Wetting Behavior and Reactivity of Molten Silicon with h-BN Substrate at Ultrahigh Temperatures up to 1750 °C

For a successful implementation of newly proposed silicon-based latent heat thermal energy storage systems, proper ceramic materials that could withstand a contact heating with molten silicon at temperatures much higher than its melting point need to be developed. In this regard, a non-wetting behavior and low reactivity are the main criteria determining the applicability of ceramic as a potential crucible material for long-term ultrahigh temperature contact with molten silicon. In this work, the wetting of hexagonal boron nitride (h-BN) by molten silicon was examined for the first time at temperatures up to 1750 °C. For this purpose, the sessile drop technique combined with contact heating procedure under static argon was used. The reactivity in Si/h-BN system under proposed conditions was evaluated by SEM/EDS examinations of the solidified couple. It was demonstrated that increase in temperature improves wetting, and consequently, non-wetting-to-wetting transition takes place at around 1650 °C. The contact angle of 90° ± 5° is maintained at temperatures up to 1750 °C. The results of structural characterization supported by a thermodynamic modeling indicate that the wetting behavior of the Si/h-BN couple during heating to and cooling from ultrahigh temperature of 1750 °C is mainly controlled by the substrate dissolution/reprecipitation mechanism.     

Investigation of Serine‐Proteinase‐Catalyzed Peptide Splicing in Analogues of Sunflower Trypsin Inhibitor 1 (SFTI‐1)

Serine‐proteinase‐catalyzed peptide splicing was demonstrated in analogues of the trypsin inhibitor SFTI‐1: both single peptides and two‐peptide chains (C‐ and N‐terminal peptide chains linked by a disulfide bridge). In the second series, peptide splicing with catalytic amount of proteinase was observed only when formation of acyl–enzyme intermediate was preceded by hydrolysis of the substrate Lys–Ser peptide bond. Here we demonstrate that with an equimolar amount of the proteinase, splicing occurs in all the two‐peptide‐chain analogues. This conclusion was supported by high resolution crystal structures of selected analogues in complex with trypsin. We showed that the process followed a direct transpeptidation mechanism. Thus, the acyl–enzyme intermediate was formed and was immediately used for a new peptide bond formation; products associated with the hydrolysis of the acyl–enzyme were not observed. The peptide splicing was sequence‐ not structure‐specific.     

Transformation of CH4 and liquid fuels into syngas on monolithic catalysts

Active components comprised of fluorite-like Ln_x(Ce_0.5Zr_0.5)_1−xO_2−y (Ln = La, Pr, Sm) and perovskite-like La_0.8Pr_0.2Mn_0.2Cr_0.8O₃ mixed oxides and their composites with yttria-doped zirconia (YSZ) promoted by precious metals (Pt, Ru) and/or Ni were supported on several types of heat-conducting substrates (compressed Ni-Al foam, Fecralloy foil or gauze protected by corundum layer, Cr-Al-O microchannel cermets, titanium platelets protected by oxidic layer) as well as on honeycomb corundum monolithic substrate. These structured catalysts were tested in pilot-scale reactors in the reactions of steam reforming of methane, selective oxidation of decane and gasoline and steam/autothermal reforming of biofuels (ethanol, acetone, anisole, sunflower oil). Applied procedures of supporting nanocomposite active components on monolithic/structured substrates did not deteriorate their coking stability in real feeds with a small excess of oxidants, which was reflected in good middle-term (up to 200 h) performance stability promising for further up-scaling and long-term tests. Equilibrium yield of syngas at short contact times was achieved by partial oxidation of decane and gasoline without addition of steam usually required to prevent coking. For the first time possibility of successive transformation of biofuels (ethanol, acetone, anisole, sunflower oil) into syngas at short contact times on monolithic catalysts was demonstrated. This was provided by a proper combination of active component, thermal conducting monolithic substrates and unique evaporation/mixing unit used in this research.     

On the modeling of phase and chemical equilibria by equations of state for systems containing supercritical components and ionic species

A technique of modeling of phase and chemical equilibria by equations of state for systems containing supercritical components and ionic species is considered. Attention is focused on the structure of equation of states with inclusion of non-electrolyte and electrostatic contributions. A hole quasichemical model was applied to illustrate the technique and to show how an EOS can be modified for systems with chemical reactions and electrostatic interactions in the liquid phase. The concentration dependency of the density and dielectric permittivity was taken into account in describing the electrostatic contribution that is required for thermodynamic consistency of the results of modeling. A method of assessing the appropriate relationships for mixtures containing supercritical components is suggested, alongside with the way to estimate the “true” composition of mixtures where ionic species are formed due to chemical reactions. The raised questions are discussed with respect to the following systems: solutions of acid gases in water-alkanolamine mixtures and water-ammonia-carbon dioxide system in a broad interval of temperatures and pressures.     

Tunable Dielectric Function in Electric‐Responsive Glass with Tree‐Like Percolating Pathways of Chargeable Conductive Nanoparticles

The design of nanostructured materials with specific physical properties is generally pursued by tuning nanoparticle size, concentration, or surface passivation. An important step forward is to realize “active” systems where nanoparticles are vehicles for controlling, in situ, some specific, tuneable features of a responsive functional material. In this perspective, this work focuses on the rational design of a nanostructured glass with electrically tuneable dielectric function obtained by injection and accumulation of charge on embedded conductive nanocrystals. This enables electrically controlled switching of semiconducting nanophases to charged polarisable states to be achieved, which could lead to smart, field‐enhancement applications in nanophotonics and plasmonics. Here, it is shown that such response switching can be obtained if a percolating charge‐transport mechanism is activated through a disordered tree‐like network, as is demonstrated to be possible in SiO₂ films where suitable dispersions of SnO₂ nanocrystals, with conductive interfaces, are obtained as a result of a new synthesis strategy.     

