Differential scanning calorimetric studies on the glass transition temperature of polyhydroxystyrene derivatives containing sorbed water

Poly(4-acetoxystyrene) (PAS) and poly(4-acetoxy-3-methoxystyrene) (PAMS), poly(4-hydroxystyrene) (PHS) and poly(4-hydroxy-3-methoxystyrene) (PHMS) have been prepared. The effects of hydrogen bonding on the glass transition temperatures (T_g) of these polymers have been studied by differential scanning calorimetry. The T_g′s of partially hydrolyzed PAS and PAMS increased with the degree of hydrolysis. Partially hydrolyzed PAS and PAMS are estimated to be random copolymers, judging from the correspondence between the calculated and observed T_g′s of these polymers. The effect of water on the glass transition was also studied, and it was clarified how water adsorbed on the polymers acts as a hydrogen-bond breaker. The ‘critical water content’ is calculated from the decrease of T_g by water absorption, and the relation between hydrogen bonding and T_g is discussed.     

Synthesis of Monodispersed Spherical β-Silicon Carbide Powder by a Sol-Gel Process

Monodispersed spherical β-SiC powder was synthesized by heating spherical gel powder derived from the hydrolysis of a mixture of phenyltriethoxysilane and tetraethyl orthosilicate. The solution was prepared in a beaker and hydrolyzed by NH₄OH without stirring. The monodispersed spherical gel powder of submicrometer size was obtained when the added amount of NH₄OH was greater than 16 moles per mole of silane plus alkoxide, and it became monodispersed spherical β-SiC powder by heat-treating at 1500°C for 4 h in an Ar atmosphere. The SiC content of the powder was 92.6 wt%.     

Copolymerizations of macromonomer prepared by addition-fragmentation chain transfer polymerization of methyl acrylate trimer

Summary An oligomer of the methyl acrylate unsaturated trimer bearing 2-carbomethoxy-2-propenyl ω-end group (M _n = 1300, M _w/M _n = 1.7, and functionality > 0.7) was copolymerized as a macromonomer (0.02 mol/L) with styrene (1.0 mol/L) in benzene at 60 °C. The amounts of monomer and macromonomer in the feed simultaneously decreased with increasing time to indicate copolymer formation, and the macromonomer was found to be as reactive as styrene toward poly(styrene) radicals. The M _ns of the copolymers were 13900–22000 depending on conversion. No resonance due to the unsaturated <ω-end group bound to the poly(styrene) chain was detected by ¹H-NMR spectroscopy, indicating that no fragmentation of adduct radical of the end group to expel the poly(methyl acrylate trimer) radical. Polymerization of ethyl methacrylate (1.0 mol/L) in the presence of the macromonomer (0.02 mol/L) resulted in a mixture of the unreacted macromonomer and homopolymer of ethyl methacrylate. No end group bound to the poly(ethyl methacrylate) was detected by ¹H-NMR spectroscopy, excluding the possibility of addition fragmentation chain transfer to the macromonomer to expel an oligomer radical of the methyl acrylate trimer. Addition of the poly(methacrylate) radical to the macromonomer is extremely slow under the present conditions of copolymerization. Received: 27 March 2003/Revised version: 30 April 2003/ Accepted: 30 April 2003 Correspondence to Bunichiro Yamada     

Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Thermal behaviors and flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives

The thermal behaviors and the flame‐retardancy of styrene–ethylene–butadiene–styrene–block copolymer containing various additives were studied. The combustion was measured by the Underwriter laboratory (UL) test and cone calorimeter test and thermogravimetric analysis and program‐mass spectroscopy were applied to analyze the thermal behaviors. The blend with halogen additives showed the best result in the UL test. However, the blend with red‐phosphorous was the best in the cone calorimeter test. As the styrene sequence in the copolymer tended to degradate at a lower temperature, the major scission products spouted out from the polymer surface originated from polystyrene. The shorter the ignition times of the blends with red‐phosphorous were, the lower the peak heat release rates were. It was an interesting phenomenon because it suggested that the chemical structure of the residue changed to more stable polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 156–161, 2007     

Formation of phase structure and crystallization behavior in blends containing polystyrene–polyethylene block copolymers

