Differential formation of allophane and imogolite: experimental and molecular orbital study

Allophane and imogolite are naturally occurring aluminum silicate soil constituents with nano-ball and nano-tube morphology. Wall of the both materials is composed of Al(OH)₃ sheet with orthosilicic acid attached to it. Synthesis of allophane and imogolite can be controlled by addition of alkali and alkaline-earth metal ions. The main reaction product without or with small amounts addition of the metal ions is imogolite, while allophane forms when the metal ions were much added. The effect of metal ions on facilitating allophane formation and inhibition of imogolite formation were greater in the following order of Na, K < Ca, Mg. These metal ions affect the degree of dissociation of Si–OH group of orthosilicic acid, which may causes differential formation of allophane and imogolite. Structure optimization of the proto-imogolite model, precursor of allophane and imogolite, showed that when the Si–OH was undissociated, the shape of proto-imogolite model was transformed to asymmetrical in molecular configuration. This caused curling of the proto-imogolite model, which lead to formation of imogolite tube. On the other hand, when the Si–OH was dissociated, the shape of the proto-imogolite model was transformed to symmetrical configuration. This model curved to make a hollow sphere with placing the orthosilicic acid inside the sphere (allophane). Both of the experimental and molecular orbital calculation results proved that the dissociation of the Si–OH has an important role during the differential formation of allophane and imogolite.     

Fabrication of silicon nitride nanoceramics—Powder preparation and sintering: A review

Fine-grained silicon nitride ceramics were investigated mainly for their high-strain-rate plasticity. The preparation and densification of fine silicon nitride powder were reviewed. Commercial sub-micrometer powder was used as raw powder in the “as-received” state and then used after being ground and undergoing classification operation. Chemical vapor deposition and plasma processes were used for fabricating nanopowder because a further reduction in grain size caused by grinding had limitations. More recently, nanopowder has also been obtained by high-energy milling. This process in principle is the same as conventional planetary milling. For densification, primarily hot pressing was performed, although a similar process known as spark plasma sintering (SPS) has also recently been used. One of the advantages of SPS is its high heating rate. The high heating rate is advantageous because it reduces sintering time, achieving densification without grain growth. We prepared silicon nitride nanopowder by high-energy milling and then obtained nanoceramics by densifying the nanopowder by SPS.     

Photorefractive device using self-assembled monolayer coated indium-tin-oxide electrodes

Photorefractive (PR) performances of methyl-substituted poly(triarylamine) (PTAA)-based PR device were demonstrated using chemically modified electrodes (CMEs) of self-assembled monolayer (SAM) coated indium-tin-oxide (ITO) electrodes. The SAM-ITO electrodes successfully suppressed dark current which blocks the formation of space-charge field and also causes the dielectric breakdown. The PR device consisted of composite of PTAA, 4-azacycloheptylbenzylidenemalononitrile (7-DCST), N-ethylcarbazole (ECz), and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) sandwiched between the SAM-ITO electrodes. The PR devices showed the PR performances: optical gain Γ, refractive index Δn, diffraction efficiency η, response time τ, sensitivity S, phase shift Φ, trap-limited field E_q, number density of traps N_T, and space-charge field E_SC. The remarkable response time of 11.3 ms was achieved at the low electric field of 20 V μm⁻¹, which was comparable to the response time of high-definition television (HDTV) quality of 16 ms. Our approach will widen the usage of higher mobility materials to photorefractive field and give us more favorable materials to achieve the best performance of photorefractivity in the future.     

Preparation of diamondlike carbon films using nanopulse generator employing SI thyristor

Diamondlike carbon (DLC) films show high hardness, high electric resistivity, and the self‐lubricant characteristic, and many applications and synthesis methods have been reported. Pulse plasma chemical vapor deposition (CVD) is one of the synthesis methods suitable for DLC films on complicated form work, such as molding and extruding die. Ordinary, microsecond‐order pulse is used in this method. This paper describes the development of the synthesis method using nanosecond‐order pulse plasma CVD for DLC films. To realize this process, a static induction (SI) thyristor with an inductive energy storage (IES) circuit was used. Compared with microsecond, nanosecond‐order pulse plasma CVD method shows the characteristics of high electron temperature and exponential relationship between pulse frequency and growth rate. The characteristics of the thus‐obtained DLC films show two broad peaks of the disordered band at 1360 cm^?1 and the graphitic band at 1580 cm^?1 by Raman spectroscopy and hardness of 16.0 GPa and elastic modulus of 170 GPa. © 2007 Wiley Periodicals, Inc. Electr Eng Jpn, 159(4): 1–7, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20341     

Effects of polyglycerol esters of fatty acids and ethylene‐vinyl acetate co‐polymer on crystallization behavior of biodiesel

Biodiesel fuels (BDF) have many problems in the cold due to their crystallization properties. In particular, precipitation of large crystals of high‐melting fractions in BDF at low temperatures remarkably changes cold flow property of BDF and, thereby, it increases the values of cold filter plugging point. In this study, we evaluated polyglycerol esters of fatty acids (PGE) and ethylene‐vinyl acetate co‐polymer (EVA) as chemical additives to improve the cold flow property of palm oil‐based FAME (PFME). The results of solid fat content measurement indicate that the simultaneous addition of PGE and EVA showed synergistic effects on suppression of crystallization of PFME, however such effect was not observed when EVA was used alone. DSC thermograms indicated that the PGE additives not only decreased the crystallization temperature but also kinetically suppressed the crystal growth. Polarized light microscopy showed that the simultaneous addition of PGE and EVA led to the formation of considerably small and fine‐dispersed crystals of PFME. These results indicate that combined effects of PGE and EVA caused the formation of fine‐dispersed PFME crystals, which could improve the viscous properties of palm oil‐based BDF at relatively cold temperatures.     

Photoluminescence of Rare-Earth-Doped Ca-α-SiAlON Phosphors: Composition and Concentration Dependence

Rare-earth-doped Ca-α-SiAlON phosphors, with the compositions of (Ca_{1−3/2 x} RE _x ) _{m /2}Si_{12− m − n} Al _m+n O _n N_{16− n} (RE=Ce, Sm, and Dy, 0.5≤ m =2 n ≤3.0), were prepared by sintering at 1700°C for 2 h under 10 atm N₂. The concentration of rare earths varied from 3 to 30 at.% with respect to Ca. The photoluminescence (PL) properties were investigated as functions of the composition of the host matrix (i.e., m ) and the concentration of rare earths (i.e., x ). The results show that the emission properties can be optimized by tailoring m and x . The Ce³⁺ luminescence originating from the 4 f –5 d interconfigurational transitions is greatly affected by the environment surrounding the Ce³⁺ ions, which differs from the Sm³⁺ or Dy³⁺ luminescence arising from the 4 f –4 f intraconfigurational transitions. X-ray diffraction and scanning electron microscopy were used to explain the composition and concentration dependence of PL properties.     

Optimal periodic maintenance strategy under an intermittently used environment

In this paper, the optimal periodic replacement-like strategy with minimal repairs is considered under an intermittently used environment. Suppose that transactions or jobs with exponential service times arrive at a system according to a homogeneous Poisson process and the system is alternatively in either a busy or an idle period subject to demand for use. We derive approximately the optimal preventive maintenance schedule which minimizes the relevant expected cost criterion for the system which behaves intermittently on an M/M/1 queueing process, and compare it with the usual maintenance schedule for the continuously used system.