Plasma etching treatment for surface modification of boron-doped diamond electrodes

Boron-doped diamond (BDD) thin film surfaces were modified by brief plasma treatment using various source gases such as Cl₂, CF₄, Ar and CH₄, and the electrochemical properties of the surfaces were subsequently investigated. From X-ray photoelectron spectroscopy analysis, Cl and F atoms were detected on the BDD surfaces after 3 min of Cl₂ and CF₄ plasma treatments, respectively. From the results of cyclic voltammetry and electrochemical AC impedance measurements, the electron-transfer rate for Fe(CN)₆^3−/4− and Fe^2+/3+ at the BDD electrodes was found to decrease after Cl₂ and CF₄ plasma treatments. However, the electron-transfer rate for Ru(NH₃)₆^2+/3+ showed almost no change after these treatments. This may have been related to the specific interactions of surface halogen (C-Cl and C-F) moieties with the redox species because no electrical passivation was observed after the treatments. In addition, Raman spectroscopy showed that CH₄ plasma treatment of diamond surfaces formed an insulating diamond-like carbon thin layer on the surfaces. Thus, by an appropriate choice of plasma source, short-duration plasma treatments can be an effective way to functionalize diamond surfaces in various ways while maintaining a wide potential window and a low background current.     

Processing and Thermal Conductivity of Sintered Reaction-Bonded Silicon Nitride. I: Effect of Si Powder Characteristics

This paper will present sintered reaction-bonded silicon nitride (SRBSN) material with a high thermal conductivity of 121 W·(m·K)⁻¹, which has been successfully prepared from a coarse Si powder with lower levels of oxygen and aluminum impurities, using a mixture of Y₂O₃ and MgSiN₂ as sintering additives, by nitriding at 1400°C for 8 h and subsequent post-sintering at 1900°C for 12 h at a nitrogen pressure of 1 MPa N₂. This thermal conductivity value is higher than that of the materials prepared from high-purity α-Si₃N₄ powder (UBE SN-E10) with the same additive composition under the same sintering conditions. In order to study the effects of Si powder characteristics on the processing, microstructure, and thermal conductivity of SRBSN, the other type of fine powder with higher native oxygen and metallic impurity (typically Al and Fe) contents was also used. The effects of Si particle size, native oxygen, and metallic impurities on the nitriding process, post-sintering process, and thermal conductivity of the resultant SRBSN materials were discussed in detail. This work demonstrates that the improvement in thermal conductivity of SRBSN could be achieved by using higher purity coarse Si powder with lower levels of oxygen and aluminum impurities. In addition, this work also shows that the nitriding temperature has no significant effect on the microstructure and thermal conductivity of SRBSN during post-sintering, although it does affect the characteristics of RBSN formed during nitridation.     

Leaching behavior of heat-treated waste ash

The leaching behavior of heat-treated waste ash was studied to verify the possibility of the thermal treatment of waste incineration ash in existing incinerators and boiler combustion chambers. The influence of temperature, oxygen concentration and treatment time on the leaching behaviors of harmful heavy metals, especially lead (Pb) and chromium(VI) (Cr (VI)) were studied to clarify effective treatment conditions to suppress leaching. By examining the leaching behavior of Pb and Cr from ash heat-treated under various conditions, it was found that leaching can be suppressed by heat-treating the ash under conventional combustion conditions of around 900-1000 °C at 5-10% oxygen concentration. The leaching behaviors of Pb and Cr (VI) from real ash with different particle sizes and from model samples were also investigated in detail to find an effective method to suppress Pb leaching. It was found that the formation and growth of gehlenite (SiO₂·2CaO·Al₂O₃) in the ashes led to the decrease in the amount of Pb leaching. Therefore it was considered that the addition of an inorganic matrix with a high silica content that can promote gehlenite growth in the ash, for example, coal ash or waste glass is effective to suppress of Pb leaching.     

