From Isonitriles to Unsaturated NHC Complexes of Gold,Palladium and Platinum

In a modular template synthesis, unsaturated NHC complexes of gold, palladium and platinum were synthesized from simple metal salts, isonitriles and amines with acetal or ketal groups. Upon the addition of amines with tethered acetal or ketal moieties to the metal‐activated isonitrile, first nitrogen acyclic carbene (NAC) complexes are formed. These undergo ring closure and elimination to the unsaturated NHC complexes upon addition of acid. This simple strategy opens an attractive and fast approach to NHC complexes of gold, palladium and platinum. The modular approach allows a fast modification and is well‐suited for the synthesis of unsymetrically and symmetrically substituted unsaturated NHC complexes.

     

Investigations on High Amylose Corn Starch Films. Part 3: Stress Strain Behaviour

By autoclaving a watery high amylose corn starch suspension, homogenous and isotrope films were obtained with different processing parameters. The films were used for investigations on the stress strain behavior. A systematical dependence on the water content and the relationship between native lipids and the starch chains was observed. Especially for films obtained from defatted corn starch, a clear transition was obtained, depending on the water content, from a brittle behavior far below the glass transition temperature T_G with a very high Youngsmodulus to a ductile failure behavior above T_G. The results led to a microscopical model for the native high amylose corn starch films, which in addition outlines the very interesting possibility of controlling in detail changes of the macroscopic stress strain behavior through variations on a molecular scale.     

C/C-SiC component for metallic phase change materials

Thanks to their high energy density and thermal conductivity, metallic Phase Change Materials (mPCM) have shown great potential to improve the performance of thermal energy storage systems. However, the commercial application of mPCM is still limited due to their corrosion behavior with conventional container materials. This work first addresses on a fundamental level, whether carbon-based composite-ceramics are suitable for corrosion critical components in a thermal storage system. The compatibility between the mPCM AlSi₁₂ and the Liquid Silicon Infiltration (LSI)-based carbon fiber reinforced silicon carbide (C/C-SiC) composite is then investigated via contact angle measurements, microstructure analysis, and mechanical testing after exposure. The results reveal that the C/C-SiC composite maintains its mechanical properties and microstructure after exposure in the strongly corrosive mPCM. Based on these results, efforts were made to design and manufacture a container out of C/C-SiC for the housing of mPCM in vehicle application. The stability of the component filled with mPCM was proven nondestructively via computer tomography (CT). Successful thermal input- and output as well as thermal storage ability were demonstrated using a system calorimeter under conditions similar to the application. The investigated C/C-SiC composite has significant application potential as a structural material for thermal energy storage systems with mPCM.     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.     

Mechanisms and Kinetics of Reaction-Bonded Aluminum Oxide Ceramics

Reaction-bonded Al₂O₃ (RBAO) ceramics were fabricated starting from mechanically alloyed Al₂O₃/Al, Al₂O₃/ Al/ZrO₂, and Al₂O₃/Al/ZrO₂/Zr mixtures. Isopressed compacts were heat-treated in air up to 1550°C. Reaction-bonding mechanisms, kinetics, and the influence of ZrO₂ and Zr additions are investigated. Independent of additive, oxidation of Al proceeds both as solid/gas and liquid/gas reaction, and the reaction kinetics follow a parabolic rate law. The reaction rate depends strongly on the particle size of Al. The activation energy of the reaction depends essentially on green density. Below the melting temperature of Al, in samples containing 45 vol% Al and 55 vol% Al₂O₃, it is 112 and 152 kJ/mol at ∼64% and ∼74% TD, respectively, while above the melting temperature, it lies in the range ∼ 26–33 kJ/mol. Zr additions reduce the activation energy to some extent. Samples with only ZrO₂ additions exhibit nearly the same activation energies as ZrO₂-free samples, though ZrO₂ has a very positive effect on the microstructural development in RBAO ceramics. Microstructure evolution and some strength data of RBAO bodies are also reported.     

Influence of growth conditions on biofilm development and mass transfer at the bulk/biofilm interface

In a long-term study on heterotrophic biofilms in tube reactors, this investigation focused on mass transfer at the bulk/biofilm interface, biofilm density and substrate conversion rates. Several biofilms were cultivated under different substrate and hydrodynamic conditions. Oxygen concentration profiles were measured with microelectrodes in the biofilm and in the boundary layer directly in the biofilm tube reactors. The thickness of the concentration boundary layer was found to depend on the surface structure of the biofilm. The hydrodynamic conditions and the substrate load during the growth phase of the biofilm in biofilm systems are two key parameters that influence the biofilm growth, particularly the structure, density and thickness. The measured substrate conversion rates, biofilm densities and the boundary layer thickness were used to formulate an equation for the mass transfer in biofilm tube reactors.     

MgAl2O4-Spinel Synthesized by High-Energy Ball Milling and Reaction Sintering

A new way to prepare magnesia-alumina-spinel was investigated making use of a mixed powder system of MgO and metallic Al-3 wt% Mg. Intensive ball milling was applied which provides the formation of new powder particles as composite of both components in intimate contact. The new configuration of the particles had a significant impact on the reaction sintering behavior leading to single phase spinel microstructures at moderate temperatures below 1400°C. Optimized milling of the powder mixture was therefore required providing reduced crystallite sizes and strongly enlarged interfacial area shared by the reacting components. The optimal milling time was identified by the complete reaction of the starting powders to spinel during sintering. Shorter milling times led to incomplete reactions and longer milling times contaminated the milling product by debris from the milling tools. The amount of interfaces generated by the intimate mixing dominated the sintering reaction kinetics whereas the specific surfaces area was of secondary importance.     

Optimal sensor placement for joint parameter and state estimation problems in large-scale dynamical systems with applications to thermo-mechanics

We consider large-scale dynamical systems in which both the initial state and some parameters are unknown. These unknown quantities must be estimated from partial state observations over a time window. A data assimilation framework is applied for this purpose. Specifically, we focus on large-scale linear systems with multiplicative parameter-state coupling as they arise in the discretization of parametric linear time-dependent partial differential equations. Another feature of our work is the presence of a quantity of interest different from the unknown parameters, which is to be estimated based on the available data. In this setting, we employ a simplicial decomposition algorithm for an optimal sensor placement and set forth formulae for the efficient evaluation of all required quantities. As a guiding example, we consider a thermo-mechanical PDE system with the temperature constituting the system state and the induced displacement at a certain reference point as the quantity of interest.