A fully bio-based monomer derived from undecylenic acid,glycerol, and CO2 useful for the synthesis of polyhydroxyurethanes

Undecylenic acid, glycerol, and CO₂ were used as building blocks for obtaining a fully bio-based carbonated monomer, useful for polyurethanes. The functionality of the monomer was close to 3 cyclic carbonates/mol, located in terminal positions. In a first stage, a synthetic triglyceride was obtained with 99% selectivity by esterification of glycerol and undecylenic acid at 160°C. The triglyceride was then epoxidized using H₂O₂ and Amberlyst 15 or Amberlite IR-120 acidic exchange resins at 57°C. The selectivity to epoxide was kept constant at 98% using Amberlite IR-120. Terminal cyclic carbonates were then inserted through epoxide moieties under mild conditions by the chemical fixation of CO₂ at 80°C and 6 MPa in 6 h. A complete conversion was obtained in 6 h reaction while the selectivity to carbonate groups was near to 99% during all the reaction time. An elastomeric polyhydroxyurethane was obtained by aminolysis of the carbonated monomer with ethylenediamine at 70°C, affording a Young's modulus of 22.6 MPa and T_g of −15.2°C. The material showed a good thermal stability below 240°C.     

Profiling glucosinolates in vegetative and reproductive tissues of four Brassica species of the U‐triangle for their biofumigation potential

Glucosinolates are amino acid derived allelochemicals present in all plants of the order Capparales. These compounds are degraded by myrosinase isoenzymes, releasing a series of biologically active products defined by the parent glucosinolate and the reaction conditions. Species within the Brassicaceae are found to differ in their glucosinolate profile and glucosinolate concentrations. Different tissues within a single plant also show such variations, which are further influenced by the growth stage and environmental conditions. In the experiments described in this paper, four Brassica species of the U‐triangle (B. carinata, B. nigra, B. juncea and B. rapa) were compared with respect to their glucosinolate profiles in roots, stems, leaves and reproductive organs at different developmental stages. The glucosinolate profile of corresponding ripe seeds was also determined. Prop‐2‐enylglucosinolate was identified as the major glucosinolate in the three mustards, where it represented over 90% of the total glucosinolate concentration of ripe seeds and over 50% of green tissues. The relative concentration of this glucosinolate increased in all tissues during plant growth. Brassica rapa showed a different glucosinolate profile than the three mustards, with higher concentrations of but‐3‐enylglucosinolate, 2‐hydroxybut‐3‐enylglucosinolate and 2‐hydroxypent‐4‐enylglucosinolate. The concentration of indol‐3‐ylmethylglucosinolates was also higher in B. rapa than in the mustard plants, with 4‐hydroxyglucobrassicin representing 30% of the total glucosinolate concentration in ripe seeds. The total glucosinolate concentration of the species studied varied with growth stage and the mustards achieved a maximum towards the end of the period monitored. Glucosinolate concentration decreased in roots and leaves but increased in reproductive tissues. The determined glucosinolate profiles are an initial step in assessing the biofumigation potential of these species of the Brassicaceae family. Copyright © 2007 Society of Chemical Industry     

Characterization of Edible Active Coating Based on Alginate–Thyme Oil–Propionic Acid for the Preservation of Fresh Chicken Breast Fillets

Chicken meat presents serious problems of processing and storage. Edible coatings are used commercially to improve the shelf life of fresh foods. The aim of this study is to develop an effective antimicrobial edible coating to improve the shelf life and safety of fresh chicken meat. The effect of propionic acid and thyme essential oils as antimicrobial and antioxidant compounds incorporated into alginate‐based edible coating was evaluated. Physical, antimicrobial and sensorial analyses were performed in coated and uncoated samples. Sensorial analysis showed no significant differences between coated and uncoated samples, which do not influence the buying decisions of consumers. The pH of the meat surface, color and sensorial analysis changed during storage time, showing similar behavior between coatings, the principal parameters to determine the shelf life of this product were weight loss and microbiological deterioration, where coatings had different behaviors. The selected coating increased the shelf life by about 33% with the lowest dehydration.     

Formation Routes of Nanocomposite Coatings in Detonation Spraying of Ti3SiC2-Cu Powders

In thermally sprayed coatings, nano-sized features of the microstructure may be either inherited from the nanostructured agglomerates of the feedstock powder or form as a result of rapid cooling of molten particles upon deposition. Applying a process of the computer-controlled detonation spraying (CCDS) to Ti₃SiC₂-Cu composite powders produced by high-energy mechanical milling, we show that both routes are possible depending on the spraying conditions. When the nanostructure of the Ti₃SiC₂-Cu coating is inherited from the feedstock powder—under very mild conditions of detonation spraying, which exclude melting, so is the phase composition of the coating. In higher-temperature conditions of spraying, a significant fraction of the copper matrix melts and the interaction between Ti₃SiC₂ and Cu occurs. The TiC _x -Cu(Si) coatings that form show crystallites of both phases in the nano-range. In this case, rapid solidification of the molten fraction of the particles is responsible for the formation of the coatings with a nanostructured matrix. Due to the flexibility of the CCDS process, conditions of spraying were found such that a composite coating with very fine crystallites of the Cu(Si) matrix (30 nm) and a hardness of 273 HV could be obtained.