Synthesis and characterization of soluble hyperbranched polymer via initiator‐fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′‐azobisisobutyrate

The homopolymerization of divinylbenzene (DVB) as an excellent crosslinker (0.20 mol/L) with dimethyl 2,2′‐azobisisobutyrate (MAIB) proceeded homogeneously without any gelation at 80°C in benzene when the MAIB concentrations as high as 0.30–0.50 mol/L were used, yielding soluble polymers. In the polymerization at the concentrations of [DVB] = 0.20 mol/L and [MAIB] = 0.50 mol/L, the polymer yield increased with time and leveled off over 90 min. The molecular weight and molecular weight distribution increased with polymer yield. The vinyl groups of DVB were observed to be almost completely consumed in about 80 min, by FT near‐IR spectroscopic analysis. The homogeneous polymerization system involved ESR‐observable polymer radical, the concentration of which increased with time up to 3.4 × 10^?5 mol/L. The polymer formed in the polymerization for 2 h consisted of 46 mol % of DVB unit and 54 mol % of the methoxycarbonylpropyl group as MAIB fragment, indicating that an initiator‐fragment incorporation radical polymerization proceeds in the present polymerization. The polymer was soluble in benzene, tetrahydrofuran, ethyl acetate, chloroform, acetone, and N,N‐dimethylformamide, while it was insoluble in n‐hexane, acetonitrile, dimethyl sulfoxide, methanol, and water. The results of the multiangle laser light scattering and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched polymer nanoparticles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 664–670, 2006     

Construction and development of a time-resolved x-ray magnetic circular dichroism-photoelectron emission microscopy system using femtosecond laser pulses at BL25SU SPring-8

A femtosecond pulsed laser system has been installed at the BL25SU soft x-ray beamline at SPring-8 for time-resolved pump-probe experiments with synchronization of the laser pulses to the circularly polarized x-ray pulses. There are four different apparatuses situated at the beamline; for photoemission spectroscopy, two-dimensional display photoelectron diffraction, x-ray magnetic circular dichroism (XMCD) with electromagnetic coils, and photoelectron emission microscopy (PEEM). All four can be used for time-resolved experiments, and preliminary investigations have been carried out using the PEEM apparatus to observe magnetization dynamics in combination with XMCD. In this article, we describe the details of the stroboscopic pump-probe XMCD-PEEM experiment, and present preliminary data. The repetition rate of the laser pulses is set using a pulse selector to match the single bunches of SPring-8's hybrid filling pattern, which consists of several single bunches and a continuous bunch train. Electrons ejected during the bunch train, which do not provide time-resolved signal, are eliminated by periodically reducing the channel plate voltage using a custom-built power supply. The pulsed laser is used to create 300 ps long magnetic field pulses, which cause magnetic excitations in micron-sized magnetic elements which contain magnetic vortex structures. The observed frequency of the motion is consistent with previously reported observations and simulations.     

Automated identification of partially exposed metal object

This paper describes a method for automated shape and pose (position and orientation) identification of partially exposed metal objects that enables safe and efficient excavation of hazardous materials. The method estimates the object pose by matching a model of the object with the area that is extracted from the range image using the characteristics of metal objects. The paper introduces a method for an initial search area for object matching in order to obtain the accurate shape and pose of the partially exposed objects with reasonable calculation time. The experimental results show feasibility of the shape and pose identification of partially exposed objects.     

Development of a contact-type probe for measurements of ultra-fine-pitch gears and application to pseudo roughness evaluation

Gears used in actuators for robot articulations are showing a trend toward having smaller modules. Thus, profile measurements of small module gears are strongly desired. Our aim was to develop a probe artifact that enables ultra-fine-pitch cylindrical gears to be measured, by minimizing the size of the probe head. The configurations of the contact-type probe and holder were designed under consideration of interference with an adjacent tooth during profile measurements of an objective tooth. After manufacturing the artifact, a 0.1-module spur gear was measured as a trial, and reasonable results were obtained. In addition, a calibration plate for roughness was measured using the developed probe artifact. The evaluated roughness showed a strong correlation with the “true roughness”. Therefore, the developed probe can be expected to enable “pseudo” roughness to be evaluated.     

Relevance of graphene oxide as nanofiller for geometrical variation in unidirectional carbon fiber/epoxy composite

Curved geometry in unidirectional CFRP (UD-CFRP) demands ideal shape optimization to attain superior performance while maintaining the desired high strength to weight ratio. Herein, the effect of graphene oxide (GO) as the potential filler to improve the mechanical and thermal properties of flat and curved specimens of UD-CFRP was investigated. The GO was synthesized using Hummer's method and introduced in the epoxy resin by wet transfer technique. Three-point and four-point bending analysis of UD-CFRP showed maximum flexural strength and modulus at 0.3 wt% GO addition in UD-CFRP. The improved interfacial adhesion of 0.3 wt% GO incorporated UD-CFRP was realized by calculating storage modulus, reinforcement efficiency factor (r), C-factor, adhesion factor, cross-linking density, and glass transition temperature (T_g) from dynamic mechanical analyzer. Fracture analysis by scanning electron microscope showed the superior interlocking in carbon fiber, and epoxy polymer at 0.3 wt% GO addition.     

