Review on Advanced EB-PVD Ceramic Topcoats for TBC Applications

Development of electron beam physical vapor deposited (EB-PVD) thermal barrier coatings (TBC) aims at low conductivity, increased temperature capability, and longer life. Considerable progress has been achieved by comprehensive understanding of the evolvement of the porous microstructure in columnar ceramic topcoats and its application to tailoring optimized micro-structures. New ceramic compositions such as alternative stabilizers in zirconia, hafnia modified coatings, and pyrochlores are addressed. They have demonstrated their potential for future TBC applications. New results of both microstructure and chemistry are presented together with a summary of recent research results.     

Two Subtle Amino Acid Changes in a Transaminase Substantially Enhance or Invert Enantiopreference in Cascade Syntheses

Amine transaminases (ATAs) are powerful enzymes for the stereospecific production of chiral amines. However, the synthesis of amines incorporating more than one stereocenter is still a challenge. We developed a cascade synthesis to access optically active 3‐alkyl‐substituted chiral amines by combining two asymmetric synthesis steps catalyzed by an enoate reductase and ATAs. The ATA wild type from Vibrio fluvialis showed only modest enantioselectivity (14 % de) in the amination of (S)‐3‐methylcyclohexanone, the product of the enoate‐reductase‐catalyzed reaction step. However, by protein engineering we created two variants with substantially improved diastereoselectivities: variant Leu56Val exhibited a higher R selectivity (66 % de) whereas the Leu56Ile substitution caused a switch in enantiopreference to furnish the S‐configured diastereomer (70 % de). Addition of 30 % DMSO further improved the selectivity and facilitated the synthesis of (1R,3S)‐1‐amino‐3‐methylcyclohexane with 89 % de at 87 % conversion.     

Recovery of mineral fertiliser N and slurry N in continuous silage maize using the <Superscript>15</Superscript>N and difference methods

The stable isotope technique and the difference method are common approaches for estimating fertiliser N uptake efficiency. Both methods, however, have limitations and their suitability may depend on N management and environmental conditions. A field experiment was conducted on a humus sandy soil in northern Germany to estimate fertiliser N uptake efficiency of silage maize in the year of application (Zea mays L.) by the stable isotope and the difference method as influenced by the type of N fertiliser (mineral vs. cattle slurry), the application mode (separate or combined application), and N rate. Seven N treatments were included (0, 50, 100 and 150 kg mineral N ha⁻¹; 20, 40 m3 cattle slurry ha⁻¹; 50 kg mineral N ha⁻¹ plus 40 m3 slurry ha⁻¹), where either mineral N or slurry N was labelled, and mineral N was split into two dressings. In addition, 4.1 kg ha⁻¹ labelled mineral N was incorporated into otherwise unlabelled treatments (0, 20, 40 m3 ha⁻¹, and 50 kg mineral N ha⁻¹ plus 40 m3 ha⁻¹) to estimate N uptake from the upper soil layer. Uptake of ¹⁵N was followed in leaves, stalk, ear, and the whole crop. Fertiliser N uptake efficiency (FNUE_15N) of mineral fertiliser N obtained by the isotope technique ranged between 51 and 61%. Recovered fertiliser N was mainly found in the ear, while less labelled N remained in leaves and the stalk. The nitrogen rate tended to increase the amount of recovered N, but the effect was not consistent among plant parts and the whole crop. Plant N uptake from non-fertiliser N was found to increase N input up to 100 kg N ha⁻¹. Nitrogen recoveries of the two mineral N dressings were similar for the different plant parts as well as for the whole crop. Fertiliser N uptake efficiency (FNUE_diff) of mineral N estimated by the difference method resulted in substantially higher values compared to FNUE_15N, varying between 56 and 98%. More N was taken up from the upper soil layer with increasing N supply, which is regarded as a major error source of the difference method. Slurry N was taken up less efficient in the year of application than mineral fertiliser N as indicated by recovery rates of 21–22% (FNUE_15N) and 39–62% (FNUE_diff), respectively. When mineral N and slurry were applied together, the difference method estimated significantly lower N uptake efficiencies for both mineral and slurry N compared to a single application, while values obtained by the isotope method were not affected.     

