Phase Relations and Volume Changes of Hafnia under High Pressure and High Temperature

Using multi-anvil high-pressure devices and synchrotron radiation, X-ray in situ observations of HfO₂ under high pressure and high temperature have been performed to investigate its phase relations and compression behavior. An orthorhombic phase (orthoI) is stable from 4 to 14.5 GPa below 1250°–1400°C and transforms to a tetragonal phase, which is one of the high-temperature forms of HfO₂, above these temperatures. Another orthorhombic phase (orthoII) with a cotunnite-type structure appears above 14.5 GPa. OrthoII is stable up to 1800°C at 21 GPa. OrthoII is quenchable to ambient conditions. The orthoI-to-orthoII transition is accompanied by ∼8 vol% decrease. The bulk moduli of orthoI and orthoII at room temperature are 220 and 312 GPa, respectively. This low compressibility of orthoII indicates that it is a potential candidate for very hard materials.     

Agglomeration Characteristics of Aluminum Particles in AP/AN Composite Propellants

Most solid rockets are powered by ammonium perchlorate (AP) composite propellant including aluminum particles. As aluminized composite propellant burns, aluminum particles agglomerate as large as above 100 μm diameter on the burning surface, which in turn affects propellant combustion characteristics. The development of composite propellants has a long history. Many studies of aluminum particle combustion have been conducted. Optical observations indicate that aluminum particles form agglomerates on the burning surface of aluminized composite propellant. They ignite on leaving the burning surface. Because the temperature gradient in the reaction zone near a burning surface influences the burning rate of a composite propellant, details of aluminum particle agglomeration, agglomerate ignition, and their effects on the temperature gradient must be investigated. In our previous studies, we measured the aluminum particle agglomerate diameter by optical observation and collecting particles. We observed particles on the burning surface, the reaction zone, and the luminous flame zone of an ammonium perchlorate (AP)/ammonium nitrate (AN) composite propellant. We confirmed that agglomeration occurred in the reaction zone and that the agglomerate diameter decreased with increasing the burning rate. In this study, observing aluminum particles in the reaction zone near the burning surface, we investigated the relation between the agglomerates and the burning rate. A decreased burning rate and increased added amount of aluminum particles caused a larger agglomerate diameter. Defining the extent of the distributed aluminum particles before they agglomerate as an agglomerate range, we found that the agglomerate range was constant irrespective of the added amount of aluminum particles. Furthermore, the agglomerate diameter was ascertained from the density of the added amount of aluminum particles in the agglomerate range. We concluded from the heat balance around the burning surface that the product of the agglomerate range and the burning rate was nearly constant irrespective of the added amount of aluminum particles. Moreover, the reduced burning rate increased the agglomerate range.     

Multiple uses of Essential Oil and By-Products from Various Parts of the Yakushima Native Cedar (Cryptomeria Japonica)

This article presents multiple potential uses of the Yakushima native cedar (Cryptomeria japonica), known in Japan as the Yaku-sugi tree. The Yaku-sugi was divided into four parts: leaves, branches with leaves, branches, and stems. We obtained the essential oil, hydrosol, distillation residue, and distillation wastewater from the trees. Essential oil and hydrosol were determined to be volatile organic compounds. All samples were screened for the following bioactivities: antioxidative, antibacterial, and anti-melanogenesis activities. Freeze-dried distillation residue was tested to assess whether it had a deodorizing effect. The main component of the leaf essential oil was found to be monoterpenes. In contrast, the stem essential oil mainly contained sesquiterpenes. In terms of bioactivities, the leaf essential oil showed antibacterial activity and the stem essential oil showed anti-melanogenesis activity. Distillation residue and wastewater showed many activities, including antioxidant, antibacterial, and anti-melanogenesis activities. Moreover, the residue had a deodorizing effect against ammonia.     

The alkylation of biphenyl over three-dimensional large pore zeolites: The influence of zeolite structure and alkylating agent on the selectivity for 4,4′-dialkylbiphenyl

Catalytic properties of three-dimensional zeolites, Y (FAU), Beta (BEA), and CIT-1 (CON) zeolites were examined in the alkylation, isopropylation, sec-butylation, and tert-butylation, of biphenyl (BP), and compared to those of H-mordenite (MOR). The selectivities for 4,4′-dialkylbiphenyl (4,4′-DABP) varied with the types of zeolite and of alkylating agent. FAU, BEA, and CON gave only low selectivities for 4,4′-diisopropylbiphenyl (4,4′-DIPB) in the isopropylation, and predominant isomers were bulky and thermodynamically unstable 2,x′-DIPB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and bulky and thermodynamically stable 3,4′- and 3,3′-DIPB at higher temperatures: this is quite different from catalytic features over MOR, which gave 4,4′-DIPB with high selectivities at moderate temperatures. These results suggest that FAU, BEA, and CON have no shape-selective nature in the isopropylation, and that the reaction is principally controlled kinetically at lower temperatures, and thermodynamically at higher temperatures. The sec-butylation gave similar results to the isopropylation. Although the selectivities for 4,4′-di-sec-butylbiphenyl (4,4′-DSBB) were higher than those in the isopropylation, predominant isomers were 2,x′-DSBB (2,2′-, 2,3′-, and 2,4′-) at lower temperatures, and 3,4′- and 3,3′-DSBB at higher temperatures. The tert-butylation gave 4,4′-di-tert-butylbiphenyl (4,4′-DTBB) in moderate to high selectivities over all zeolites at moderate temperatures: the selectivity for 4,4′-DTBB was higher than 80% over BEA and CON; however, it still remained at 50% over FAU. FAU channels with super cages are too large for selective formation of 4,4′-DTBB.