The microphase separation structure in the molten state and the structure formation in crystallization from such ordered melt were investigated for the blends of polystyrene–polyethylene block copolymers (SE) with polystyrene homopolymer (PS) and polyethylene homopolymer (PE) and for the blends consisting of two kinds of SE with different copolymer compositions from each other, using synchrotron small-angle X-ray scattering techniques (SAXS). The copolymer compositions of SE block copolymers employed were 0.34, 0.58 and 0.73 wt. fraction of PE, and their melt morphologies were cylindrical, lamellar and lamellar, respectively. Macrophase separation or the morphology change in the melt occurred depending on the molecular weight and the blend composition, as reported so far. In crystallization from such macrophase-separated and microphase-separated melts, the melt morphology was completely kept for all the blends. Crystallization behavior was also investigated for the blends. The crystallization within the spherical and cylindrical domains surrounded by glassy PS was not observed for SE/PS blends. In the crystallization from the macrophase-separated melt, two exothermal peaks were observed in the DSC measurements, while a single peak was observed for other blends. For the blends with PS, the degree of crystallinity was depressed and the apparent activation energy of crystallization was high, compared to those for the corresponding neat SE. For SE/PE and SE/SE blends, those were changed depending on the blend composition.     

Scanning electron microscopy of nerve fibers in human fetal cochlea

The cochleas of four human fetuses ranging 22–25 weeks gestation were studied by scanning electron microscopy (SEM) for the purpose of obtaining a better understanding of the nerve fiber arrangement in the human ear. After critical point drying, the specimens were dissected and the floor of the tunnel of Corti and the outer wall of Nuel's space were exposed for observation. Upper cochlear turns, especially the apical turn, seemed to be still immature. Observed nerve fibers were classified into three types:

• 1 Spiral fibers: Fibers traveling basalward and following the shape of the cochlea were found in both the tunnel of Corti and Nuel's space and believed to be the afferent nerves responsible for innervating the outer hair cells
• 2 Radial fibers: radiating outward from the osseous spiral lamina—one such radial fiber transversing high in the tunnel space (supposedly the efferent nerve servicing the outer hair cells), and another sort of radial fiber (found crossing the tunnel floor), the nature of which was uncertain.
• 3 Irregular fibers: Consisting of thin, randomly running fibers within the cochlea. The destination of these fibers was not determined, but possibly they represent transitory nerve branchings of afferent or more probably efferent nerves, which would later regress during maturation.

     

Fault tolerant approach for biosignal-based robot control

This paper proposes a fault tolerant framework for biosignal-based robot control with multiple sensor electrodes. In this approach, to cope with sensor faults, a reliable joint torque estimation model is selected from a group of estimation models based on sensor failure classifiers. The correlation among the electromyography (EMG) signal streams is used as input feature vectors for fault detection. To validate our proposed method, we artificially disconnect an EMG electrode or detach one side of an EMG probe from the skin surface during elbow-joint torque estimation experiments with five participants. When one EMG sensor electrode experiences one of the problems, the experimental results show that the joint torque can be estimated with significantly fewer errors using our proposed approach than a joint torque estimation method without sensor fault detection or than a method with a conventional sensor fault detection algorithm. Furthermore, we controlled a mannequin-arm-attached one-DOF exoskeleton based on the estimated torque profiles by generating movements with the estimated torque derived from the selected model.     

Predicting viewer-perceived activity/dominance in soccer games with stick-breaking HMM using data from a fixed set of cameras

We attempted to predict activity/dominance for soccer games, where activity is defined as the degree of activity of the game as perceived by the viewer, whereas dominance is the degree at which the viewer perceives a particular team to dominate over the other team. Such activity/dominance information would help a layman viewer understand the game. It would also enable construction of an automatic digest creation system that extracts scenes having high activity/dominance. There are two facets of this study: 1. The main part of the underlying prediction model consists of a Stick-Breaking Hidden Markov Model, where the data automatically estimates the number of states of the Markov process behind the data. 2. The data used in this paper is vector time-series data consisting of player, referee, and ball positions, together with team information, acquired by a set of fixed cameras. The problem was approached with a Bayesian framework where learning and prediction were implemented by three different methods: Markov Chain Monte Carlo, Expectation Maximization, and Variational Bayes. The proposed method was tested using a dataset consisting of 10 professional soccer games and was compared against standard regression methods.