Chemical Reaction Engineering and Research and development of gas solid systems

A general procedure is proposed for innovative research and development of gas-solid reactor systems, with a brief explanation of the significance of each step in the procedureBased upon the contacting mode between gas and solid phases, as well as the ways of supplying thermal energy to the reacting regions, various types of gas-solid reactor systems are classified by using tables of so called “matrix” form, for thermal cracking and gasification of heavy oils, gasification of coal, gasification of solid waste, calcination of limestone, clinkering of cement and reduction of iron ore.The importance of fundamental concepts is emphasized for successful research and development by presenting several examples; namely, calcination of limestone, thermal cracking of heavy oils and gasification of solid waste materials.In connection with the direction in which fundamental research should be oriented, four primary ways of thinking are proposed, which can be applied to obtain innovative ideas for further research and development in this field.One example of the author's practical experience was selected to show the role of the fundamental research in the course of large scale development. Finally the author outlines the role of chemical reaction engineering to innovate the novel gas-solid reactor systems which may be inevitable for simultaneous solution of the three big E's; namely, Energy, Environment and Economy.     

Comparative study on the preparation and properties of radiation‐grafted polymer electrolyte membranes based on fluoropolymer films

In this study the fluoropolymers, poly(ethylene‐co‐tetrafluoroethylene) (ETFE) and poly(vinylidene fluoride) (PVDF) films, together with the radiation‐induced crosslinked polytetrafluoroethylene (cPTFE) film were compared on the basis of their preparation and properties of radiation‐grafted polymer electrolyte membranes. The polymer electrolyte membranes were prepared by radiation grafting of styrene into the base films and subsequent sulfonation. The proton conductivity and chemical stability of the three types of membranes with a similar ion exchange capacity (IEC) near 1.0 mmol/g were investigated and are discussed in detail. Although the ETFE‐based polymer electrolyte membrane was relatively more stable, its proton conductivity was lower than those of the PVDF‐ and cPTFE‐based membranes. On the other hand, the cPTFE‐based membrane showed a significantly higher proton conductivity, but its chemical stability was shorter than that of the ETFE‐based membrane. It is considered that the difference in the preparation and properties of the polymer electrolyte membranes was due to the difference in the degree of crystallinity as well as in the chemical structure of the fluoropolymer base films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1966–1972, 2007     

Synthesis of γ-Ga2O3–Al2O3 Solid Solutions by the Glycothermal Method

The reaction of mixtures of aluminum isopropoxide and gallium acetylacetonate in 1,4-butanediol or 1,5-pentanediol at high temperatures (glycothermal reaction) directly gave the γ-Ga₂O₃–Al₂O₃ solid solutions, which had high catalytic activities for selective reduction of NO using methane as the reducing agent. However, the reaction with a higher Al/(Ga+Al) charged ratio yielded the glycol derivative of boehmite as a by-product and the catalytic activity of the solid solution decreased. Therefore, synthesis of the solid solution using various glycols was examined and it was found that solid solutions with high Al contents without contamination of the glycol derivative of boehmite were obtained by using 1,6-hexanediol as a reaction medium. The solid solution exhibited a higher NO conversion than that synthesized in other glycols.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Aging and availability of binocular disparity and pictorial depth cues in 3D graphics contents

Some stereoblind observers do not perceive depth of 3D stimuli that depends on binocular disparity. These individuals, who have no disabilities, comprise over 5% of the general population. In addition, 17–30% of nonstereoblind young and young–middle people do not use disparity information in certain 3D environments, a phenomenon known as pseudo‐stereoblindness. This study aimed to investigate the relationship between aging and the proportion of pseudo‐stereoblindness in the general population. In an experiment, 134 nonstereoblind participants, ranging in age from 17 to 83 years, judged subjective depth of 3D stimuli containing binocular disparity and pictorial depth cues. Results showed that the proportion of pseudo‐stereoblindness among young (17–24 years old) and young–middle aged observers (25–39 years old) was 29%, in both cases. However, the proportion of pseudo‐stereoblind observers increased in older populations: 65% and 82% in the middle (40–54 years old) and senior (55–83 years old) age groups, respectively. These results suggest that a number of people, especially in elderly populations, have trouble perceiving depth from binocular disparity in 3D graphic contents despite their essential ability to use disparity information.     

