Development and properties of nanostructured thermal spray coatings

Nanostructured thermal spray coatings have been intensively studied because of their potential in a wide variety of industrial applications. In the present paper, current development status of nanostructured thermal spray coatings is presented, mainly based on the results of the authors. In the nanostructured WC–Co wear-resistant coatings, the influence of feedstock characteristics on the coating properties was discussed to suggest the desirable morphology of feedstock for thermal spraying. For the nanostructured Cr₂O₃ based solid-lubricant coatings, the advanced feedstock has been developed in order to solve the inhomogeneity problem of the conventional coatings. Various properties of the nanostructured coatings were evaluated and compared with those of the conventional counterparts. These results clearly demonstrate that the significant improvement in coating performance can be achieved by utilizing proper nanostructured coatings.     

An optical study of cobalt nanowires dispersed in liquid phase

The Co nanowires were electrodeposited in polycarbonate membrane (PCT). SEM, TEM and XPS techniques were used to characterize the morphology, structure and size of nanowires as well as chemical composition. The influence of different mediums was studied on the optical absorption of dispersed cobalt nanowires. The absorption spectrum of cobalt nanowires in water showed a broad shoulder at 290 nm, but in ethanol solution it was not observed in the visible region of the spectra up to 200 nm. Cobalt nanowires dispersed in methanol presented a peak at 236 nm. We attribute the data to oxidation of cobalt in water and low dielectric constant of methanol relative to ethanol and water. We found rather good agreement between the experimental results and the calculation based on Gans’ theory.     

Thermal Conversion of Gels Prepared by the Complex Sol-Gel Process (CSGP) from Li+-Me2+-CH3COO−-Ascorbic Acid (ASC)-NH4 +-OH−-H2O Systems to LiMn2O4 and LiNi x Co1 − x O2

The spinel LiMn₂O₄ and layered oxides LiNi _x Co_{1 – x} O₂ (x = 1; 0.75; 0) have been prepared by Complex Sol-gel Process (CSGP). The appropriate sol compositions were obtained from acetate aqueous solution of metals containing ascorbic acid by alkalizing it with aqueous ammonia. Gels were produced from the systems by evaporation of water and other volatilies at elevated temperatures. A very intense foaming was observed during the heating at the temperatures higher than 140°C. To avoid foaming in the course of the final thermal treatment, a very long (lasting several days) soaking step was found necessary. However pretreated materials exhibit self-ignition at temperature range 320–500°C dependent on socking conditions. The dependence of self-ignition temperature on carbon content in bed as well as on specific surface has not been proved. Final thermal transformation of gel to solid was studied by TG, DTA, XRD, and IR methods. It was observed that final compounds are formed faster from precursors which did not contain Ni (e.g. LiMn₂O₄ and LiCoO₂), while Li carbonate is not formed in these systems. In contrast, in Li-Ni(Co)-O the formation of Li(or Ni)CO₃ was always proved. In addition, during the thermal treatment Ni species are partially reduced even to metallic phase. This effect evidently restrains the formation of pure layered oxides phase. Electrochemical properties of carbonate free compounds are definitely better than of those containing CO₃.     

Conversion of cyclohexene on supported molybdenum- and tungsten-oxide catalysts

The hydro-dehydrogenation of cyclohexene has been studied on: alumina supported Co-, Ni-, Pd-, Pt-promoted and non promoted MoO_x, monometallic Co, Ni and Pt, two - alumina and silica-alumina supported - Ni-promoted WO_x-s. Two groups of characteristically different catalytic behavior of the promoted MoO_x and WO_x samples were identified dependent of the presence and nature of the zerovalent metal on the catalyst surface. No additivity of activities but some interaction between metals and oxides was expressed in the catalytic behavior of the M(8-10)MoO_x catalysts. This revised version was published online in June 2006 with corrections to the Cover Date.     

Thermal decomposition study of cobalt(II)-mixed ligand complexes with aliphatic or aromatic dicarboxylic acids and imidazole

The thermal decomposition study of Co(II)–malate, tartarate and phthalate complexes with imidazole was monitored by TG, DTG and DTA analysis in static atmosphere of air. The complexes and their calcination products were characterized by IR spectroscopy. The decomposition course and steps were analyzed and the kinetic parameters of the non-isothermal decomposition were calculated. The results revealed that the decomposition processes of these complexes are the best described by a random nucleation mechanism. The stability order found for these complexes follows the trend tartarate>phthalate>malate in terms of the dicarboxylic acid ligands.     

