Effect of Mo on corrosion behavior of Ni20Cr–xMo alloys in air with NaCl–KCl–CaCl2 vapor at 570°C

The effect of Mo on the corrosion behavior of Ni20Cr–xMo alloys in an oxidizing chlorine-containing atmosphere using air mixed with the salt-vapor mixture of NaCl–KCl–CaCl₂ at 570°C was investigated. The results revealed that the corrosion performance of the Ni20Cr alloys in the oxidizing chlorine atmosphere was improved by Mo addition of up to 3 wt%. The Mo-free alloy formed a potassium chromate during corrosion as a result of the reaction between the Cr₂O₃ scale and KCl vapor. The chromate formation increased the chlorine potential at the scale surface and induced the breakdown of the protective Cr₂O₃ scale, resulting in internal chromium chloride precipitates and a Cr-depleted zone. In contrast, the presence of Mo resulted in the formation of a NiO scale, which did not react with the salt vapors and, therefore, prevented the formation of chromates. The beneficial effect of Mo on the high-temperature chlorination of Ni–Cr alloys in salt-vapor-containing atmospheres was ascribed to the suppression of chlorine generation due to NiO scale formation.     

Differential Scanning Calorimetric Study of Solidification Behavior of Monoacylglycerols to Investigate the Cold-Flow Properties of Biodiesel

Monoacylglycerols (MAG) are impurities present in biodiesel as a result of incomplete reactions. MAG often solidify in biodiesel even at room temperature because of their high melting points. This worsens the cold-flow properties such as the cloud point and pour point. We hypothesized that several types of MAG solidify simultaneously; therefore, we performed differential scanning calorimetry of binary mixtures of MAG to elucidate their interactions during solidification. Three thermodynamic formulas were then applied to the experimental results: (1) non-solid-solution, (2) solid-solution, and (3) compound formation models. Binary mixtures of MAG showed complicated liquidus curves with multiple upward convex shapes, with which only the compound formation model fitted well. This model was applied to multicomponent mixtures that consisted of MAG and fatty acid methyl esters (FAME) as surrogate biodiesel fuels. We confirmed that the model still worked well. The results show that the compound formation model has good potential for predicting the cold-flow properties of biodiesel.     

Bottom-up synthesis of oxygen-containing carbon materials using a Lewis acid catalyst

Oxygen-containing carbon materials have been studied extensively because of their excellent dispersibility, absorptivity, separability, and supportability of catalysts. However, structural control by existing top-down methods is almost impossible. Our group has demonstrated that phloroglucinol (PG, 1,3,5-trihydroxybenzene) can be a promising raw material to synthesize structurally controlled oxygen-containing carbon materials. In this study, in addition to PG, hexahydroxybenzene (HHB), which has more oxygen and high symmetry, was used as the raw material, and a Lewis acid catalyst, tris (pentafluorophenyl) borane (TPB), was used to enhance the structural control rate and the removability of catalysts from the carbonized samples. The solubility of heat-treated HHB was lower than that of heat-treated PG, but the oxygen content of heat-treated HHB was higher than that of heat-treated PG even at 673 K. By adding TPB to PG, dibenzofuran-like structures formed, and the structural control rate increased up to 93.6%. Besides, the content of fluorine in the catalyst was reduced to 0%, indicating that TPB can be a promising recyclable catalyst to promote the structural control rate of carbonized PG.

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Effect of TiO2 on morphology and mechanical properties of PVDF/PMMA blend films prepared by melt casting process

Effect of titanium dioxide (TiO₂) on morphology and mechanical properties of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blend films prepared at different TiO₂ contents by a melt casting process was studied. The results showed that tensile moduli in both the machine direction (MD) and the transverse direction (TD) increased with increasing TiO₂ content, and calculated tensile moduli based on the Halpin–Tsai and the Kerner model were consistent with experimental ones in both the MD and TD of films containing 10 wt % TiO₂. However, experimental tensile moduli exhibited smaller values compared with calculated ones, as the TiO₂ content increased to 30 wt %_, and it was assumed that this is due to the decrease of crystallinity of PVDF. Morphological observations indicated that TiO₂ particles did not affect crystal structures of PVDF and the morphology of PVDF/PMMA amorphous phase, but hindered the crystallization of PVDF. The MD and TD elongation at break exhibited >200 and <20%, respectively. The SEM micrographs revealed that spherulites could deform along the MD when the tensile force was applied along the direction. By contrast, spherulites could not deform along the TD and fractured at very small elongation, owing to the anisotropic morphology of spherulites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40454.     

Identification and Characterization of D‐Succinylase,and a Proposed Enzymatic Method for D‐Amino Acid Synthesis

Chiral amino acids are important intermediates for the pharmaceutical industry. We have developed a novel one‐pot enzymatic method for D ‐amino acid synthesis by the dynamic kinetic resolution of N‐succinyl‐dl ‐amino acids using D ‐succinylase (DSA) and N‐succinylamino acid racemase (NSAR, EC 4.2.1.113). The DSA from Cupriavidus sp. P4‐10‐C, which hydrolyzes N‐succinyl‐D ‐amino acids enantioselectively to their corresponding D ‐amino acids, was identified for the first time by screening soil microorganisms. Subsequently, the DSA gene was cloned and overexpressed in Escherichia coli. DSA was shown to comprise two subunits with molecular masses of 26 kDa and 60 kDa. Additionally, the NSAR gene from Geobacillus stearothermphilus NCA1503, which racemizes N‐succinylamino acids, was also cloned and overexpressed in E. coli. The highly purified DSA and NSAR prepared from each recombinant E. coli were characterized and used for D ‐amino acid synthesis. A one‐pot enzymatic method converted 100 mM N‐succinyl‐dl ‐phenylalanine to D ‐phenylalanine in 91.1% conversion with 86.7% ee. This novel enzymatic method may be useful for the industrial production of many D ‐amino acids.