Formation, Characterization, and Hot Isostatic Pressing of Cr2O3-Doped ZrO2 (0,3 mol% Y2O3) Prepared by Hydrazine Method

In the ZrO₂-Cr₂O₃ system, metastable t -ZrO₂ solid solutions containing up to 11 mol% Cr₂O₃ crystallize at low temperatures from amorphous materials prepared by the hydrazine method. The lattice parameter c decreases linearly from 0.5149 to 0.5077 nm with increased Cr₂O₃ content, whereas the lattice parameter a is a constant value ( a = 0.5077 nm) regardless of the starting composition. At higher temperatures, transformation (decomposition) of the solid solutions proceeds in the following way: t (ss)→ t (ss) + m + Cr₂O₃→ m + Cr₂O₃. Above 11 mol% Cr₂O₃ addition, c-ZrO₂ phases are formed in the presence of Cr₂O₃. The t -ZrO₂ solid solution powders have been characterized for particle size, shape, and surface area. They consist of very fine particles (15–30 nm) showing thin platelike morphology. Dense ZrO₂(3Y)-Cr₂O₃ composite ceramics (∼99.7% of theoretical) with an average grain size of 0.3 μm have been fabricated by hot isostatic pressing for 2 h at 1400°C and 196 MPa. Their fracture toughness increases with increased Cr₂O₃ content. The highest K _Ic value of 9.5 MPa·;m^1/2 is achieved in the composite ceramics containing 10 mol% Cr₂O₃.     

Structural characterization of 1,2-polybutadiene by 13C-n.m.r. spectroscopy: 2. Sequence distribution of 1,2-unit in hydrogenated polybutadienes

The configurational sequences of 1,2-unit in a series of hydrogenated syndiotactic 1,2-polybutadienes were determined in relation to the sequence distribution of 1,2- and 1,4-units on the basis of the ¹³C-n.m.r. signal assignment of the methyl carbons. The observed triad distributions of 1,2- and 1,4-units and configurational distributions of the 1,2-unit are in good agreement with the calculated distributions from transition probabilities. The number average sequence lengths of the 1,2-unit and the 1,2-unit in the racemic addition are 5.7 to 8.0 and 4.1 to 5.4, respectively. From the extrapolation of the plot of the number average sequence length against the crystallinity of the starting 1,2-polybutadienes, the minimum sequence length for crystallization is estimated to be 3.7 for the 1,2-unit in the racemic addition.     

VGQ-Vor: extending virtual grid quadtree with Voronoi diagram for mobile k nearest neighbor queries over mobile objects

Performing mobile k nearest neighbor (MkNN) queries whilst also being mobile is a challenging problem. All the mobile objects issuing queries and/or being queried aremobile. The performance of this kind of query relies heavily on the maintenance of the current locations of the objects. The index used for mobile objects must support efficient update operations and efficient query handling. This study aims to improve the performance of the MkNN queries while reducing update costs. Our approach is based on an observation that the frequency of one region changing between being occupied or not by mobile objects is much lower than the frequency of the position changes reported by the mobile objects. We first propose an virtual grid quadtree with Voronoi diagram(VGQ-Vor), which is a two-layer index structure that indexes regions occupied by mobile objects in a quadtree and builds a Voronoi diagram of the regions. Then we propose a moving k nearest neighbor (kNN) query algorithm on the VGQ-Vor and prove the correctness of the algorithm. The experimental results show that the VGQ-Vor outperforms the existing techniques (Bx-tree, Bdual-tree) by one to three orders of magnitude in most cases.     

Thermal management of edge‐lit wide color gamut backlight for LCD using red laser diodes and cyan LEDs

The color gamut is one of the critical parameters that dictate the image quality of displays. The liquid crystal displays using white color light‐emitting diodes (LEDs) as the backlight, though having been widely employed recently, are not very satisfactory in terms of their color gamut because of the broad spectrum inherent to white LEDs. This prompted the authors to develop improved liquid crystal displays using an edge‐lit wide color gamut backlight that used red laser diodes and cyan LEDs. Generating laser beams with high color purity, the laser diodes are light sources with a significant effect on expanding the color gamut. However, laser diodes, red ones in particular, have unfavorable thermal characteristics. To cope with this shortcoming, the authors clearly defined the restrictive criteria for laying out two kinds of light source on the edge‐lit backlight and made a prototype 55‐type laser backlight for performance evaluation.     

Cylindrical coils created with 3D X-ray lithography and metallization

The demand for microactuators is increasing recently. The key technology to realizing practical microactuators is microfabrication process. In the production of microminiature components, the technologies for processing high-aspect-ratio structures are essential. As one of these technologies, the LIGA process is widely known. Our laboratory researches the LIGA process to three-dimensional microfabrication and established the cylindrical-microcoil production process. In this paper, we have fabricated the cylindrical-microcoil for the solenoidal electromagnetic type microactuator. We designed and analyzed microactuators, and fabricated and evaluated microactuator coils produced by the combination of three-dimensional X-ray lithography and level copper plating. We succeeded in creating threaded groove-shaped structures with 10 μm line width, 20 μm pitch, and aspect ratio of 5 on the surface of an acrylic pipe by means of three-dimensional X-ray lithography. As a measure to suppress void generation, which is one of the shortcomings of electrolytic plating processes, the sputtering apparatus and plating equipment were improved, a pretreatment process was additionally provided, and the actual electrolytic plating method was improved. As a result, a void-free metallic deposit could be formed on a thin coil line. The processing technology enables the formation of thin-wire coil lines whose current paths feature a large allowable current-carrying capacity, enabling the production of miniature, high-output microactuators.