Characterization of carbonaceous films deposited on metal substrates by liquid-phase electrodeposition in methanol

In this study, we report the characterization of carbonaceous films deposited on metal substrates by liquid-phase electrodeposition in methanol. The characterization of carbonaceous films by electrodeposition was examined by means of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (EELS), secondary ion mass spectrometry (SIMS), atom probe (AP) and high resolution-elastic recoil detection analysis (HR-ERDA). From these results, it was found that the films deposited on the metal substrates were composed of the sp² and sp³ carbon contents, of which the ratio was about 7:3. Furthermore, the films by electrodeposition contained much hydrogen. The hydrogen contents in the surface were about 60 at.% and those in the subsurface were a few 10 at.%.     

Enzymatic syntheses of N-lauroyl-β-alanine homologs in organic media

Enyzmatic amidation of the primary amines β-alanine ethyl ester and 3-aminopropionitrile with methyl laurate by means of immobilized lipase (Candida antarctica lipase, CAL) resulted in the formation in good yield of N-lauroyl-β-alanine ethyl ester and 3-(N-lauroylamino)-propionitrile, respectively. When 3-amino-propionitrile was used as substrate, diisopropyl ether was a suitable solvent. Changing the reaction temperature (12–80°C) did not affect the yields, and room temperature was a suitable temperature for this reaction. In the investigation of reaction conditions, the use of equimolar amounts (5 mmol) of substrate and ester, along with 0.5 g of CAL, in diisopropyl ether gave the best yield (99.3%) after 24 h of incubation at 24°C. The enzyme activity in the amidation reaction did not decrease even after six uses. With β-alanine ethyl ester hydrochloride as substrate, diisopropyl ether was unsuited as a solvent owing to the low solubility of the substrate in this solvent. In this reaction, the best yield (82.0%) was attained by using dioxane as solvent. CAL achieved higher extents of amide synthesis with long-chain than with short-chain ester substrates. The enzyme accepted only nonbulky primary amines as substrates.     

Quasi-Chemical Viscosity Model for Fully Liquid Slag in the Al2O3-CaO-MgO-SiO2 System—Part I: Revision of the Model

A model has been developed that enables the viscosities of the fully liquid slag in the multi-component Al₂O₃-CaO-FeO-Fe₂O₃-MgO-Na₂O-SiO₂ system to be predicted within experimental uncertainties over a wide range of compositions and temperatures. The Eyring equation is used to express viscosity as a function of temperature and composition. The model links the activation and pre-exponential energy terms in the viscosity expression to the slag internal structure through the concentrations of various Si_0.5O, $ {\text{Me}}^{n + }_{2/n} {\text{O}} $ , and $ {\text{Me}}^{n + }_{ 1/n} {\text{Si}}_{0. 2 5} {\text{O}} $ viscous flow structural units (SUs). The concentrations of these SUs are derived from a quasi-chemical thermodynamic model of the liquid slag using the thermodynamic computer package FactSage. The model describes a number of slag viscosity features including the charge compensation effect specific for the Al₂O₃-containing systems. The predictive capability of the model is enhanced by the physical aspects of the model parameters—the correlation with other physicochemical properties as well as experimental viscosity data is used to determine model parameters. The present series of two papers outlines (a) recent significant improvements introduced into the model formalism and (b) application of the model to the Al₂O₃-CaO-MgO-SiO₂ system, review of experimental viscosity data, and optimization of the corresponding model parameters for this system.     

Effect of substituting elements on hydrogen uptake for Pd–Rh–H and Pd–Ag–H systems evaluated by magnetic susceptibility measurement

The magnetic susceptibility and the pressure-composition isotherm were measured simultaneously for Pd–Rh–H and Pd–Ag–H systems in order to clarify the effect of Rh or Ag substitution on the hydrogen uptake from viewpoint of the electronic band structure. The magnetic susceptibility of all Pd binary alloys prepared decreased monotonically with increasing hydrogen content. At high hydrogen contents, the magnetic susceptibility became approximately zero for Pd–Rh–H and Pd–Ag–H system, and the hydrogen content at which the magnetic susceptibility gives zero corresponded with the terminal of the plateau region in the isotherm curve. The results indicated that the magnetic susceptibility of hydride phase was almost zero for all Pd binary alloys. On the basis of the band structure of Pd metal, we concluded that atom substitution only affected shift of the energy at Fermi level, and the amount of the hydrogen uptake was dominated by the number of unoccupied d-band in the alloys.     