Influence of acid–base properties of cobalt–molybdenum catalysts supported on magnesium orthophosphates in isomerization of 3,3-dimethylbut-1-ene

Synthesis and physico-chemical characterization of a pure magnesium phosphate (MgP) prepared by coprecipitation, and MgP modified by introduction of cobalt–molybdenum (4–12 wt.% of MoO₃ with the Co/Mo ratio fixed at 0.5) have been carried out. The structural properties of these catalysts were characterized by X-ray diffraction, their textural properties were determined by N₂ adsorption–desorption isotherms and the dispersion of cobalt–molybdenum was studied by XPS spectroscopy. Their acid properties have been investigated by in situ FT-IR spectroscopy of adsorbed molecules, often, 2,6-dimethylpyridine (pK_a = 6.7), pyridine (pK_a = 5.3). Co–Mo incorporation leads to a modification in the MgP acid–base properties, especially on the acid sites type and number. Thus, lower loading of cobalt–molybdenum species decreased the number of strong Lewis acid sites whereas higher loading increased it. It was found that Lewis acid sites on magnesium phosphates play an important role in the isomerization of 3,3-dimethylbut-1-ene.The 3,3-dimethylbut-1-ene (33DMB1) conversion increases with the reaction temperature from 493 to 653 K for MgP, but decreases after 573 K for MgP supported by Co–Mo. A linear relationship between both types of acid sites and conversion values was found. The deactivation of the catalysts appears at high reaction temperature (>573 K).     

HVOF制备的多峰WC-12Co涂层摩擦磨损特性

本文采用超音速火焰喷涂(HVOF)工艺制备了2种多峰结构和1种亚微米结构WC-12Co涂层,并采用SEM、XRD等方法对3种涂层进行了显微组织、孔隙率、相结构及显微硬度分析;在进行涂层球盘摩擦磨损试验的基础上,探讨了多峰WC-12Co涂层的磨损机理.研究结果表明:由含30% 纳米WC-12Co的粉末制备的多峰涂层WC氧化脱碳程度最低,显微硬度最高;采用含50%纳米WC-12Co的粉末制备的多峰涂层孔隙率最低、耐磨损性能最为优良.     

Solvothermal Synthesis and Crystal Structure of a 1D Helical-chain Cobalt（II） Complex Containing （Quinolin-8-yloxy）acetate

The cobalt(II) complex with (quinolin-8-yloxy)acetate, [CoCl(C11H8NO3)]n (1), has been prepared via the solvothermal method and characterized by IR, elemental analysis, UV- Vis diffuse-reflection spectra and single-crystal X-ray diffraction analysis. Complex 1 is a novel carboxylate-bridged one-dimensional helical cobalt(II) polymer, and the Co(II) centre exhibits an approximately square pyramidal CoClNO3 coordination geometry. It crystallizes in monoclinic, space group P21/n, with a = 9.1594(10), b = 6.8864(7), c = 17.290(2) , β = 102.629(3)o, C11H8ClCoNO3, Mr = 296.56, V = 1064.2(2) 3, Z = 4, Dc = 1.851 g/cm3, F(000) = 596, μ = 1.856 mm-1, the final R = 0.0308 and wR = 0.0807. Interestingly, the chain complexes are assembled to form two-dimensional networks through intermolecular face-to-face π-π stacking interactions with the centroid-to-centroid distance of 3.559(1)  and the dihedral angle of 8.4(1)° between the aromatic rings.     

Development and validation of a highly sensitive LC-MS/MS method for simultaneous quantitation of acetyl-CoA and malonyl-CoA in animal tissues

A highly sensitive and specific LC‐MS/MS method was developed for simultaneous estimation of acetyl co‐enzyme A (ACoA) and malonyl co‐enzyme A (MCoA) in surrogate matrix using n‐propionyl co‐enzyme A as an internal standard (IS). LC‐MS/MS was operated under the multiple reaction‐monitoring mode using the electrospray ionization technique. Simple acidification followed by dilution using an assay buffer process was used to extract ACoA, MCoA and IS from surrogate matrix and tissue samples. The total run time was 3 min and the elution of both analytes (ACoA, MCoA) and IS occurred at 1.28 min; this was achieved with a mobile phase consisting of 5 mM ammonium formate (pH 7.5)–acetonitrile (30:70, v/v) delivered at a flow rate of 1 mL/min on a monolithic RP‐18e column. A linear response function was established for the range of concentrations 1.09–2187 and 1.09–2193 ng/mL for ACoA and MCoA, respectively. The intra‐ and inter‐day precision values for ACoA and MCoA met the acceptance as per FDA guidelines. ACoA and MCoA were stable in a battery of stability studies viz. bench‐top, auto‐sampler and long‐term. The developed assay was used to quantitate ACoA and MCoA levels in various tissues of rat. Copyright © 2011 John Wiley & Sons, Ltd.