Anodic dissolution of titanium in NaCl-containing ethylene glycol

Anodic dissolution behavior of titanium in NaCl-containing ethylene glycol has been examined to obtain electropolished titanium surface. During anodic polarization in 1 mol dm^?3 NaCl ethylene glycol solution at 293 K, the titanium electrode covered with oxide dissolves with gas evolution at potentials higher than 10 V (Ag/AgCl) while it is in passive state at potentials lower than 5 V. However, after removal of the oxide layer by pre-polarization at gas-evolving potentials, no gas evolution is observed, and the titanium electrode shows a limiting dissolution current as tetravalent species at potentials higher than 5 V, producing a smooth surface. The polarization of the rotating disk titanium electrode reveals that the kinetics of the mass transfer reaction for electropolishing of titanium is controlled by titanium species dissolved into the solution, not by chloride ions or water containing in the solution. Repetition of dynamic polarization gives a well-electropolished surface.     

Phase separation and dewetting in polystyrene/poly(vinyl methyl ether) blend thin films in a wide thickness range

Phase separation and dewetting processes of blend thin films of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in two phase region have been studied in a wide film thickness range from 65 μm to 42 nm (∼2.5R_g, R_g being radius of gyration of a polymer) using optical microscope (OM), atomic force microscope (AFM) and small-angle light scattering (LS). It was found that both phase separation and dewetting processes depend on the film thickness and were classified into four thickness regions. In the first region above ∼15 μm the spinodal decomposition (SD) type phase separation occurs in a similar manner to bulk and no dewetting is observed. This region can be regarded as bulk. In the second region between ∼15 and ∼1 μm, the SD type phase separation proceeds in the early stage while the characteristic wavelength of the SD decreases with the film thickness. In the late stage dewetting is induced by the phase separation. In the third region between ∼1 μm and ∼200 nm the dewetting is observed even in the early stage. The dewetting morphology is very irregular and no definite characteristic wavelength is observed. It is expected that the irregular morphology is induced by mixing up the characteristic wavelengths of the phase separation and the dewetting. In the fourth region below ∼200 nm the dewetting occurs after a long incubation time with a characteristic wavelength, which decreases with the film thickness. It is considered that the layered structure is formed in the thin film during the incubation period and triggers the dewetting through the capillary fluctuation mechanism or the composition fluctuation one.     

Cross-section corrosion-potential profiles of aluminum-alloy brazing sheets observed by the flowing electrolyte scanning-droplet-cell technique

The scanning-droplet-cell (SDC), recently used for studying electrochemistry of electrodes in micro-areas, was modified to a flowing electrolyte-type one (f-SDC), in which fresh electrolyte was continuously supplied on the surface to be examined. The f-SDC with a coaxial double capillary structure could avoid the contamination of electrolyte by species dissolved from the measuring electrode surface. In the present study, the f-SDC technique was applied successfully to obtain profiles of the corrosion potential for the cross-sections of aluminum-alloy brazing sheets, used for the heat exchanger of the automobile. The brazing sheets consist of an Al-Zn alloy sacrificial anode layer, an Al-Mn-Cu core layer and an Al-Si brazing filler. The profiles of the corrosion potential, important to evaluate the corrosion protection performance of the sacrificial anode, revealed that the potential gradient arising from the sacrificial anode to the core layer is mainly controlled by zinc, which diffuses from the former layer to the latter during the cladding treatment and the post-heat treatment.     

Preparation of nanocomposites by melt compounding polylactic acid/polyamide 12/organoclay at different screw rotating speeds using a twin screw extruder

This study analyzes the effect of different screw rotating speeds on the clay dispersion and mechanical properties of nanocomposites prepared by melt compounding polylactic acid (PLA) with an organoclay in a co‐rotating twin screw extruder. Polyamide 12 (PA12) was used as an additive. Two different screw rotating speeds, 65 rpm and 150 rpm, were used in this study. According to the tensile strength data, the Young's modulus of the PLA/clay nanocomposites showed improvement at a screw rotating speed of 150 rpm. The Young's modulus improved with the addition of the organoclay to PLA matrix, but decreased when PA12 was added to the PLA matrix. The tensile strengths and elongations become small by adding organoclay to PLA matrix. The tensile strengths of the PLA/organoclay nanocomposites increased for the higher screw rotating speed (150 rpm). The d‐spacing of PLA/PA12/Clay nanocomposites was independent of the addition of PA12. The size of the clay aggregates in the PLA/PA12/Clay nanocomposites is smaller than that of PLA/Clay. Furthermore, the thermal stability of the PLA/Clay nanocomposite increases with addition of PA12, while on the whole, it had little influence on the tensile properties. POLYM. COMPOS., 29:1–8, 2008. © 2007 Society of Plastics Engineers     

Effect of Polymer Dispersant Structure on Electrosteric Interaction and Dense Alumina Suspension Behavior

The present paper reports on research on the effect of molecular structure of polymer dispersants on the relationship between the electrosteric interaction of dispersants on solid surfaces and the viscosity of suspensions. Ammonium polyacrylate with different hydrophilic to hydrophobic ratios ( m:n ) was prepared and added to dense Al₂O₃ suspensions (40 vol%). The steric interactions and adsorbed structures of dispersants on Al₂O₃ powders were examined under an atomic force microscope (AFM). An optimum hydrophilic to hydrophobic group ratio, which was obtained from the maximum repulsive force and the minimum viscosity of suspension, was determined at m :n = 3:7. The changing mechanism of the adsorbed structure and the steric interaction of dispersants and the suspension viscosity by the hydrophilic to hydrophobic molecular ratio were discussed by comparing the experimental force curve and DLVO theory.     

