Combinatorial pulsed laser deposition and thermoelectricity of (La1−xCax)VO3 composition-spread films

La_1−xCa_xVO₃ composition-spread film library was fabricated by combinatorial pulsed laser deposition and their thermoelectric properties were evaluated paralelly by the multi-channel probes of Seebeck coefficient and electric conductivity. Concurrent X-ray analysis verified the formation of solid soluted films in the full composition range (0x1) as judged from the linear variation of the lattice constants. The Seebeck coefficients of La_1−xCa_xVO₃ changed from a large negative value to almost zero with the increase of x, due presumably to the variation of valence in vanadium ions.The power factor in this library was as high as 0.6 μW/cm K², which was obtained at x=0, i.e. pure LaVO₃ grown at 800 °C.     

Thermal Stability of Hexaaluminate Film Coated on SiC Substrate for High-Temperature Catalytic Application

A coating of barium hexaaluminate (Ba_0.75Al_11.0O_17.25) on an α-SiC substrate and the thermal stability of the formed film were investigated for a high-temperature catalytic application. The film prepared by sol coating consisted of BaAl₂Si₂O₈ and α-Al₂O₃ phases and always contained many cracks or exfoliations after heating at 1200C. A hexaaluminate porous film was successfully formed by slurry coating without void formation at the interface between the film and the substrate and exfoliation due to the formation of the intermediate layer after heating at 1200°C. The microstructure of the film remained unchanged, even after heating at 1300°C.     

Spray-dry synthesis of β-Cu1.8Zn0.2V2O7 ceramic fine particles showing giant negative thermal expansion

We used spray-dry method to synthesize fine powder of β-Cu_1.8Zn_0.2V₂O₇ showing large negative thermal expansion (NTE) linearly to temperature over a wide temperature range. The NTE of β-Cu_1.8Zn_0.2V₂O₇ is produced by microstructures consisting of voids and anisotropic thermal deformation of crystal grains in ceramics. By reducing the size of the microstructures that produce NTE, large NTE equivalent to that of bulk was realized, even for ceramic particles of about 2 μm size. Comparison with particles produced using a conventional method demonstrates that the particle size distribution is narrow and that the particles are nearly spherical. This achievement is expected to pave the way to use of NTE materials in micrometer-scale control of thermal expansion.     

A 31P-NMR study of peroxo species formed during oxidation of cyclohexene with hydrogen peroxide in tri-n-butylphosphate catalyzed by heteropolyacids

In the oxidation of cyclohexene with H₂O₂in monophasic tri-n-butylphosphate (TBP) solution catalyzed by Keggin-type 12-heteropolyacids, i.e., H₃PMo_12-xW _x O₄₀(x=0–12), several peroxo species were observed by ³¹P-NMR spectroscopy in lower field than the original heteropolyacids. Their composition varied regularly with that of the starting catalyst. The P-containing peroxo species formed was deduced as [PM₄O₈(O₂)₈]^3-(M = Mo, W). The peroxo species formed more easily with a decrease in the W content, x of H₃PMo_12-xW_xO₄₀. It was further indicated from the reactivity with cyclohexene and the comparison with catalytic performance that W-rich peroxo species were catalytically more active than Mo-rich peroxo species for the oxidation of cyclohexene in this reaction system.     

Stable and super‐low friction of amorphous carbon nitride coatings in nitrogen gas by using two‐step ball‐on‐disk friction test

Effect of running‐in process on friction behaviour of carbon nitride (CNx) coating in N₂ gas stream was investigated with a newly introduced two‐step ball‐on‐disk friction test, where the rubbed Si₃N₄ ball in the pre‐sliding (step 1) was replaced by a new CNx‐coated Si₃N₄ ball in the subsequent sliding stage under N₂ gas (step 2). The two‐step friction test is clarified to be a simple but effective technique for obtaining contact material combination of self‐mated CNx coatings and for achieving stable and low frictions of CNx coatings. Friction coefficients of CNx/CNx in N₂ gas stream decrease greatly from 0.07 without pre‐sliding to less than 0.025 in two‐step friction tests. The minimum friction coefficient of 0.004 was obtained by introducing 500 cycles of pre‐sliding in ambient air. These stable and low frictions are attributed to the generation of self‐mated CNx coatings and the formation of a lubricious layer on the disk surface. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparative study on the growth mechanisms of PAHs

The efficiencies of recently proposed, phenyl addition/cyclization (PAC), methyl addition/cyclization (MAC) and a popular hydrogen abstraction/acetylene addition (HACA) mechanisms have been examined experimentally by detecting the gas phase reaction products of pyrolysis of toluene with/without addition of benzene + acetylene by using vacuum ultraviolet (VUV) single photon ionization (SPI) time of flight mass spectrometry (TOFMS). Besides the observation of verities of large polycyclic aromatic hydrocarbons (PAHs), intense mass peaks of indene, phenylacetylene and propyne confirmed a remarkable quenching of the major active species, benzyl, phenyl and methyl radicals by acetylene. In spite of quenching, only benzyl contributed products were diminished while phenyl and methyl contributed products were enhanced. Uniquely observed symmetrical PAHs; corrannulene/coronene; formed by the active involvement of PAC, HACA and/or MAC mechanisms, reflects the interdependencies of these mechanisms. Individually, PAC was found highly efficient for endless growth, HACA for filling triple fusing site and MAC for expanding cyclotetra/pentafused into benzenoid structure, respectively.     

Copolymerization of glycidylmethacrylate–methylmethacrylate–divinylbenzene in cyclohexane

The copolymerization of glycidylmethacrylate–methylmethacrylate–divinylbenzene in cyclohexane was studied as an example of crosslinking precipitation copolymerization. The resultant copolymer is fine spheroidal. The copolymerization proceeds acceleratively at first, then steadily, and gradually slows down. The larger the divinylbenzene concentration, the smaller is the copolymerization rate. Glycidylmethacrylate is preferentially incorporated in the copolymer.     

Effect of Contact Stiffness on Creep-Groan Occurrence on a Simple Caliper-Slider Experimental Model

In this paper, a fundamental mechanism for creep-groan generation is investigated by adopting a simple yet effective caliper-slider experimental model. Contact condition, which is a function of three parameters, namely normal force, contact roughness, and material combination, is connected with the creep-groan phenomenon in terms of contact stiffness. Creep-groan generation is determined by analyzing the frequency characteristic of the generated vibration acceleration when the sliding commences due to a simultaneous application and release of force in the tangential and normal directions, respectively. As per the obtained results, creep-groan occurrence or absence in the employed experimental model may be classified into three regions based upon the value of the contact stiffness, i.e., occurrence, non-occurrence, and mixed regions. The results also indicate that creep-groan occurrence in this caliper-slider experimental model can be avoided by controlling the value of contact stiffness in an effective manner.     

Effect of oxygen content on impact toughness of a fine-grained magnesium alloy

Fine-grained Mg-3Al-Zn alloys with various oxygen contents were prepared by a powder metallurgy process, and the effect of oxygen content on the impact toughness of the fine-grained magnesium alloys was quantitatively investigated. It is found that the impact toughness of magnesium alloys with mean grain size smaller than 3 μm is extremely high when the oxygen content is less than 400 pp, but it becomes very low as the oxygen content is higher than 1000 ppm. Both magnesium oxides and hydroxides are detected in the magnesium alloys. The presence of excessive magnesium oxides and hydroxides deteriorates the dynamic plastic deformation ability of the fine-grained magnesium alloys.