Polymerization of methyl methacrylate in the presence of a nonpolar hydrocarbon solvent. I. Construction of a complete ternary phase diagram through an in situ polymerization

This article presents the ternary phase diagram for methyl methacrylate (MMA), poly(methyl methacrylate) (PMMA), and n‐hexane system at 70°C. It was constructed by both theoretical calculations and online laser light scattering (LLS) technique. In situ polymerization of MMA in a nonpolar nonsolvent carried out in a LLS cell provides a new means for the accurate detection of the cloud points of highly viscous polymer mixtures, with polymer weight fractions over 0.6. The ternary phase diagram measured in this study can be used to design the reaction conditions for the precipitation and/or dispersion polymerization in a nonpolar nonsolvent medium where polymerization kinetics as well as polymer particle morphologies are strongly affected by thermodynamic phase separation phenomena. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Supported hybrid early and late transition metal catalysts for the synthesis of polyethylene with tailored molecular weight and chemical composition distributions

Supported hybrid catalysts using metallocenes and a nickel diimine catalyst were synthesized and used for ethylene slurry polymerization and ethylene/1-hexene copolymerization. Two types of metallocenes, together with a nickel diimine catalyst were supported onto SiO₂ through chemical bonding, and a borate compound was physisorbed for the activation of the catalysts. These supported hybrid catalysts had high catalyst activities and made free-flowing polymer particles. The chemical composition distribution, molecular weight averages and distributions of resultant polymers were controlled by catalyst structure and polymerization conditions such as reaction temperature and the use of α-olefin. According to GPC-IR, ¹³C NMR and CEF characterization results of some polymers, more 1-hexene was incorporated in the high molecular weight region, short chain branches were generated by the chain walking mechanism in low molecular weight region. The morphologies of the resulting particles were investigated by SEM.     

Selective chromogenic and fluorogenic signalling of Hg ions using a fluorescein-coumarin conjugate

A novel, Hg²⁺-selective chemosensor was prepared via Mannich reaction of dichlorofluorescein with piperazinyl-coumarin moiety. The dichlorofluorescein–coumarin derivative exhibited well-defined Hg²⁺-selective chromogenic behavior, indicated by a green to pink colour change in solution, as well as fluorogenic signalling. Significant changes in fluorescence of the dichlorofluorescein subunit were analyzed in reference to the rather constant coumarin emission as an internal standard yielding Hg²⁺ selectivity. The Hg²⁺ selectivity of the chemosensor was not appreciably affected by the presence of common coexisting alkali, alkaline earth, and transition metal ions. The detection limit of the dichlorofluorescein–coumarin conjugate for the determination of Hg²⁺ ions was 4.3 × 10⁻⁶ mol L⁻¹ and the conjugate dye could be used as a chemosensor for the analysis of Hg²⁺ ions in aqueous environments.     

Physical degradation of MEA in PEM fuel cell by on/off operation under nitrogen atmosphere

The durability of PEMFCs is one of the most important issues for application in automotive vehicles with a repeated start-up and shut-down system. The understanding of degradation phenomena such as causes, mechanisms and influence of working condition is essential to improving the performance and lifetime of PEMFC. We conducted on/off cyclic operation in a single cell configuration with ultra purity nitrogen gas to investigate the physical degradation of membrane electrode assembly (MEA). After on/off cycle operation for 100,000 cycles under different humid condition, the characteristics of the MEAs were examined by in situ and ex situ analyses techniques. The physical degradation of MEA by on/off cycling led to a change in the membrane-electrode interfacial structure, which is mainly attributed to the loss of cell performance.     

Power generation/energy storage by a fuel cell/battery system: Regeneration of the MnO2 positive electrode with gaseous oxygen

Fuel cell/battery (FCB) systems are promising power generation/energy storage systems because of their bi-functionality as fuel cells and as secondary batteries. We investigated the required charging after the discharged manganese dioxide (MnOOH) by oxygen gas under the rest condition and during the fuel cell operation mode using manganese dioxide as a positive electrode for the FCB system. Electrochemical characterization was performed using cyclic voltammetry and galvanostatic measurements. Additionally, changes in the crystal structure and the chemical functional groups during the electrode reactions were monitored by X-ray diffractometry and Fourier transform infrared spectroscopy. The results indicated that MnOOH formed via the electrochemical discharge of manganese dioxide (MnO₂) and that the oxyhydroxide can be chemically transformed back to MnO₂ with gaseous oxygen (O₂). The recharged MnO₂ can be used as the cathode in a fuel cell with an O₂ supply and it can also be electrochemically discharged without an O₂ supply. In addition, we confirmed that MnO₂ does not convert to Mn₃O₄ during the charge/discharge cycles if the redox reaction is maintained within a restricted range where a homogeneous process exists between MnO₂ and MnOOH. The results in this study suggest that the FCB system can be constructed using MnO₂ as the positive electrode and a metal hydride (MH) as the negative electrode, which can be rapidly charged to more than 70% of the theoretical capacity within 10 min using pressurized H₂ and electrochemically discharged, in an alkaline electrolyte. This system possesses a high-power generation efficiency, a high-energy density and a high load-following capability.     

