Hilfsmittel zum Auffinden einer ersten Gestalt beim methodischen Konstruieren: Gestaltbeeinflussung durch die Verwendung physikalischer Effekte

Zusammenfassung Ziel des Teilvorhabens, über das hier berichtet wird, was es, für eine Auswahl von physikalischen Effekten eine Zuordnung von gestaltbeeinflussenden Merkmalen auf sehr abstrakter Ebene zu erreichen und damit eine n?here Charakterisierung der Wirkfl?chen und Wirkr?ume zu erreichen die zur Umsetzung eines physikalischen Effektes notwendig sind. Die hieraus resultierenden Ergebnisse sind dem Abschlu?bericht zu entnehmen [1]. Weiterführende Themen, die basierend auf den vorliegenden Erkenntnissen bearbeitet werden, haben zum Ziel, die wesentlichen und entscheidenden Parameter einer Konstruktionsaufgabe zu erkennen und zukünftig zielgerichtet L?sungsvarianten zu erstellen, um somit für eine Neukonstruktion sinnvolle L?sungsfelder sehr frühzeitig abzugrenzen.     

Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy Characterization of Glass Phase in Sol-Gel-Derived Mullite

Sol-gel-derived mullite ceramics were processed by pressureless sintering at 1600°, 1650°, and 1700°C for 4 h. Microstructural and microchemical characterization of the mullite materials was performed using transmission electron microscopy, in conjunction with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy (EELS). Apart from mullite grain diameter and triplepocket size, no major microstructural changes were observed with increasing sintering temperature. Residual glass was present at triple pockets and along two-grain junctions. Not all grain boundaries revealed the presence of a continuous amorphous intergranular film. Clean interfaces were observed only at boundaries with one grain parallel to the [001] orientation (low-energy configuration). Quantitative EELS analysis of mullite grains and glass pockets revealed only small changes in composition with increasing sintering temperature; i.e., the alumina:silica ratio slightly increased for mullite and glass. The analysis implied that mullite with this relatively high aluminum content would not be stable adjacent to residual glass. However, a stable glass-mullite system has been proposed, because impurity cations were detected within glass pockets, which suggested a slight shift of the subsolidus line (glass-mullite/ mullite) to a higher amount of alumina. Energy-loss nearedge structure studies of the Si- L _2,3 edge revealed a similar near-edge structure for the mullite, residual glass, and quartz. Thus, SiO₄ tetrahedra were thought to be the main building units of the glass contained in sintered mullite.     

Interactions in compatible polymer systems

Summary Dynamic mechanical measurements on polystyrene — poly(vinylmethylether) blends are demonstrating that the relaxation processes in the blends are mainly connected with the motions of the poly(vinylmethylether) chain.Concerning the effect of mixing on topological properties of the blends, an increase of the polydispersity of the relaxation processes is detected in blends with high molecular weight polystyrene while low molecular weight polystyrene exerts an effect of dilution upon the relaxation of the high molecular poly(vinylmethylether) chains.From these measurements as well as from thermoanalytical data it results that the energetic interaction is more pronounced in the blends with oligomeric than with high molecular weight polystyrene. The glass transition temperature shows a larger deviation from additivity for blends with high molecular polystyrene than for those with oligomeric polystyrene.Herrn Prof. Dr. M. Kryszewski zum 60. Geburtstag herzlichst gewidmet     

Grain-Boundary Wetting-Dewetting in z= 1 SiAlON Ceramic

The grain-boundary structure of a model SiAlON polycrystal with nominal composition Si₅AlON₇ was characterized by transmission electron microscopy (TEM) both in an equilibrium (as-processed) state at room temperature and after quenching from elevated temperature. In addition, low-frequency (1–13 Hz) internal friction data were recorded as a function of temperature, showing a pronounced grain-boundary sliding peak positioned at 1030°C. High-resolution transmission electron microscopy (HRTEM) of the equilibrated low-temperature microstructure revealed residual glass only at multigrain junctions, but no amorphous intergranular films were observed. The detection of clean interfaces in the as-processed sample contradicts the internal friction data, which instead suggests the presence of a low-viscosity grain boundary phase, sliding at elevated temperatures. Therefore, a thin section of the as-sintered material was heated to 1380°C and rapidly quenched. HRTEM analysis of this sample showed, apart from residual glass pockets, wetted grain boundaries, which is in line with the internal friction experiment. This wetting-dewetting phenomenon observed in z = 1 SiAlON is expected to have a strong impact not only on high-temperature engineering ceramics but also on geological, temperature-activated processes such as volcanic eruptions.     

Statistical Analysis of the Intergranular Film Thickness in Silicon Nitride Ceramics

Silicon nitride materials typically reveal thin amorphous intergranular films along grain boundaries, with only the exception of special boundaries. It is known that such grainboundary films strongly affect the high-temperature properties of the bulk material. High-resolution electron microscopy (HREM) was used to study these amorphous films in different Si₃N₄ ceramics. The observed film thicknesses at grain boundaries in these materials varied between 5and 15 Å. It was shown that the grain-boundary film thickness strongly depends on film chemistry. Careful inspections of film-thickness measurements across grain boundaries in a given material suggest that the film widths vary on the order of 1 Å. Therefore, a quantitative evaluation should allow for the determination of the standard deviation of the film thickness. The amorphous film widths along grain boundaries in four materials were measured over the entire length (up to 1 μm) of the grain boundary between two triple points. Forty to fifty data points were evaluated for each boundary, giving a Gaussian-like distribution of the film thickness around a median value, which corresponded well with the film width measured from single HREM micrographs. The accuracy achieved by the statistical method was better than ± 1 Å.     

Ca15(CBN)6(C2)2O- a new cubic structure type containing CBN-anions together with acetylide and oxo anions

Ca₁₅(CBN)₆(C₂)₂O contains CBN⁴⁻ anions as well as C₂⁻ units and isolated O²⁻ anions. The compound is obtained by heating a stoichiometric mixture of CaO, C and BN with an excess of Ca in sealed niobium ampoules to 1270 K. It crystallizes in the space group Ia d with a = 1656.84(9) pm. Preparation, crystal structure, NMR and IR-spectroscopic properties are discussed.     

Diazoverbindungen. 72. (Diazoalkyl)phosphane – Synthese durch elektrophile Diazoalkansubstitution und oxidative Additionsreaktionen am Phosphor

Diazo Compounds. 72. Diazoalkylphosphanes – Synthesis by Electrophilic Diazoalkane Substitution and Oxidative Addition Reactions at Phosphorus Electrophilic diazoalkane substitution of the diazomethyl compounds 1a,b with the chloro phosphanes 2a-o in the presence of lithium diethylamide yields the diazoalkyl phosphanes 3a-z . Oxidative addition of oxygen, sulfur and selenium at phosphorus leads into the series of oxo, thioxo and selenoxo phosphanes having diazoalkyl substituents ( 4a-d, 5a-m and 7a-d ). The silyl group of 5n,o is cleaved by chromatography on aluminium oxide to yield the (diazomethyl)phosphane sulfides 6a,b .     

Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical Termination The photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides ( 1 – 4 ) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the S S bond, which was determined by spin trapping experiments with phenyl tert-butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.