, we give a characterization of domains satisfying Serre’s condition (R₁) in terms of their canonical modules. In the special case of toric rings, this generalizes a result of the second author [9 Yanagawa, K. (2015). Dualizing complexes of seminormal a?ne semigroup rings and toric face rings. J. Algebra 425:367–391.[Crossref], [Web of Science ®] , [Google Scholar]] where the normality is described in terms of the “shape” of the canonical module.     

Structural design sensitivity analysis in context of non-linear buckling

Structural stability is an important issue to ensure the safety of thin walled structures. Shell structures are considered in context of linear and non-linear buckling. The design sensitivity analysis with respect to modifications in shape is motivated. Analytically derived gradient information is employed for shape optimisation purposes using solid shells. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Hidden Brønsted acid catalysis: pathways of accidental or deliberate generation of triflic acid from metal triflates

The generation of a hidden Br?nsted acid as a true catalytic species in hydroalkoxylation reactions from metal precatalysts has been clarified in case studies. The mechanism of triflic acid (CF(3)SO(3)H or HOTf) generation starting either from AgOTf in 1,2-dichloroethane (DCE) or from a Cp*RuCl(2)/AgOTf/phosphane combination in toluene has been elucidated. The deliberate and controlled generation of HOTf from AgOTf and cocatalytic amounts of tert-butyl chloride in the cold or from AgOTf in DCE at elevated temperatures results in a hidden Br?nsted acid catalyst useful for mechanistic control experiments or for synthetic applications.