Electrochemical reactivity at graphitic micro-domains on polycrystalline boron doped diamond thin-films electrodes

This paper deals with the electrochemical reactivity of boron doped diamond (BDD) electrodes. A comparative study has been carried out to show the influence of the presence of graphitic micro-domains upon the surface of these films. Those graphitic domains are sometimes present on as-grown boron doped diamond electrodes. The effect of doping a pure Csp³ diamond electrode is established by highly oriented pyrolytic graphite (HOPG) abrasion onto the diamond surface. In order to establish the effect of doping on a pure Csp³ diamond electrode, the amount of graphitic domains was increased by means of HOPG crystals grafted onto the BDD surface. Indeed that method allows the enrichment of the Csp² contribution of the electrode.The presence of graphitic domains can be correlatively associated with the presence of kinetically active redox sites. The electrochemical reactivity of boron doped diamond electrodes shows a distribution of kinetic constants on the whole surface of the electrode corresponding to different active sites. In this paper, we have studied by cyclic voltammetry and electrochemical impedance spectroscopy the kinetics parameters of the ferri/ferrocyanide redox couple in KCl electrolyte. A method is proposed to diagnose the presence of graphitic domains on diamond electrodes, and an electrochemical “pulse cleaning” procedure is proposed to remove them.     

Ammoxidation activity of in situ synthesized ammonium salt of molybdophosphoric acid on VOPO4 catalysts

Two isomorphous VOPO₄ samples were synthesized by means of well-known aqueous and organic preparation methods. These materials are further used for the in situ generation of ammonium salt of 12-molybdophosphoric acid (AMPA) from their solid phase phosphate components. Formation of AMPA was confirmed by XRD, FTIR, Raman and XPS analyses. The activity of the catalysts was tested in a fixed bed tubular glass reactor at atmospheric pressure for the selective ammoxidation of 2-methylpyrazine (MP) to 2-cyanopyrazine (CP). The reaction was carried out in the temperature range of 360–420 °C. Between the two mono-phosphates tested, the α-VOPO₄ is observed to show somewhat better activity compared to β-VOPO₄. Interestingly, in situ synthesized AMPA catalysts displayed significantly better performance compared to their corresponding parent VOPO₄ solids. Among all catalysts tested, AMPA-α-VOPO₄ exhibited the best performance (conversion (MP) = ca. 90%, selectivity (CP) = 65% at T = 420 °C). The differences in catalytic performance of the tested catalysts are ascribed to the structural differences of the used VOPO₄ solids.     

Joining of C<Subscript>f</Subscript>/SiC Ceramics to Nimonic Alloys

C_f/SiC ceramic composites have been brazed to Nimonic alloys using TiCuAg filler metal. In order to improve wettability and to provide compatibility between ceramic and metal, the C_f/SiC surface was metallized through the deposition of a chromium layer. Subsequent heat treatments were carried out to develop intermediate layers of chromium carbides. Excellent wetting of both the composite ceramic and the metal from the filler metal is observed in the fabricated joints. Shear tests show that failure occurs always within the ceramic material and not at the joint. In the filler region depletion of Ti and formation of Ag and Cu rich regions are observed. At the C_f/SiC-filler interface a layered structure of the filler metallic elements is observed. Titanium interacts with the SiC matrix to form carbides and silicides.     

Single‐walled carbon nanotube/poly(methyl methacrylate) composites for electromagnetic interference shielding

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites were prepared using coagulation method. The electrical conductivity and the electromagnetic interference (EMI) shielding of SWNT/PMMA composites over the X‐band (8–12 GHz) and the microwave (200–2000 MHz) frequency range have been investigated. The electrical conductivity of composites increases with SWNT loading by 13 orders of magnitude, from 10^?15 to 10^?2 Ω^?1 cm^?1 with a percolation threshold of about 3 wt% SWNTs. The effect of the sample thickness on the shielding effectiveness has been studied, and correlated to the electrical conductivity of composites. The data suggest that SWNT/PMMA composites containing higher SWNT loading (above 10 wt%) be useful for EMI shielding and those with lower SWNT loading be useful for electrostatic charge dissipation. The dominant shielding mechanism of SWNT/PMMA composites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

DRIFTS Study on the Decomposition Mechanism of Mn Acetylacetonates Supported on SBA-15

Manganese oxides supported on mesoporous SBA-15 catalysts have been prepared by molecularly designed dispersion method, using Mn(II) and Mn(III) acetylacetonate organic precursors. XRD and in situ Raman studies demonstrate the formation of highly dispersed Mn₂O₃ and Mn₃O₄ nanoparticles on SBA-15 for the calcined samples. The detailed decomposition mechanism was studied by using in situ DRIFTS. Acetylacetonate ligands are stable up to 573 K and can only be completely removed by oxygen treatment.     