From these results, it is concluded that the selectivity for 4,4′-DABP in the alkylation over MOR, FAU, BEA, and CON is determined by the exclusion of bulky isomers at their transition states, and that the exclusion is caused by the steric restriction at the transition states of bulky isomers by the zeolite channels.     

Adsorption of cationic monomeric and gemini surfactants on montmorillonite and adsolubilization of vitamin E

Adsorption of a cationic gemini surfactant (1,2-bis(dodecyldimethylammonio) ethane dibromide, 12-2-12) and the corresponding monomeric surfactant (dodecyltrimethylammonium bromide, DTAB) on montmorillonite has been characterized with a combination of adsorption isotherm, interlayer spacing and FT-IR spectroscopic data. Adsolubilization of vitamin E into the adsorbed surfactant layers has also been studied. The adsorption isotherm data reveal that the adsorption of the two surfactants is driven by the two factors: one is the cation exchange that occurs on the interlayer basal planes and the other is the hydrophobic interaction between hydrocarbon chains of the surfactants. Although the adsorbed amount measured in the saturation region (in mol g(-1)) is almost identical for the two surfactants, the conformation of the intercalated surfactant molecules differs significantly from each other. The adsorption of DTAB results in a lateral bilayer arrangement in the limited interlayer space, whereas 12-2-12 gives a normal bilayer arrangement in the expanded interlayer space. Adsolubilization of vitamin E takes place into the adsorbed surfactant layers, and interestingly, all the vitamin E molecules added in the montmorillonite suspensions are hybridized at lower surfactant concentrations due to the great specific surface area of the clay material. Since the maximum adsolubilization amount is usually obtained just below the critical micelle concentration, the gemini surfactant is deemed to be more efficient than the corresponding monomeric one to achieve the great adsolubilization amount.     

The micro-nanoformability of Pt-based metallic glass and the nanoforming of three-dimensional structures

Pt_48.75Pd_9.75Cu_19.5P₂₂ amorphous alloy exhibits obvious glass transition behavior at a temperature of T_g=502 K, which is below the crystallization temperature T_x=588 K, and develops a supercooled liquid state in a wide temperature range of ΔT_x (=T_x−T_g)=86 K. The present paper investigates the macroscopic and microscopic deformation behavior of the material and the possibility of micro-nano forming as a fabrication method and material for nano-devices. On a macroscopic scale, the material exhibits a Newtonian viscous flow in a supercooled liquid state. An index of the microformability is also evaluated by the geometrical transferability of a die shape to the material. For this study, we fabricated V-grooved micro dies of (100) Si by a silicon process. The V-groove dies are from 100 nm to 1 μm wide. The material exhibits superior formability on micrometer and nanometer scales and may possibly be applied to micro-nanomaterials for micro-nano devices.     

Fin efficiency of serrated fins. Part 4. Correction factor for inline arrangement

A correction factor to the theoretical fin efficiency of serrated fins, reported in Part 1 and Part 2 of this report, was derived for an inline arrangement experimentally. The experiment was performed using an open‐type wind tunnel with six kinds of test finned‐tubes made of copper, carbon steel and stainless steel, which were arranged in one to five rows. Heat transfer measurement was done by the local thermal simulation method. The derived correction factor for the 1st row was the same as for staggered arrangement reported in Part 3, for the 2nd and deeper rows, however, a further correction was needed, which may be caused by the difference in the nonuniformity in heat transfer coefficient over the fin surface. © 2004 Wiley Periodicals, Inc. Heat Trans Asian Res, 33(4): 258–269, 2004; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20008     

Monte Carlo simulation of circular double-stranded polymers

Double-helix structure of DNA provides an appropriate model system for studying equilibrium properties of macromolecule. In contrast to the models of linear polymers, the secondary structure as well as most of interaction parameters can be introduced into the model. We present studies of double-stranded twisted circular polymer chain by mean of computer simulation. The attention was focused on the effect of polymer chain twisting on the properties of macromolecule. We found that the number of double helical turns affects the scaling of the polymer chain and markedly changes system properties, for example, coil to globule transition temperature.     

Speech recognition using pulse-coupled neural networks with a radial basis function

We have developed a novel pulse-coupled neural network (PCNN) for speech recognition. One of the advantages of the PCNN is in its biologically based neural dynamic structure using feedback connections. To recall the memorized pattern, a radial basis function (RBF) is incorporated into the proposed PCNN. Simulation results show that the PCNN with a RBF can be useful for phoneme recognition. This work was presented in part at the 7th International Symposium on Artificial Life and Robotics, Oita, Japan, January 16–18, 2002     

Characteristics of particle mixtures in a liquid‐fluidized bed

Behavior of particle mixtures was investigated in a liquid‐fluidized bed experimentally. In the experiment, two kinds of particles of different diameters, and of the same or different materials, were charged in a fluidization column and fluidized by water. Based on the observation of fluidization, a flow pattern map was proposed using the Archimedes number ratio and the terminal velocity ratio, which classifies the two patterns, that is, separation and homogeneous mix. Measured mean void fractions of particle mixtures agreed well with the values calculated from those for each particle independently. © 2001 Scripta Technica, Heat Trans Asian Res, 30(3): 175–184, 2001