On continuity of solutions for parabolic control systems and input-to-state stability

We study minimal conditions under which mild solutions of linear evolutionary control systems are continuous for arbitrary bounded input functions. This question naturally appears when working with boundary controlled, linear partial differential equations. Here, we focus on parabolic equations which allow for operator-theoretic methods such as the holomorphic functional calculus. Moreover, we investigate stronger conditions than continuity leading to input-to-state stability with respect to Orlicz spaces. This also implies that the notions of input-to-state stability and integral-input-to-state stability coincide if additionally the uncontrolled equation is dissipative and the input space is finite-dimensional.     

Crystal Structure of Iron(II) Acetate

In this paper the X‐ray structure and magnetic properties of iron(II) acetate – starting material for the synthesis of a wide range of iron complexes – are presented. The compound crystallises in the space group Pbcn and was identified as 2D coordination polymer consisting of iron atoms and acetate moieties with all the iron atoms hexacoordinate and different coordination modes for the acetate moieties. Additional hydrogen bond contacts lead to a porous coordination polymer with 1D channels in the size of mesopores. Temperature dependent magnetic measurements confirm that the complex is a high‐spin compound in the entire temperature range investigated with a room temperature magnetic moment of 5.4 μ_B. Field‐dependent magnetisation measurements reveal a slightly sigmoidal curve progression typical for metamagnetism.     

Novel Synthetic Strategy for the Production of Fully Bio-Based Binders Using 2,5-Diformylfuran

In this work, resol based binders were prepared with lignin, resorcinol and the bio-based aldehydic platform chemicals 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran (DFF). In preliminary studies, the solubility and stability of DFF in aqueous-alkaline conditions was investigated. Various binders were prepared to investigate the influence of the HMF-DFF ratio and the influence of the aldehyde concentration on the molar mass, rheological properties and curing characteristics of the final binders. It is shown that significantly higher molecular weights and viscosities are obtained by using DFF instead of HMF. The properties of the final binder could also be affected by the precise choice of DFF concentration, as this resulted in higher levels of crosslinking. This work offers a novel type of fully bio-based binder that consists of non-toxic components and is therefore less hazardous than some conventional binders.     

Development of a closed-loop control system for production of medium-chain-length poly(3-hydroxyalkanoates) (mcl-PHAs) from bacteria

Large scale availability of bacterial polyhydroxyalkanoates (PHAs) is still limited to a few types of short-chain-length PHAs, namely poly(3-hydroxybutyrate) (PHB) and its copolymer Biopol™, consisting of 3-hydroxybutyrate and 3-hydroxyvalerate repeating units. In order to increase the number of available medium-chain-length PHA (mcl-PHA) copolymers a flexible high-cell-density fed-batch process was developed. Continuous process monitoring and substrate control were achieved by coupling on-line gaschromatography (on-line GC) to a software-based Proportional Integral (PI) substrate controller. System development time and continuous system upgrading were considerably shortened by using LABView™, a powerful graphical programming environment. The control of octanoic acid and 10-undecenoic acid at 1.5 and 0.5 gL⁻¹ respectively, enabled the production of high levels of biomass (30 gL⁻¹) and mcl-PHA (10.5 gL⁻¹) by avoiding substrate limitations or toxicities. The resulting mcl-PHA was an amorphous copolyester consisting of 37 mol% unsaturated monomers. The present system represents a valuable tool for the production of tailor-made mcl-PHAs, where the desired monomer composition is determined by the ratio of added cosubstrates.     

Synthesis and properties in solution of rodlike polyelectrolytes

Efficient synthetic strategies are described for the preparation of rodlike polyelectrolytes based on the intrinsically rigid poly(p-phenylene). Uncharged precursors were first prepared via the Suzuki coupling and then characterized by different methods of polymer analysis. Finally, they were transformed into polyelectrolytes using macromolecular substitution reactions. Depending on the substitution pattern, the obtained polyelectrolytes are either soluble or insoluble in water. Using water-soluble derivatives, the Poisson-Boltzmann cell model was tested by osmotic measurements and small-angle X-ray scattering. It is shown that the cell model provides a good first approximation of the distribution of the counterions around the macroion but still underestimates their correlation. Moreover, the PPP polyelectrolytes show a very pronounced polyelectrolyte effect. Since the rodlike PPPs are very rigid in shape, this observation proves that the polyelectrolyte effect is caused by long-range intermolecular electrostatic repulsion of the dissolved macroions rather than due to conformational changes.     

Quantitative Phase Analysis of Mixtures Containing α-, β-Tungsten and WO2

For incandescent lamp wire fabrication various powder metallurgical steps are necessary. The stepwise reduction of WO₃ to the tungsten metal powder is one of these. During reduction chemical reactions take place under participation of doping elements (K, Si and Al) causing the structure of non-sag wires. The origin of secondary β-W like an indicator for the activity of dopings has been attributed importance. Therefore it has been developed a method for quantitative phase analysis of α-W, β-W, WO₂ mixtures consisting of oxidation value determination to establish the WO₂ content and X-ray phase analysis for a quantitative separation of the α-W and β-W content. The influence of extinction effects caused by particle size has been investigated and it is proposed a correction method of the measured integral intensities as a function of half-width of the (110) α-W reflex. In regard of the obtained results the formation of the tungsten suboxide W₃O has been excluded.     

Design of a flexible but robust setup for temperature-dependent electrochemistry down to cryogenic temperatures

Electrochemistry and its analytics are essential in a variety of scientific and technological fields where properties related to reduction-oxidation reactions, so-called redox properties, are to be explored. While methodological standards for experiments are well established at room temperature, this is still untrue at sub-zero/cryogenic temperatures, the conditions required for the survey of (ultra−)rapid processes and their intermediates. Problems due to “hand-waving” temperature regulation/conditioning and common usage of pseudo-reference electrodes renders cryo-electrochemistry a great challenge. Herein, we describe a robust setup for performing reliable cryo-electrochemical experiments down to −80 °C. It combines highly stable but flexible temperature conditioning with gas-tight sealing of the electrochemical cell setup. Modification of a commercial palladium hydride reference electrode (PdH RE) allows for rapid temperature cycling under cryogenic conditions in aprotic organic solvents. Validation of the setup with the well-known Ferrocene|Ferrocenium (Fc|Fc⁺) redox couple gave good compliance with literature data at room temperature in a range of organic solvent-based electrolytes. Evaluation of temperature-dependent diffusion kinetic parameters, such as diffusion coefficients (D) and diffusional activation energies (E_a,D) from CVs at multiple potential scan-rates and temperature levels emphasize the reliability of the presented cryo-electrochemical setup.     

Contributions to Forming and Analytical Investigations of Solutions of Cellulose and Cellulose Derivatives – A Research and Development Topic of the TITK eV

Modification, forming and analytical characterisation of cellulose and cellulose solutions represents one of the most important research topics of the Thuringian Institute for Textiles and Plastics Research (TITK). The presentation provides information on the current capabilities of the institute and on the analytical methods developed in these fields.