Unusual CC Bond Isomerization of an α,β‐Unsaturated γ‐Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family

An unexpected, redox‐neutral C?C bond isomerization of a γ‐butyrolactone bearing an exo‐methylene unit to the thermodynamically more favoured endo isomer (k_cat=0.076 s^?1) catalysed by flavoproteins from the Old Yellow Enzyme family was discovered. Theoretical calculations and kinetic data support a mechanism through which the isomerization proceeds through FMN‐mediated hydride addition onto exo‐Cβ, followed by hydride abstraction from endo‐Cβ′, which is in line with the well‐established C?C bond bioreduction of OYEs. This new isomerase activity enriches the catalytic versatility of ene‐reductases.     

Highly Exfoliated Natural Rubber/Clay Composites by “Propping‐Open Procedure”: The Influence of Fatty‐Acid Chain Length on Exfoliation

A high degree of exfoliation of MMT in NR is achieved by using the so‐called “propping‐open approach” in which a stepwise expansion of the interlayer spacing of MMT takes place. The nanostructure is characterized by WAXD and TEM which indicate different extents of clay dispersion depending on the fatty‐acid chain length. Curing kinetics of different nanocomposites is studied and interestingly low activation energies of the vulcanization process are observed in the case of NR/EMMT nanocomposites. The incorporation of EMMT dramatically affects composite properties whereas DMA indicates significant reduction of tan δ peak height and the tensile strength approximately doubles from 14 to 30 MPa with only 5 phr EMMT.

     

Silica Transfer in Ternary Rubber Blends: Calculation and Experimental Determination

A novel model is presented for predicting the phase selective filler localization in an equilibrium state for ternary rubber blends of SBR, NBR, and NR. It is based on surface tension data of the rubber components and the filler. Phase‐selective filler localization in ternary rubber blends is determined experimentally by means of FTIR spectroscopy on the basis of the wetting concept. It is found that by preparation of ternary blends with certain silica loadings, pre‐mixed in each blend phase using the masterbatch technology, silica transfer processes between blend phases take place until the equilibrium filler distribution is reached. The sequence of the silica transfer processes can be explained by taking into consideration the formation of a phase‐in‐phase morphology of the ternary blend.

     

Synthesis of a Series of Structurally Diverse MB327 Derivatives and Their Affinity Characterization at the Nicotinic Acetylcholine Receptor

A novel series of 30 symmetric bispyridinium and related N‐heteroaromatic bisquaternary salts with a propane‐1,3‐diyl linker was synthesized and characterized for their binding affinity at the MB327 binding site of nicotinic acetylcholine receptor (nAChR) from Torpedo californica. Compounds targeting this binding site are of particular interest for research into new antidotes against organophosphate poisoning, as therapeutically active 4‐tert‐butyl‐substituted bispyridinium salt MB327 was previously identified as a nAChR re‐sensitizer. Efficient access to the target compounds was provided by newly developed methods enabling N‐alkylation of sterically hindered or electronically deactivated heterocycles exhibiting a wide variety of functional groups. Determination of binding affinities toward the MB327 binding site at the nAChR, using a recently developed mass spectrometry (MS)‐based Binding Assay, revealed that several compounds reached affinities similar to that of MB327 (pK_i=4.73±0.03). Notably, the newly prepared lipophilic 4‐tert‐butyl‐3‐phenyl‐substituted bispyridinium salt PTM0022 ( 3 h ) was found to have significantly higher binding affinity, with a pK_i value of 5.16±0.07, thus representing considerable progress toward the development of more potent nAChR re‐sensitizers.     

