Evaluation of delayed fracture property of outdoor-exposed high strength AISI 4135 steels

Delayed fracture properties of AISI 4135 high strength steels with 1490 and 1310 MPa of tensile strength, represented as B15 and B13, respectively, have been studied by means of slow strain rate test (SSRT) of notched bar specimens after outdoor exposure at rural and coastal areas. The exposed specimens were kept at humid medium before SSRT to reproduce active hydrogen entry influenced by the rust layer and to homogenize hydrogen distribution. The influences of exposure site and exposure time on fracture stress have been investigated. The susceptibility of B15 to delayed fracture was obviously higher than that of B13.     

Micro machining for control of wettability with surface topography

A micro fabrication is presented to manufacture hydrophobic surfaces with micro-scale structures. Hydrophobicity is controlled with the shape and the alignment of micro pillars in the structure. The structures are manufactured in large areas at high production rates in the following processes: (1) the structure is fabricated on a tool by focused ion beam sputtering; (2) the reverse structure is formed on a metal plate by incremental stamping using the structured tool; and (3) the structure is transferred onto plastic plates by molding. A consecutive stamping is also proposed to fabricate several structures on a surface accurately with a structured tool, in which the moving pitch of the structured tool is numerically controlled. The effect of the surface topography on hydrophobicity is discussed with measuring contact angles on the structured surfaces in the water droplet tests. Hydrophobicity on the plastic plate is associated with the solid fraction on the structured surface based on the Cassie–Baxter model. A larger contact angle is observed for a smaller solid fraction of the surface.     

Demulsification of oil-in-water emulsion under freezing conditions: Effect of crystal structure modifier

The demulsification of oil-in-water (O/W) emulsions under freezing conditions is connected to fat crystallization in the oil droplet. Therefore, demulsification can be prevented by the use of oil with a low melting point, and also by lowering the O/W ratio. However, an oil with a low melting point, such as sunflower, is rather expensive, and the O/W ratio has a significant effect on the texture of emulsions. We searched for an oil that is suitable for the production of a freeze-stable emulsion and found that soybean oil has unique characteristics. Normally, emulsions are more unstable at lower temperatures; soybean oil emulsion is unstable at −10°C and stable at −20°C. This unique characteristic results from the following two reasons. First, the solid fat content of soybean oil is almost the same at −10 and −20°C. Second, small crystals form a larger network over a period of time, and the higher temperature promotes faster restructuring. This structure formation was microscopically observed with the use of a thermostated stage. Structure formation was suppressed with the addition of a crystal structure modifier, polyglycerol fatty acid full ester, which also suppressed coalescence.     

Reducing the Photocatalytic Activity of Zinc Oxide Quantum Dots by Surface Modification

The use of zinc oxide (ZnO) nanoparticles as ultraviolet (UV) absorbers for many organic substrates is limited because of the high photocatalytic activity of ZnO. In this study, a facile and efficient technique for the preparation of a hybrid material of silica-coated ZnO nanoparticles was used to reduce the photocatalytic activity of ZnO. Monodispersed ZnO nanopartcles were prepared by wet chemistry and the particle surface was modified by tetraethylorthosilicate to form a silica coating via the Stöber method. ZnO samples, both before and after the coating process, were investigated by transmission electron microscopy, X-ray diffraction, dynamic light scanning, infrared, and UV-Vis absorption spectroscopy. The effect of the surface modification on the photocatalytic activity of ZnO was studied by monitoring the degradation of Rhodamine B caused by photo-generated free radicals. The results implied that the photo-generation of free-radicals was strongly quenched by the presence of silica on the particle surface.     

Carbon dioxide pressure induced heterogeneous and homogeneous Heck and Sonogashira coupling reactions using fluorinated palladium complex catalysts

The Heck reaction of iodobenzene and methyl acrylate was investigated with CO₂-philic Pd complex catalysts having fluorous ponytails and the organic base triethylamine (Et₃N) in the presence of CO₂ under solventless conditions at 80 °C. The catalysts are not soluble in the organic phase in the absence of CO₂ and the reaction occurs in a solid-liquid biphasic system. When the organic liquid mixture is pressurized by CO₂, CO₂ is dissolved into the organic phase and this promotes the dissolution of the Pd complex catalysts. As a result, the Heck reaction occurs homogeneously in the organic phase, which enhances the rate of reaction. This positive effect of CO₂ pressurization competes with the negative effect that the reacting species are diluted by an increasing amount of CO₂ molecules dissolved. Thus, the maximum conversion appears at a CO₂ pressure of around 4 MPa under the present reaction conditions. The catalysts are separated in the solid granules by depressurization and are recyclable without loss of activity after washing with n-hexane and/or water. When the washing is made with hexane alone, the catalytic activity tends to increase on the repeated Heck reactions, probably due to the accumulation of such a base adduct as Et₃NHI on the catalysts. When the washing is further made with water, however, the base adduct is taken off from the catalysts and they show similar activity levels in the repeated runs. The potential of CO₂ pressure tunable heterogeneous/homogeneous reaction system has also been investigated for Sonogashira reactions of iodobenzene and phenylacetylene under similar conditions.     