Coating the inner walls of metal tubes with carbon films by physical vapor deposition at low temperature

Tubes are often required to exhibit better performance in corrosion and wear behavior than the material the tube is made of can offer. The situation can be improved when the tube is coated with a protective film. This can be achieved by sputter coating with an ion beam. A sputter target is located inside the tube. Energetic ions are accelerated into the tube and impinge onto the target. Thus, material is sputtered from the target onto the inner walls of the tube. Two apparatus for coating tubes of different lengths and diameters are described. Aluminum and stainless steel tubes were coated with amorphous carbon films. Results on adhesion, corrosion performance in aqueous media and thickness uniformity are shown.     

Thermal,mechanical and γ-ray shielding properties of micro- and nano-Ta2O5 loaded DGEBA epoxy resin composites

In this work, we have investigated the synergistic effect of micro- and nano-Ta₂O₅ fillers in the epoxy matrix on the thermal, mechanical, and radioprotective properties of the composites. Morphological analysis revealed uniform dispersion of fillers in the matrix. Both the thermal stability and tensile properties of matrices have enhanced in the presence of fillers. Although the nanocomposites showed significantly higher tensile strength and Youngs modulus compared to micro-composites, the enhancement in these properties was predominant at low loadings. Dynamic mechanical analysis indicated good interfacial adhesion and positive reinforcing effect on the matrix even at higher loading (30 wt%) of nano-Ta₂O₅. γ-Ray attenuation studies performed in the energy range of 0.356–1.332 MeV revealed better γ-ray shielding ability of nanocomposites compared to microcomposites at same weight fraction of fillers. In particular, γ-ray attenuation at 0.356 MeV for 30 wt% nano-Ta₂O₅ loaded epoxy composite was enhanced by around 13% compared to the microcomposite at the same loading. Increased surface-to-volume ratio of nanofillers and consequent increase in matrix-filler adhesion and radiation-matter interaction have manifested in an overall enhancement in the thermal, mechanical, dynamic mechanical, and radiation shielding characteristics of nano-Ta₂O₅/epoxy composites, proving them as promising γ-ray shields.     

Phase selection and microstructure formation in undercooled Co–61.8 at.% Si melts under various containerless processing conditions

The hypoeutectic composition Co–61.8 at.% Si was undercooled and solidified using electromagnetic levitation, electromagnetic levitation under a static magnetic field, electrostatic levitation and glass-fluxing. The samples generally showed two thermal events, either separated or continuous depending on undercooling. In situ monitoring of the two thermal events with a high-speed camera revealed a sudden decrease of dendritic growth velocities of primary phases at a critical undercooling of 88 K. Scanning electron microscopy studies of the solidified samples showed that the CoSi compound and the CoSi₂ compound nucleate as the primary phase for low and high undercoolings, respectively. The microstructure of the samples depends not only on undercooling, but also on the onset temperature or delay time of the second thermal event. Melt convection has no effect on the primary phase selection in undercooled melts, but it has a significant effect on the delay time and therefore on microstructure formation of the samples for high undercoolings.     

In situ synchrotron tomography estimation of toughening effect by semi-ductile fibre reinforcement in a tungsten-fibre-reinforced tungsten composite system

Tungsten-fibre-reinforced tungsten composites (W_f/W) are supposed to enable enhanced toughness owing to extrinsic energy dissipation mechanisms such as interface debonding and plastic deformation of fibre. In particular, the latter is an effective source of toughening, since ductile tungsten fibres can absorb a considerable amount of plastic work. For a precise evaluation of the toughening capability, the energy dissipation mechanisms need to be analysed in detail. To this end, single-fibre tungsten composite specimens are fabricated and the stress–strain behaviour of the tungsten fibre bridging a matrix crack is measured by means of in situ high-energy synchrotron microtomography during a uniaxial tensile test. Despite the high X-ray attenuation in tungsten, a sufficiently high resolution is achieved and clear images of crack extension and deformation are obtained. The amount of absorbed energy due to plastic deformation of the tungsten fibre is determined and compared with values obtained conventionally from single-fibre tensile tests.