Thermal Transformation of Ring-Opened [2 2] C60 Dimer into a Wide-Bridged C120 Isomer. A Computational Evaluation of Fulvalene-Naphthalene Rearrangements

As a continuation of the studies on thermal transformation of the [2+2] C₆₀ dimer (1), the consequence of the pyracylene-rearrangement-like valence isomerization of the fulvalene partial structure at the bridge of the ring-opened product from 1, namely 2, was searched by dynamic reaction coordinate /AM1 semiempirical MO calculations. It is predicted that the fulvalene bridge of 2 rearranges into naphthalene partial structure by the concerted 'in-plane' mechanism to give a wide-bridged C₁₂₀ intermediate having twenty five-membered rings and two ten-membered rings (3). The computed energy of activation (145 kcal/mol) is 40 kcal/mol lower than those computed for pyracylene rearrangements. In contrast, the recently reported analogous rearrangement of indigo (13) to dibenzonaphthyridindione (14) is computed to occur by the stepwise 'sp³' mechanism.     

Theory and characteristics of novel variable reluctance 1X resolver

Although brushless resolvers have been used widely as angular position transducers, they are expensive due to their intricate construction, involving a rotary transformer to supply the exciting coils wound on the rotor poles with the current. It is shown theoretically in this paper that the resolver without rotary transformer or brushes can be realized by simple construction, which consists of the stator core with both 4-poles exciting windings and 2-poles output ones and the rotor core carrying no windings. In this resolver the rotor core has minimum gap at one side and a maximum gap at another side of the diameter. It is characterized by an outer surface form that makes the fluctuation part of gap permeance very in proportion to cos θ, where θ represents the angular position of a point in the air gap with respect to the origin on the rotor, the point of minimum air gap. The method determining the rotor form to embody the aforementioned gap permeance variation is also shown. It has been confirmed not only by simulation but also experiment that the 2-phase output voltages of a model designed based on the theory have sinusoidal waveforms with very small harmonic contents. Moreover, the rotor position detected by processing the output voltages through the conventional resolver/digital converter was within acceptable engineering accuracy.     

Transdermal Absorption of Zidovudine from Ethanol-Isopropyl Myristate Mixed System and Influence of Probenecid on It in Rats

Transdermal absorption of zidovudine (AZT) from an ethanol-isopropyl myristate (IPM) mixed system was examined in rats. For comparison of bioavailability (BA) after topical applications, 0.25 ml of the ethanol/IPM system containing 40% ethanol and 60 mM AZT was applied as a standard formulation. Values of the area under the plasma concentration-time curves of AZT for 8 hr (AUC_0-8), as indices of BA, following application of various formulations were compared with that of the standard formulation. Then the influence of content of the drug and ethanol, and application volume of the system was evaluated. BA was effectively improved only when the total amount of ethanol applied on the skin was increased. On the other hand, simultaneous transdermal application of AZT and probenecid increased the AU_0-8, of AZT without necessitating the increase in ethanol content in the formulation. In addition, coadministered probenecid improved cerebrospinal fluid/plasma concentration ratio of AZT.     

Sensitivity of an anadically oxidized aluminium film on a surface acoustic wave sensor to humidity

The sensitivity, transient response and sensitivity mechanism of a surface acoustic wave humidity sensor using porous anodically oxidized aluminium (alumina) films as mechanical interfaces have been studied theoretically and experimentally. It is found that the sensitivity of alumina films of 1.0 μm thickness is -0.034 m/(s %RH) and is the same order as that of polyimide films. The transient response of alumina films to humidity is about one order faster than that of polyimide films. For the sensitivity mechanism, the phase-velocity change is attributed to the mechanical perturbation caused by the absorption of water molecules. The equivalent density change of alumina films between 0 and 100%RH is about 0.7%. In addition, the actual stiffness constants of alumina films are two orders less than those of bulk alumina.     

Spherical Yttrium Aluminum Garnet Embedded in a Glass Matrix

Containerless processing was used to investigate the glass-forming behavior of Al₂O₃–Y₂O₃ glass. The amorphous bulk samples were obtained at compositions with 25–37.5 mol% yttria when the melt was cooled at a cooling rate of ∼250 K/s. Although small spherical particles (∼10 μm) with the same composition of the matrix were detected in the amorphous samples with 32.5–37.5 mol% yttria, the microfocus X-ray diffraction result indicated that the small spherical particles were crystalline Y₃Al₅O₁₂ garnet (YAG), rather than being amorphous. This observation suggested that small YAG particles could not grow larger after their nucleation, because of the high viscosity at high undercooling and the high cooling rate, which would graze the nose of the continuous cooling temperature diagram of YAG.     

