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.     

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.     

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     

Application concepts and evaluation of small-scale catalytic combustors for natural gas

Basic application concepts of catalytic combustion are roughly classified into three types, and the development of catalysts, combustion performance and applicability are stated. On the diffusive catalytic combustion method, completeness of methane combustion and its reaction mechanism have been demonstrated by detailed combustion analysis of the burner and reaction kinetics. On the adiabatic lean premixed catalytic combustion method, applicability of a high-temperature catalyst system based on Mn-substituted hexaaluminate monolithic honeycomb to a 1.5 MW gas turbine combustor has been investigated through pressurized combustion tests and prototype engine-rig tests. As a result, a good outlook of the basic technical problems to overcome including the catalyst durability and the combustor control method was obtained, but another problem was that of the combustor capacity. In view of the progress of the non-catalytic lean premixed combustion method, it was concluded that a hybrid catalytic combustion method limiting catalytic combustion to the low-temperature range in this concept might become efficient in the future, but that it would depend on the development of efficient catalysts initiating their activity at about 350°C and having durability at 1000°C.     

Polyethylene–Carbon Nanotube Composite Film Deposited by Cold Spray Technique

Carbon nanotubes (CNTs) are high-performance materials because of their superior electrical conductivity, thermal conductivity, and self-lubrication, and they have been studied for application to polymer composite materials as fillers. However, the methods of fabricating polymer composites with CNTs, such as injection molding, are too complicated for industrial applications. We propose a simple cold spray (CS) technique to obtain a polymer composite of polyethylene (PE) and CNTs. The composite films were deposited by CS on polypropylene and nano-porous structured aluminum substrates. The maximum thickness of the composite film was approximately 1 mm. Peaks at G and D bands were observed in the Raman spectra of the films. Scanning electron microscopy images of the film surface revealed that PE particles were melted by the acceleration gas and CNTs were attached with melted PE. The PE particles solidified after contact with the substrate. These results indicate that PE–CNT composite films were successfully deposited on polypropylene and nano-porous structured aluminum substrates by CS.     

Depassivation-repassivation behavior of a pure iron surface investigated by micro-indentation

Depassivation-repassivation behavior on a pure iron surface in borate buffer solution was examined under potentiostatic control by a micro-indentation test. Current peaks emerge during both downward and upward drives of the indenter due to depassivation which is caused by plastic deformation of the substrate but not elastic deformation and repassivation. The total electric charge of the current peaks is proportional to the maximum load. The total electric charge also increases with increase in intermission time of the indentation, indicating that the passive film is ruptured even during stress relaxation. It is estimated from the electric charge balance that 82% and 18% of the film rupture occurs during the downward drive and intermission, respectively, and that no rupture occurs during the upward drive. Furthermore, the film-ruptured area is estimated to be 80% of the plastic deformed surface area. The partial retainment of the passive film on iron suggests that the ductility of the passive film is higher than that of the substrate.     

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.     

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.     

Enhancement of Anti-Tumoral Immunity by β-Casomorphin-7 Inhibits Cancer Development and Metastasis of Colorectal Cancer

β-Casomorphin-7 (BCM) is a degradation product of β-casein, a milk component, and has been suggested to affect the immune system. However, its effect on mucosal immunity, especially anti-tumor immunity, in cancer-bearing individuals is not clear. We investigated the effects of BCM on lymphocytes using an in vitro system comprising mouse splenocytes, a mouse colorectal carcinogenesis model, and a mouse orthotopic colorectal cancer model. Treatment of mouse splenocytes with BCM in vitro reduced numbers of cluster of differentiation (CD) 20⁺ B cells, CD4⁺ T cells, and regulatory T cells (Tregs), and increased CD8⁺ T cells. Administration of BCM and the CD10 inhibitor thiorphan (TOP) to mice resulted in similar alterations in the lymphocyte subsets in the spleen and intestinal mucosa. BCM was degraded in a concentration- and time-dependent manner by the neutral endopeptidase CD10, and the formed BCM degradation product did not affect the lymphocyte counts. Furthermore, degradation was completely suppressed by TOP. In the azoxymethane mouse colorectal carcinogenesis model, the incidence of aberrant crypt foci, adenoma, and adenocarcinoma was reduced by co-treatment with BCM and TOP. Furthermore, when CT26 mouse colon cancer cells were inoculated into the cecum of syngeneic BALB/c mice and concurrently treated with BCM and TOP, infiltration of CD8⁺ T cells was promoted, and tumor growth and liver metastasis were suppressed. These results suggest that by suppressing the BCM degradation system, the anti-tumor effect of BCM is enhanced and it can suppress the development and progression of colorectal cancer.     

Hairpin-based state machine and conformational addressing: Design and experiment

In this paper, we propose a new architecture for a multi-state DNA machine whose conformation of repeated hairpin structures changes sequentially in response to input oligomers. As an application of the machine, we also propose molecular memory in which the machine is used as a memory unit. Addressing in the memory is realized through state transitions of the machine. We then describe a method for designing DNA sequences of the machine, which exhaustively checks conformational changes of the machine by dividing its secondary structure into hairpin units. The method is based on the minimum free energy of the structure, the structure transition paths, and the total frequency of optimal and suboptimal structures. DNA sequences designed by the method were tested in a chemical experiment in which a machine consisting of two hairpins was actually constructed. As a result, we verified that the multi-state DNA machine realized the expected changes in its secondary structure.