Untersuchung des einflusses molekularer parameter auf morphologie und eigenschaften von polyethylenen niedriger dichte

Based on the example of PE-LD grades and on model substances obtained by preparative fractionation (fractions in the molecular weight range M?_w = 1.2 ? 390·10⁴ g/mol), comprehensive investigations regarding the problems of structure/properties have been carried out. The correlations of M?_w with 15 physical and application technological perameters have been investigated taking into account the reaction mechanism during the manufacturing of PE-LD in the tubular and agitated autoclave reactor, resulting in the formation of so-called primary structure perameters M?_n, M?_w, molar mass distribution, short chain branching and long chain branching. For the interpretation of the results, among other factors, also the morphological conditions have been taken into consideration, which in connection with the molecular parameters reveal — for specific M?_w-ranges — strong changes and saturation ranges, resp., for the physical and application technological properties.     

Intensification of Convective Heat Transfer

Theoretical Foundations of Chemical Engineering -     

Stationäre Chemische Energieumwandlung als Herausforderungen für den Verfahrensingenieur

Meeting future energy demands with more efficient, lower emission, and safe energy technologies has top priority in the medium term. Consumer-friendly energy concepts, integrated into regional and supraregional energy supply structures, represent further elements. These will make important contributions to resource-conserving and environmentally compatible power supplies utilizing local energy sources including renewable resources. Supplying energy to large areas involves additional tasks, from compensation of large amounts of fluctuating energy to the transport of fluctuating energy to the transport of renewable energy over long distances. Solar dish, parabolic section, and tower power generating plant have considerable economic and CO₂-reduction potential in sunny countries, such as in the Mediterranean region, However, the costs of solar-thermal electricity generation have to be reduced by a factor of 1.5 to 2. Fuel cell systems can attain particular significance as efficient low-emission energy conversion systems in power plant and automative engineering once their technical and economic potential can be realized.     

Enzymatic esterification of glycerol II. Lipase-catalyzed synthesis of regioisomerically pure 1(3)-rac-monoacylglycerols

Regioisomerically pure 1(3)-rac-monoacylglycerols are conveniently prepared in high yields (>75%) and in multigram quantities by enzymatic esterification of glycerol in the presence of various lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) with a variety of different acyl donors, such as free fatty acids, fatty acid alkyl esters, vinyl esters and triacylglycerols, as well as natural fats and oils. All reactions are carried out in aprotic organic solvents with low water content, namelyn-hexane, diethyl ether, tBuOMe or mixtures of these solvents. Essential for the success of these transformations were the following two factors. First, the creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction medium by its adsorption onto a solid support. Second, a facile system for the separation of the desired monoacylglycerol from the reaction mixture, coupled with the continuous recycling of acyl donor and undesirable by-products.     

Enzymatic esterification of glycerol I. Lipase-catalyzed synthesis of regioisomerically pure 1,3-sn-diacylglycerols

Regioisomerically pure 1,3-sn-diacylglycerols are conveniently prepared in high yields (>80%) and in large quantities by enzymatic esterification of glycerol in the presence of various 1,3-selective lipases(Chromobacterium viscosum, Rhizopus delemar, Rhizomucor miehei) and a variety of different acyl donors like free fatty acids, fatty acid alkyl esters and vinyl esters. All reactions are carried out in aprotic organic solvents of low water content, namelyn-hexane, diethyl ether or tBuOMe. The creation of an artificial interphase between the solvent-immiscible hydrophilic glycerol and the hydrophobic reaction media by the adsorption of glycerol onto a solid support prior to use was essential for the success of these transformations. The effects of reaction conditions and the regioselectivities of the lipases on the product yields are described in detail.     

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.     

Alumina Grown during Deposition of Thermal Barrier Coatings on NiCrAlY

The microstructure of Al₂O₃ formed by oxidation of a model NiCrAlY alloy during electron-beam physical vapor deposition of ZrO₂–7.6 mol% YO_1.5 is examined and compared with that formed on the bare substrate. The growth rate, morphology, and chemical composition of the oxide vary among the different constituents of the alloy surface and are further influenced by the O₂ partial pressure and the physical presence of the thermal barrier coating (TBC) layer. These differences, however, are largely limited to the outer oxide layer. The interplay between the TBC and the growing oxide leads to the formation of a fine-grain Al₂O₃–ZrO₂"mixed zone" within the thermally grown oxide. A mechanism is outlined to explain this behavior, based on the dissolution of ZrO₂ in a transient Al₂O₃ structure growing by outward diffusion of Al, and its subsequent reprecipitation when the metastable phase transforms to the stable α-Al₂O₃ form.