Power characteristics of unsteadily forward–reverse rotating impellers in an unbaffled aerated agitated vessel

Power characteristics of an unbaffled aerated agitated vessel with unsteadily forward‐reverse rotating impellers, ie a new type of gas–liquid agitator named ‘AJITER’, treating viscous Newtonian liquids were studied experimentally. Measurements were first made on the agitation torque, ie the torque on the drive shaft on which forward–reverse rotating impellers with four delta‐type blades were attached, and the data obtained were analyzed by fitting them to an equation consisting of two terms with respect to the resistance of the fluid, one due to viscous drag and the other due to added moment of inertia. The effects of operating conditions and physical properties of liquids on the drag and added moment of inertia coefficients were then evaluated, and empirical relationships which estimate values of these coefficients, useful to predict the unsteady behavior and magnitude of agitation torque, were presented. Furthermore, equations were developed for estimating the average and maximum power consumptions as a function of the drag and added moment of inertia coefficients. Prediction of respective power levels in AJITER by these equations was also discussed. © 2001 Society of Chemical Industry     

Amphiphilic Poly(Amino Acid) Nanoparticles Induce Size‐Dependent Dendritic Cell Maturation

Size‐regulated amphiphilic poly(amino acid) nanoparticles (NPs) composed of poly(γ‐glutamic acid) (γ‐PGA) and the hydrophobic amino acid derivative, L ‐phenylalanine ethyl ester (Phe) are prepared to evaluate the effects of particle size on dendritic cell (DC) uptake of NPs and their immune stimulatory activities as delivery carriers and adjuvants. The size of the Phe‐conjugated γ‐PGA NPs (γ‐PGA–Phe NPs) is easily controlled by regulating the aggregated γ‐PGA–Phe numbers. Each of the differently sized γ‐PGA–Phe NPs could efficiently encapsulate ovalbumin (OVA), and the amount of encapsulated OVA per milligram of NPs is almost the same despite the differences in size. The DC uptake of small NPs is lower than for the larger NPs, but the effect of DC activation by NPs is high in the small sizes. The DC activation is significantly affected by the size of the NPs, which suggests that not only the uptake process of the NPs, but also the surface interactions between the NPs and DCs, is important for the induction of DC maturation. The precisely size‐controllable γ‐PGA–Phe NPs have significant potential as an antigen carrier and vaccine adjuvant. These results should provide guidelines for adjuvant design in the development of an effective vaccine.     

First-Principles Investigation of the Atomic and Electronic Structures of α-Al2O3(0001)/Ni(111) Interfaces

Atomic and electronic structures of α-Al₂O₃(0001)/Ni(111) interfaces have been investigated using the first-principles pseudopotential method. Models with different rigid-body translations parallel to the interface for both the O-terminated and Al-terminated interfaces are examined in order to clarify the overall features. Results indicate that the interface stoichiometry as well as the interface configuration has significant effects on the adhesive and electronic properties. The bonding nature of the O-terminated interfaces is explained by strong ionic and Ni-3d/O-2p orbital hybridization interactions, and that of the Al-terminated interfaces is explained mainly by image-charge like electrostatic and Ni–Al hybridization interactions, although there is some Ni–O hybridization for the O-site model. Orbital hybridization and adhesive energies are larger than those in the corresponding Al₂O₃/Cu interfaces, because Ni has higher activity for making bonds with ceramics than Cu.     

A feasibility study for the removal of copper from solid ferrous scrap

A new approach for the removal of copper from solid ferrous scrap is described. With this proposal, solid ferrous scrap intermingled with copper is brought into contact with molten aluminium, which preferentially dissolves copper. After a duration of 5 to 10 minutes at a temperature of 1018 ± 5 K, steel scrap is removed from the bath, resulting in being free of copper contamination. The present method offers the advantage of far lower costs than any other processes ever suggested for copper removal.     

Analysis of electromagnetic force in wire-EDM

This paper clarifies the mechanism of how electromagnetic force applied to the wire electrode in wire electrical discharge machining (wire-EDM) is generated. This electromagnetic force is caused not only by DC component but also by AC components of the discharge current supplied to the wire. We therefore developed and used a two-dimensional finite element method (FEM) program to analyze the electromagnetic field taking into account electromagnetic induction. Assuming that trapezoidal pulse current is supplied to the wire, distributions of the current density and magnetic flux density were analyzed and changes in the electromagnetic force applied to the wire were calculated. Wire movement when the electromagnetic force alone was applied to the wire was also calculated. The calculated wire movement agreed with the measured wire movement when pulse current actually used in WEDM was supplied to the wire, clarifying the mechanism of electromagnetic force generation.