Thermal barrier coating bonded by (Al2O3–Y2O3)/(Y2O3-stabilized ZrO2) laminated composite coating prepared by two-step cyclic spray pyrolysis

Thermal barrier coating bonded by (Al₂O₃–Y₂O₃)/(Y₂O₃-stabilized ZrO₂) (YSZ) laminated coating has been developed on Ni-based superalloy by two-step cyclic pyrolysis. It is demonstrated, from cyclic oxidation tests at 1100 °C, that YSZ top coat and alloy substrate can be bonded together effectively by the (Al₂O₃–Y₂O₃)/YSZ laminated coating, showing good resistance to oxidation, cracking, spallation and buckling. These beneficial effects can be attributed to the sealing effect of the designed multi-sealed compact bond coat with α-Al₂O₃ layers, the decrease of thermal stresses, the increase of fracture toughness in such bond coat and no interdiffusion between the substrate and bond coat.     

Selenium dioxide reaction of substituted diphenacyl sulfides: generation of α -ketoacids

The attempted selenium dioxide oxidation of substituted diphenacyl sulfides in anticipation of further functionalization led to a series of α -ketoacids 3 via oxidation followed by C?S bond cleavage. Two minor products, 5 and 6, have also been isolated and a mechanistic pathway for the formation of 3, 5 and 6 has been proposed.     

Porous Perovskite Fibers – Preparation by Wet Phase Inversion Spinning and Catalytic Activity

Porous perovskite (LaMnO₃) fibers were prepared by means of wet phase inversion spinning. The influence of different spinning procedures, slurry and coagulation bath composition on fiber shape and pore morphology was studied. The catalytic activity of the prepared fibers was tested for carbon monoxide oxidation as a model reaction in a differential recycle reactor. The results revealed that by suitable choice of process conditions porous catalytically active fibers can be prepared. Catalytic measurements confirmed that the catalytic fibers exhibit an open structure that allows full utilization of the catalytically active surface without intraparticle diffusional limitations.     

Fuzzy logic control of a reverse flow reactor for catalytic oxidation of ventilation air methane

Fuzzy logic controllers of type-1 and type-2 were implemented to deal with the high nonlinearities and uncertainties in operation of a reverse flow reactor (RFR) for catalytic oxidation of ventilation air methane (VAM). The results indicated that the fuzzy logic controller is distinctly superior to the traditional logic-based controller and works well under the conditions with high nonlinearities and uncertainties. Owing to the robustness of RFR and particular control aim of regulating bed temperature within a relatively broad range, a fuzzy logic controller of type-1 is sufficient to cope with the uncertainty brought by the extensive variation of VAM concentration.     

Cyclic oxidation – guidelines for test standardisation,aimed at the assessment of service behaviour†

Abstract

This paper reviews current procedures used for cyclic oxidation testing and their ability to simulate service behaviour for life time prediction modelling. Test complexity varies from a simple laboratory, slow cycle, furnace test to the use of high velocity dynamic combustion rigs. It is shown that the response of an alloy under cyclic oxidation testing varies, depending on the exact test conditions chosen and the length of test exposure, but for many alloy systems this response has common features. It is proposed that all alloys that are protected by a stable, slow growing oxide scale conform to a common, generic behaviour under cyclic oxidation conditions. This life cycle of such alloys involves first the formation of a stable, protective oxide. At a critical thickness this may start to spall, increasing the rate of scale forming element consumption. When the activity of such elements falls below a critical level, in the near surface region, internal oxidation results together with the formation of less protective scales. Ultimately, it is no longer possible for the alloy to self repair following a thermal cycle and then breakaway corrosion ensures, marking the end of the alloys life.

Thus the choice of cyclic test procedure must be tailored to the particular phase of the alloy life cycle under investigation.     

Anaerobic methane oxidation and aerobic methane production in an east African great lake (Lake Kivu)

We investigated CH₄ oxidation in the water column of Lake Kivu, a deep meromictic tropical lake with CH₄-rich anoxic deep waters. Depth profiles of dissolved gases (CH₄ and N₂O) and a diversity of potential electron acceptors for anaerobic CH₄ oxidation (NO₃^?, SO₄^2?, Fe and Mn oxides) were determined during six field campaigns between June 2011 and August 2014. Denitrification measurements based on stable isotope labelling experiments were performed twice. In addition, we quantified aerobic and anaerobic CH₄ oxidation, NO₃^? and SO₄^2? consumption rates, with and without the presence of an inhibitor of SO₄^2?-reducing bacteria activity. Aerobic CH₄ production was also measured in parallel incubations with the addition of an inhibitor of aerobic CH₄ oxidation. The maximum aerobic and anaerobic CH₄ oxidation rates were estimated to be 27?±?2 and 16?±?8?μmol/L/d, respectively. We observed a difference in the relative importance of aerobic and anaerobic CH₄ oxidation during the rainy and the dry season, with a greater role for aerobic oxidation during the dry season. Lower anaerobic CH₄ oxidation rates were measured in presence of molybdate in half of the measurements, suggesting the occurrence of linkage between SO₄^2? reduction and anaerobic CH₄ oxidation. NO₃^? consumption and dissolved Mn production rates were never high enough to sustain the measured anaerobic CH₄ oxidation, reinforcing the idea of a coupling between SO₄^2? reduction and CH₄ oxidation in the anoxic waters of Lake Kivu. Finally, significant rates (up to 0.37?μmol/L/d) of pelagic CH₄ production were also measured in oxygenated waters.     

Study on the Mechanisms for Baeyer-Villiger Oxidation of Cyclohexanone with Hydrogen Peroxide in Different Systems

The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing ε-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H2O2 and H2O, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with ·OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Brnsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by Brnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*C=O orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H2O2 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O-O group highly electrophilic to attack the C=O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.