Synthesis and properties of novel side-chain-sulfonated polyimides from bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone

A novel side-chain-sulfonated aromatic diamine of bis[4-(4-aminophenoxy)-2-(3-sulfobenzoyl)]phenyl sulfone (BAPSBPS) was synthesized. Sulfonated copolyimides were synthesized by random and sequenced block copolymerization of 1,4,5,8-naphthalene tetracarboxylic dianhydride, BAPSBPS and nonsulfonated diamine. They displayed good solubility in common aprotic solvents and high desulfonation temperature of 350 °C, suggesting the high stability of sulfonic acid groups. The reduced viscosity was in the range of 0.4-1.8 dl/g at 0.5 g/dl and 35 °C. Flexible and tough membranes with reasonably high mechanical strength were prepared. They showed anisotropic membrane swelling with larger swelling in thickness than in plane. They displayed reasonably high proton conductivity (σ), taking their lower ion exchanging capacity (IEC) into account. For example, the membrane with IEC of 1.54 mequiv/g showed σ values of 81 and 11 mS/cm in water and 70% RH, respectively, at 60 °C.     

Quantitative imaging of Young's modulus of solids: a contact-mechanics study

We developed equipment and methods for measuring quantitatively the local Young's modulus of solids. It consists of an electrodeless langasite oscillator and line antennas, and oscillator vibrations are generated and detected contactlessly. A constant biasing force results from oscillator mass and is independent of surface roughness. The effect of material anisotropy on the measured stiffness is theoretically discussed for studying the limitation of the quantitative measurement. The microscopy has been applied to polycrystalline copper, and the measured modulus is compared to calculations based on electron-backscatter-diffraction measurements. Also, we applied it to a duplex stainless steel and an embedded silicon-carbide fiber. The results reveal textured regions, defects with high sensitivity, and even stiffness distribution in a single grain.     

Investigation of anti-wear additives for low viscous synthetic esters: Hydroxyalkyl phosphonates

Various synthetic esters are widely applied as lubricating fluid to reduce friction and wear at tribological contact. Among them low viscous synthetic esters are expected to improve fuel efficiency by minimizing the fluid friction. These low viscous esters are composed of short-chain fatty acids. Therefore, low viscous synthetic esters are inherently polar molecules. Since efficiency of anti-wear additives decreases with increase of polarity of the base oil, new additive technology is requested.In this work, hydroxyalkyl phosphates [P(O)(OCHRCH₂OH)₃], and hydroxyalkyl phosphonates [P(OH)_n(OCHRCH₂OH)_3−n, where n=1,2] are proposed as novel anti-wear additives for polar synthetic esters. The anti-wear additives are evaluated under the boundary conditions. The additives prevent wear in polar esters, in which conventional anti-wear additives do not work at all. Interestingly, effects of substituent in additive molecule on anti-wear properties are found. Alkyl and aryl derivatives reduce wear remarkably, whereas allyl derivatives exhibit poor results. It is speculated that the anti-wear inefiiciency of allylic compounds is due to auto-oxidation of the additives.A facile preparative method for hydroxyalkyl derivatives characterizes the present additive system. They are prepared in situ by simply mixing phosphonic acid and substituted epoxides. Flexiblity of lubricant design can be made possible by the present additive system.     

Effect of conformational changes and differences of proteins on frictional properties of poly(vinyl alcohol) hydrogel

In this study, albumin or γ-globulin, both of which are included in natural synovial fluid, was used as an additive into lubricants to investigate the ability to reduce the friction for poly(vinyl alcohol) hydrogel in mixed lubrication. It was found from a measurement in circular dichroism that albumin contains a large amount of α-helix structure and γ-globulin contains a large amount of β-sheet structure. The lubricant containing only albumin showed low friction compared to the lubricant containing only γ-globulin. The effect of protein boundary film was clarified by changing lubricant. Albumin kept the friction low after changing from γ-globulin used at initial rubbing, but γ-globulin increased the friction after changing from albumin at initial rubbing. From a sliding distance of 600 m, albumin showed lower friction but γ-globulin showed higher friction. Therefore, in the case of friction decreasing, γ-globulin forms a tight adsorbed layer and subsequently albumin forms a layer with low shearing strength. Hence, it is important to apply the adsorption layer of γ-globulin at the bottom and make a layered structure composed of albumin and γ-globulin to reduce both friction and wear.     

Note: detection of micro-cracks in the interlayer dielectric film by the stress based light scattering method

A phenomenon was discovered wherein light scattering strength from cracks increases when tensile stress is applied to micro-cracks produced in the interlayer dielectric film by chemical mechanical polishing treatment. It is likely that the change in light scattering intensity occurs because a region of high stress concentration (region with high variation in index of refraction) is produced near the crack tip due to stress, thus forming a type of scatterer. With this method, it is possible to detect only scatterers which respond to stress, and thus, it is possible to classify and separately detect cracks and particles.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.