Perspective on the Development of Lead-free Piezoceramics

A large body of work has been reported in the last 5 years on the development of lead-free piezoceramics in the quest to replace lead–zirconate–titanate (PZT) as the main material for electromechanical devices such as actuators, sensors, and transducers. In specific but narrow application ranges the new materials appear adequate, but are not yet suited to replace PZT on a broader basis. In this paper, general guidelines for the development of lead-free piezoelectric ceramics are presented. Suitable chemical elements are selected first on the basis of cost and toxicity as well as ionic polarizability. Different crystal structures with these elements are then considered based on simple concepts, and a variety of phase diagrams are described with attractive morphotropic phase boundaries, yielding good piezoelectric properties. Finally, lessons from density functional theory are reviewed and used to adjust our understanding based on the simpler concepts. Equipped with these guidelines ranging from atom to phase diagram, the current development stage in lead-free piezoceramics is then critically assessed.     

Finite-Element Analysis of Ceramic Multilayer Capacitors: Failure Probability Caused by Wave Soldering and Bending Loads

A two-dimensional numerical model that predicts the reliability of multilayer capacitors (MLCs) during soldering and bending is presented. The Weibull parameters used in the model are based on measurements of soldered MLC devices. The preheating and soldering temperatures have a dominant impact on the failure probability, in comparison to the thickness of the nickel layer, the soft solder geometry, and the number of inner electrodes. Comparison of calculated and measured reliability of three MLC sizes leads to the assumption that residual stresses due to the manufacturing process or size-related microstructure are important.     

Azotobacter vinelandii metal storage protein: "classical" inorganic chemistry involved in Mo/W uptake and release processes

The release of Mo (as molybdate) from the Mo storage protein (MoSto), which is unique among all existing metalloproteins, is strongly influenced by temperature and pH value; other factors (incubation time, protein concentration, degree of purity) have minor, though significant effects. A detailed pH titration at 12 degrees C revealed that three different steps can be distinguished for the Mo-release process. A proportion of approximately 15% at pH 6.8-7.0, an additional 25% at pH 7.2-7.5 and ca. 50% (up to 90% in total) at pH 7.6-7.8. This triphasic process supports the assumption of the presence of different types of molybdenum-oxide-based clusters that exhibit different pH lability. The complete release of Mo was achieved by increasing the temperature to 30 degrees C and the pH value to >7.5. The Mo-release process does not require ATP; on the contrary, ATP prevents, or at least reduces the degree of metal release, depending on the concentration of the nucleotide. From this point of view, the intracellular ATP concentration is suggested to play-in addition to the pH value-an indirect but crucial role in controlling the extent of Mo release in the cell. The binding of molybdenum to the apoprotein (reconstitution process) was confirmed to be directly dependent on the presence of a nucleotide (preferably ATP) and MgCl2. Maximal reincorporation of Mo required 1 mM ATP, which could partly be replaced by GTP. When the storage protein was purified in the presence of ATP and MgCl2 (1 mM each), the final preparation contained 80 Mo atoms per protein molecule. Maximal metal loading (110-115 atoms/MoSto molecule) was only achieved, if Mo was first completely released from the native protein and subsequently (re-) bound under optimal reconstitution conditions: 1 h incubation at pH 6.5 and 12 degrees C in the presence of ATP, MgCl2 and excess molybdate. A corresponding tungsten-containing storage protein ("WSto") could not only be synthesized in vivo by growing cells, but could also be constructed in vitro by a metalate-ion exchange procedure by using the isolated MoSto protein. The high W content of the isolated cell-made WSto (approximately 110 atoms/protein molecule) and the relatively low amount of tungstate that was released from the protein under optimal "release conditions", demonstrates that the W-oxide-based clusters are more stable inside the protein cavity than the Mo-oxide analogues, as expected from the corresponding findings in polyoxometalate chemistry. The optimized isolation of the W-loaded protein form allowed us to get single crystals, and to determine the crystal X-ray structure. This proved that the protein contains remarkably different types of polyoxotungstates, the formation of which is templated in an unprecedented process by the different protein pockets. (Angew. Chem. Int. Ed. 2007, 46, 2408-2413).