Preparation and catalytic activity of K4Zr5O12 for the oxidation of soot from vehicle engine emissions

Pure phase K₄Zr₅O₁₂ is synthesized via solid state method in the present work. Various K/Zr ratios and temperatures are applied, and the synthesis process is investigated in detail by means of X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. Its catalytic activity for soot oxidation is studied by temperature programmed oxidation with different types of soot/catalyst contacts. It is revealed that K₄Zr₅O₁₂ is very active in the presence of 2–10% O₂ for both tight and loose contacts (T_p(tight) = 335 °C, T_p(ethanol) = 355 °C and T_p(shaking) = 370 °C). Thermal stability study shows that K₄Zr₅O₁₂ is highly stable up to at least 900 °C.     

Synthesis and spectroscopic properties of novel phthalimide‐derived monoazo disperse dyes containing ester groups

The synthesis and spectroscopic properties of monoazo dye series, whose members consist of N‐alkylphthalimide diazo components combined with a coupling component containing two ester groups, are reported. Such colourants are potentially alkali‐clearable as a consequence not only of the presence of diester functionality on the coupler, but also through use of the base‐sensitive phthalimide system. Shortening the N‐alkyl group by removing one or two methylene units from a butyl chain made little difference to absorption properties, as would be expected given the relatively minor differences in inductive character produced. Shifts in the absorption maximum of the dyes associated with dibromination of the phthalimidylazo motif and its subsequent cyanodehalogenation were in agreement with theory and literature data for related series. Diester substitution on the coupling component brought about hypsochromism and hypochromism.     

Meshing wireless personal area networks: Introducing IEEE 802.15.5

This article presents an overview of the IEEE project 802.15.5 that targets providing mesh capabilities to both high-rate and low-rate wireless personal area networks. Low-rate mesh is built on IEEE 802.15.4 MAC, while high-rate mesh utilizes IEEE 802.15.3 MAC. We seek to share our insights and motivations of the approach adopted in the major components of the standard instead of presenting a la carte items drawn in the specification. We hope this article helps readers of the 802.15.5 standard to better understand the rationale and intent of the protocol design.     

Platinum Assisted Vapor–Liquid–Solid Growth of Er–Si Nanowires and Their Optical Properties

We report the optical activation of erbium coated silicon nanowires (Er–SiNWs) grown with the assist of platinum (Pt) and gold (Au), respectively. The NWs were grown on Si substrates by using a chemical vapor transport process using SiCl₄ and ErCl₄ as precursors. Pt as well as Au worked successfully as vapor–liquid–solid (VLS) catalysts for growing SiNWs with diameters of ~100 nm and length of several micrometers, respectively. The SiNWs have core–shell structures where the Er-crystalline layer is sandwiched between silica layers. Photoluminescence spectra analyses showed the optical activity of SiNWs from both Pt and Au. A stronger Er³⁺ luminescence of 1,534 nm was observed from the SiNWs with Pt at room- and low-temperature (25 K) using the 488- and/or 477-nm line of an Ar laser that may be due to the uniform incorporation of more Er ions into NWs with the exclusion of the formation of catalyst-induced deep levels in the band-gap. Pt would be used as a VLS catalyst for high performance optically active Er–SiNWs.     

A GSPN-Based Approach to Stacked Chips Scheduling Problem

This paper discusses scheduling characteristics unique in stacked chips [including multichip package (MCP) and multidie package (MDP)] production process such as reentrant work flow and synchronization constraint. It also proposes a modeling and analytical framework for stacked chips assembly operations, which is based on the formal framework of generalized stochastic Petri net. This approach allows the seamless integration of the logical and timed dynamics of stacked chip assembly operations in a single representation. Furthermore, the proposed framework supports the analytical representation of the stacked chips scheduling problem as a mathematical programming formulation, which can be effectively solved to optimality through enumerative techniques. The framework presentation and its capabilities are elucidated by detailed application on a small system configuration for MCP.