Vapor phase hydroformylation of ethene over Co/SiO2 promoted by noble metals: dynamic in situ diffuse reflectance FT-IR study of surface species

An in situ diffuse reflectance FT-IR technique was employed to investigate the active surface species and the reaction mechanism of the oxygenate formation in the vapor phase hydroformylation of ethene on Co/SiO₂ promoted with various noble metals such as Ir, Rh, Pt, Re, Ru, and Pd. Co(A)/SiO₂ and Ir(CO)/SiO₂ which were derived from cobalt(II) acetate and Ir₄(CO)₁₂, respectively, were quite inactive in the reaction, and showed only quite small peaks of adsorbed CO under the conditions of 1.1 MPa of C₂H₄/CO/H₂ at 298 K. In contrast, Co(A)-Ir(CO)/SiO₂, which were very active in the reaction, exhibited strong absorption bands of linear and bridged CO species. At 423–463 K, propanal adsorbed on the catalyst and acyl species which is suggested as the intermediate for the formation of propanal were also observed on this catalyst. By exposing CO preadsorbed on this catalyst to C₂H₄/H₂ at 289 K and 0.1 MPa, the intensity of the linear CO band decreased, and the bands of propanal and acyl species emerged simultaneously, whereas that of the bridged CO band remained constant after the initial drop. These results suggested that the oxygenates are formed via the CO insertion into adsorbed ethyl species, and linear CO species plays a major role in the CO insertion on these noble metal-promoted cobalt catalysts.     

Development of flexible organic light‐emitting diode on barrier film and roll‐to‐roll manufacturing

To come out with a successful organic light‐emitting diode (OLED) lighting business, it is very important to have clear differentiation of OLED from LEDs. Flexible OLED has merits, such as capability to be mounted on the curved wall, which is not easy for LEDs to achieve the feature. There are several approaches to make flexible OLEDs especially among those plastic barrier films that can bring high level of flexibility, which could not be achieved by any conventional lighting method. In this paper, barrier films with various water vapor transmission rate values, including 10^{? 6} order, are applied, and the conditions to have almost no dark spot growth under 85 °C and 85% high temperature/humidity test are shown. Flexible OLED panels are manufactured with the world's first roll‐to‐roll equipment using plastic barrier film.     

Texture and Formation Mechanism of Fibrous Calcium Hydroxyapatite Particles Prepared by Decomposition of Calcium–EDTA Chelates

The texture of fibrous calcium hydroxyapatite (Ca₁₀-(PO₄)₆(OH)₂, CaHAP) particles that were prepared by the decomposition of calcium–ethylenediaminetetraacetic acid (calcium–EDTA) chelates at 100°C under various pH conditions (pH values of 5–10) was investigated by various means. Well-crystallized fibrous CaHAPs were produced at pH .6. The stoichiometry of the CaHAPs with a chemical formula of Ca_{10− x} (HPO₄) _x (PO₄)_{6− x} (OH)_{2− x} (H₂O) _x was improved by increasing the decomposition pH. All the CaHAPs had unit-cell dimensions of a = 0.9436 ± 0.0003 nm and c = 0.6881 ± 0.0006 nm, exhibiting an enlarged a value. The finding of mesoporosity of CaHAPs by nitrogen gas (N₂) adsorption measurement indicated that the CaHAPs were produced by an agglomeration of primary particles. Furthermore, the nonstoichiometric CaHAPs that formed at pH 6 developed ultramicropores, which were accessible to water (H₂O) molecules but not to N₂ molecules, by the elimination of H₂O molecules that were adsorbed in interstices of primary particles in less-orderly crystallized CaHAPs and/or by dehydration of HPO₄²⁻ groups. These findings by gas adsorption techniques could give evidence for the agglomeration mechanism to attain a polycrystalline CaHAP, although they exhibited good crystallinity with large size.     

Decomposition of Mullite by Silica Volatilization

Thermal decomposition of mullite into corundum was investigated using a high-temperature X-ray single-crystal camera equipped with a gas-flame furnace and by scanning electron microscopy and electron probe microanalysis (EPMA). When heated to ∼1750°C, mullite decomposed to corundum by the liberation of the SiO₂ component with topotaxial relations of:

• (1) 

  (310)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (2) 

  (130)_mull∥(001)_cor; [001]_mull∥[110]_cor
• (3) 

  (110)_mull∥(001)_cor; [001]_mull∥[110]_cor

Thus, it was considered that, when mullite decomposed into corundum, their oxygen close-packed planes were almost preserved. The SEM photographs showed that the crystals of the developed corundum are prismatic and ∼5 μm wide. The EPMA showed that the phase boundary between mullite and developed corundum is discontinuous.     

Performance of SOR methods on modern vector and scalar processors

The building-cube method (BCM) is a new generation algorithm for CFD simulations. The basic idea of BCM is to simplify the algorithm in all stages of flow computation to achieve large-scale simulations. Calculation of a pressure field using the Successive Over Relaxation (SOR) method consumes most of the total execution time required for BCM. In this paper, effective implementations on modern vector and scalar processors are investigated. NEC SX-9 and Intel Nehalem-EX are the latest vector and scalar processors. Those processors have much higher peak performances than their previous-generation processors. However, their memory bandwidth improvement cannot catch up with the performance improvement of processors. This is the so-called memory wall problem. In our paper, we discuss optimization techniques for implementation of the SOR method based on architectural characteristics of these modern processors, and evaluate their effects on the sustained performances of these processors for BCM.