Materials for global carbon dioxide recycling

CO₂ emissions, which induce global warming, increase with the development of economic activity. It is impossible to decrease the CO₂ emissions by suppression of the economic activity. Global CO₂ recycling can solve this problem. The global CO₂ recycling consists of three district: The electricity is generated by solar cells on deserts. At desert coasts, the electricity is used for H₂ production by seawater electrolysis and H₂ is used for CH₄ production by the reaction with CO₂. CH₄ which is the main component of liquefied natural gas is liquefied and transported to energy consuming districts where CO₂ is recovered, liquefied and transported to the desert coasts. A CO₂ recycling plant for substantiation of our idea has been built on the roof of the Institute for Materials Research in 1996. Key materials necessary for the global CO₂ recycling are the anode and cathode for seawater electrolysis and the catalyst for CO₂ conversion. All of them have been tailored by us. They have very high activity and selectivity for necessary reactions in addition to excellent durability. A pilot plant consisting of minimum units in an industrial scale is going to be built in three years.     

Exchange rate constants of invisible protons in proteins determined by NMR spectroscopy

Although labile protons that are exchanging rapidly with those of the solvent cannot be observed directly, their exchange rate constants can be determined by indirect detection of scalar-coupled neighboring nuclei. We have used heteronuclear NMR spectroscopy to measure the exchange rate constants of labile protons in the side chains of lysine and arginine residues in ubiquitin enriched in carbon-13 and nitrogen-15 at neutral pH. Exchange rate constants as fast as 40x10(3) s(-1) were thus measured. These results demonstrate that NMR spectroscopy is a powerful tool for the characterization of lysine NH3(+) and arginine NH groups in proteins at physiologically relevant pH values.     

Controlled Oxygen Partial Pressure Sintering of (Pb,La)(Zr,Ti)O3 Ceramics

Transparent PLZT(7/60/40) ceramics with large piezoelectric coefficients were obtained using a two-step sintering process with controlled oxygen partial pressure. Specifically, low-oxygen-pressure and low-temperature sintering were used in the first step, followed by a high-oxygen-pressure, high-temperature sintering cycle. High-density ceramics with small grain sizes of about 3 µm were prepared. As a result, k _p= 0.71, k ₃₃= 0.78, d ₃₃= 850 × 10^-12 C/N, and a transparency of 15% (λ= 610 nm, thickness of 1 mm) have been achieved; 20% improvement of d ₃₃ was gained compared to conventional processed PLZT ceramics ( d ₃₃= 710 × 10^-12 C/N).     

Enhancement of the thermal stability and mechanical properties of a PMMA/aluminum trihydroxide composite synthesized via bead milling

The use of aluminum trihydroxide (ATH) fillers as non-halogen flame retardants for polymethylmethacrylates (PMMA) creates a conflict between the mechanical properties and heat resistance of the composites. Therefore, to ensure that the PMMA mechanical properties remain satisfactory, improvements in both the filler–polymer interactions and the ability to control the size and size distribution, morphology and dispersion of the fillers are required. Thus, in the present study, bead milling was used to control both the size distribution and dispersion of ATH fillers in MMA, which had an initial average size of 0.75 μm. The dispersion was obtained by alteration of the surface characteristics of ATH fillers using a silane-based dispersing agent, (3-acryloxypropyl) trimethoxysilane (APTMS). Bead milling successfully comminuted the ATH particles and prevented the formation of ATH agglomerates. The smallest average size of the ATH particles after bead milling was 300 nm. Highly dispersed ATH filler particles were observed in the TEM images of the PMMA/ATH composites. The filler–polymer interaction, i.e. the interaction parameter (B), was calculated. The effects of volume fraction, particle size distribution, and surface modification of the fillers on the results of dynamic mechanical analysis (DMA) are discussed. The thermal stability of the PMMA/ATH composites was also investigated using thermal gravimetric analysis (TGA).     

Very high temperature annealing effect on amorphous carbon films grown on refractory oxide substrates by pulsed laser deposition

We have carried out very high temperature heat treatment at 1400–2700 °C of about 10 nm-thick amorphous carbon thin films deposited on refractory substrates MgO, Al₂O₃, and yttria-stabilized zirconia (YSZ) using pulsed laser deposition techniques. After the annealing, a few nanometer scale sp² crystallization of the films and a large corrugation with a height of more than 1 μm were observed by Raman spectroscopy analysis and optical/atomic force microscopes, respectively. The corrugation is probably caused by the formation of gases at the film/substrate interface during the heat treatment.