Determination of the Temperature Coefficient Distribution of Dielectric Ceramics Using Scanning Photothermal Dielectric Microscopy

Two-dimensional images of the distribution showing the temperature coefficient of the dielectric constant for two types of two-phase composite ceramics composed of TiO₂-Bi₂Ti₄O₁₁ and BaTi₄O₉-BaPr₂Ti₄O₁₂ were obtained using scanning photothermal dielectric microscopy. The images of the TiO₂-Bi₂Ti₄O₁₁ ceramic showed that the TiO₂ and Bi₂Ti₄O₁₁ grains had negative and positive temperature coefficients, respectively, and that the macroscopic averaged temperature coefficient of the ceramic was relatively low because of the cancellation of the opposite signs of the coefficients. On the other hand, the images of the BaTi₄O₉-BaPr₂Ti₄O₁₂ ceramic showed that the temperature coefficient of both grains had the same sign (negative), although their absolute values were quite different.     

Laboratory corrosion tests for simulating fireside wastage of superheater materials in waste incinerators

Laboratory corrosion tests were performed to clarify the effects of relative amounts of fused salts in tube deposits on corrosion rates of superheater materials in WTE plants. All test exposures were at 550 °C and of 100 h duration. The nine synthetic ashes used as corrodents consisted of mixtures of chlorides, sulfates and oxides. The test materials were alloy steel T22, stainless steels TP347H, TP310HCbN, and alloys HR11N and 625. The gas atmosphere consisted of 500 to 3000 ppm HCl‐30 ppm SO₂‐10% O₂‐10% CO₂‐20% H₂O‐bal.N₂. Generally, the relative amount of fused salts in non‐fused ash constituents at 550 °C increased with increasing the chlorine content of the ashes. The corrosion rate of T22 steel did not depend directly on ash chlorine content, but for ashes of 7.7 wt.% Cl, the corrosion rate depended on the calculated amount of fused salt at 500 °C. The corrosion rates of TP347H steel and alloy 625 were maximum for ashes of 6–8 wt.% Cl. For ashes of 7.7 wt.% Cl, the corrosion rates of T22 steel, stainless steels, and alloys increased with ashes having higher amounts of fused salts. Increased HCl content of the gas caused higher corrosion of the stainless steels and high‐nickel alloys, but there was no clear corrosion‐exacerbating effect with T22 steel.     

Experimental analyses for electronic structure of barium zirconate-strontium zirconate proton-conducting solid solution

In proton-conducting oxides, analyses for their electronic structure contribute to the understanding of interactions between defects in them. In this study, electronic band alignment of (1−x)BaZr_0.8Y_0.2O_3−δ(BZY)–xSrZr_0.95Y_0.05O_3−δ(SZY) proton-conducting solid-solution system (BSZY) which has high defect concentration and the deep valence band is experimentally investigated. By using thin-film specimens for optical absorption measurements, absorption edges derived from electron transition from the valence band to the conduction band which was insensitive to the proton incorporation were clearly observed in spite of the high defect concentration. The obtained optical band gap energy increased from 5.61 to 5.89 eV with increasing x, which was consistent with a composition dependence of Zr(Y)O₆ octahedral tilting. Ultraviolet photon-yield spectroscopy (UV-PYS) measurements under vacuum condition revealed that BZY and SZY had ionization energy of 6.98 and 7.31 eV, respectively, and thus the absolute energy levels of the valence band maximum and the conduction band minimum of BSZY were experimentally clarified. We propose that the combination of the optical absorption measurements using thin-film specimens and the UV-PYS measurements under vacuum condition is effective in evaluating fundamental electronic structures of proton-conducting oxides.     

Relation between crystal structure and lattice oxygen content of sintered reaction-bonded silicon nitride

When reaction-bonded silicon nitride containing MgO/Y₂O₃ additives is sintered at three different temperatures to form sintered reaction-bonded silicon nitride (SRBSN), the thermal conductivity increases with sintering temperature. The β-Si₃N₄ (silicon nitride) crystals of SRBSN ceramics were synthesized and characterized to investigate the relation between the crystal structure and the lattice oxygen content. The hot-gas extraction measurement result and the crystal structure obtained using Rietveld analysis suggested that the unit cell size of the β-Si₃N₄ crystal increases with the decrease in the lattice oxygen content. This result is reasonable considering that the lattice oxygen with the smaller covalent radius substitutes nitrogen with the larger one in the β-Si₃N₄ crystals. The lattice oxygen content decreased with increasing sintering temperature which also correlated with increase in thermal conductivity. Moreover, it is noteworthy from the viewpoint that it may be possible to apply the lattice constant analysis for the nondestructive and simple measurement of the lattice oxygen content that deteriorates the thermal conductivity of the β-Si₃N₄ ceramics.     

Pervaporation via silicon-based membranes: Correlation and prediction of performance in pervaporation and gas permeation

Pervaporation (PV) is a membrane technology that holds great promise for industrial applications. To better understand the PV mechanism, PV dehydrations of various types of organic solvents (methanol, ethanol, iso-propanol, tert-butanol, and acetone) were performed on five types of organosilica and two types of silicon carbide-based membranes, all with different pore sizes. Water permeance was dependent on the types of organic aqueous solutions, which suggested that organic solvents penetrated the pores and hindered the permeation of water. In addition, water permeance of various types of membranes in PV was well correlated with hydrogen permeance in single-gas permeation. Furthermore, a clear correlation was obtained between the permeance ratio in PV and that in single-gas permeation, which was confirmed via the modified-gas translation model. These correlations make it possible to use single-gas permeation properties to predict PV performance.