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.     

Korrosion von ölgefeuerten Zentralheizungskesseln

Corrosion of oil-fired domestic boilers Depending on the surface temperature of the flue gas side the corrosion of oil fired domestic boilers proceeds either mainly by acid corrosion or by oxygen corrosion:

• – At surface temperatures of 60°C and higher the corrosion mechanism of acid corrosion prevails and the corrosion rates amount to 0.1–0.3 mm/year (values referred to continuous burner operation). The corrosion products consist of soluble iron(II)- and iron(III)sulfates. Higher corrosion rates can be attributed to an appreciable catalytic formation of sulfur trioxide on the corrosion products formed on the convective heating surfaces.
• – At surface temperatures of 40°C the mechanism of oxygen corrosion already dominates and the corrosion rates are about ten times higher (1.5–3 mm/year, referred to continous burner operation). The high portion of ioron oxide hydrates, especially goethit (α-FeOOH), makes the corrosion products difficult to remove.
• – Distinctly reduced service lives are also expected for the so called reduced temperature boilers (“Niedertemperaturkessel”) and low temperature boiers (“Tieftemperaturkessel”): According to the manufacturers these boilers may be operated at boiler water temperatures well below 60°C, as they are equipped with constructive measures to enhance the surface temperature on the flue gas side. However, these measures are only fully effective under stationary conditions.

Some of the results were obtained from weight loss measurements on test specimen made from St 35.8 and gray cast iron, that were exposed to the flue gases of an oil fired experimental boiler. Other important results come from field measurements of the sulfuric acid content of about 30 boilers that are in practical use.     

Effect of substrate surface roughness on the adherence of NiCrAlY thermal spray coatings

The adherence of plasma sprayed NiCrAlY bond coats can be improved by an appropriate substrate surface finish. The interface fracture energy for crack propagation along the coating/substrate interface has been measured for different surface roughness by means of a specially designed four-point bending test. An increase of the interface fracture energy of about 15% was observed for a three times higher surface roughness. In addition, four-point bending tests with the coating on the side face of bending specimens were performed to analyze the fracture and spalling behavior of the coatings both under large tensile and compressive substrate deformations.     

GpoSolver: a Matlab/C++ toolbox for global polynomial optimization

Global polynomial optimization can be a powerful tool when applied to engineering problems. One of the most successful methods for solving such problems is based on convex linear matrix inequality (LMI) relaxations. Software implementations of this approach can be found for example in Matlab toolboxes GloptiPoly and YALMIP. Matlab language makes it very easy when it comes to modelling polynomial problems. However, when using these toolboxes, Matlab is also required for the problem solving. GpoSolver aims at bridging this gap by providing a Matlab-based problem modelling toolbox supplemented by a problem-solving back end in a form of a C++ template library. Once a problem is conveniently modelled and parametrized in Matlab, a C++ class is automatically generated by GpoSolver. This class can be easily included into an existing codebase and used to solve different instances of the problem based on the supplied parameters.