Surface layer of Pt-O-Ce bonds on CeOx nanowire with high ORR activity converted by proton beam irradiation

To develop the state-of-the-art polymer membrane fuel cells. Both maximization of oxygen reduction reaction (ORR) activity on Pt cathode and minimization of Pt content in the cathode are required. For this challenge, the defect interface on oxide support was modified by proton beam irradiation method. Pt-CeO_x nanowire/C (Pt/C = 0.02) was fabricated using the proton beam irradiation method. Since the radical density generated by proton beam irradiation is two orders of magnitude greater than that of electron beam irradiation, the CeO_x nanowire surface was fully converted to a thin layer of Pt-O-Ce bonds under proton beam irradiation. The ORR activity observed for fabricated sample with above active surface layer was higher than that of conventional Pt/C (Pt/C = 0.2) and comparable to that of Pt-CeO_x nanowire/C (Pt/C = 0.2) fabricated by conventional methods. From the combination of microanalysis characterization and surface atomistic simulation, we concluded that the Pt-O-Ce bond was formed on defect-rich regions of the CeO_x nanowire and this leads to a maximized ORR activity on the fabricated sample. Based on all experimental data, it is concluded that the surface modification of CeO_x nanowire support using proton beam irradiation is useful for a lowering the Pt content of the cathode with high ORR activity.     

THERMAL PERFORMANCE AND EVALUATION OF SIPERHEATED STEM DRYING SYSTEM USING SOLAR-ASSISTED ABSORPTION HEAT TRANSFORMER

ABSTRACT

This paper summarizes the main results of our study carried out under the priority-area research “Energy Conversion and Utilization with High Efficiency” supported by the grant-in-aid of scientific research from the Ministry of Education, Science and Culture of Japan. In the research we focused on applications of solar energy utilization for industrial drying systems. In this paper a new concept of a closed drying system with superheated steam provided from a temperature boosting type heat pump (absorption type heat transformer) was proposed. The heat transformer is driven directly by heat from a solar collector. The performance for different three drying periods and a number of factors affecting it were predicted by a computer simulation. Furthermore the heat and mass transfer characteristics of water evaporation into superheated steam stream by radiative and convective heating were indicated experimentally. It was concluded that the system would be useful for industries where high temperature (over 100°C) drying is required.     

Lattice Strain and Dislocations in Polished Surfaces on Sapphire

Polishing of ceramics, surface defects and strain are introduced that influence the mechanical properties in the final products. In this study, the sapphire surfaces with a -plane and c -plane were polished using several kinds of diamond slurry, and the introduced damaged zones were investigated using transmission electron microscopy (TEM), high-resolution TEM, and TEM-CBED (convergent beam electron diffraction). It was found that the types of slip systems and strain distribution were different between the a -plane-polished and the c -plane-polished specimens. That is, the basal slip and the prism slip were mainly activated in the c - and a -plane-polished specimens to form the different damaged zones. This difference was probably due to the difference in the direction and angle from the slip plane and applied shear stress during the polishing. On the basis of these observations, the types of introduced dislocations and distribution of strain were discussed to clarify the mechanism of polishing.     

Effect of nitrobenzene on initiator-fragment incorporation radical polymerization of divinylbenzene with dimethyl 2,2′-azobisisobutyrate

The polymerization of divinylbenzene (DVB) with dimethyl 2,2′-azobisisobutyrate (MAIB) was conducted at 70 and 80 °C in benzene in the presence of nitrobenzene (NB) as a retarder. When the concentrations of DVB, MAIB, and NB were 0.45, 0.50, and 0.50 mol/l, respectively, the polymerization proceeded without any gelation to yield soluble polymers. The polymer yield (up to 65%) and the molecular weight (M_n=1.5-4.2×l0⁴ at 70 °C and 1.3-3.9×l0⁴ at 80 °C) increased with time. The polymer formed in the polymerization at 80 °C for 4 h consisted of the DVB units with (4 mol%) and without double bond (41 mol%), methoxycarbonylpropyl group as MAIB-fragment (48 mol%), and NB unit (7 mol%). Incorporation of such a large number of the initiator-fragments as terminal groups in a polymer molecule indicates that the polymer is of a hyperbranched structure. The polymer showed an upper critical solution temperature (40 °C on cooling) in an acetone-water [14:1 (v/v)] mixture. The results of MALLS and viscometric measurements and TEM observation supported that the polymers formed in the present polymerization have a hyperbranched structure. The polymerization system at 70 °C involved an ESR-observable nitroxide radical formed by the addition of polymer radical to the nitro group of NB. The polymerization was kinetically investigated in dioxane. The initial polymerization rate (R_p) at 70 °C was expressed by R_p=k[MAIB]^0.5[DVB]^0.9[NB]^−0.4. The kinetic results were explained on the basis of the reversible addition of polymer radical to NB and the termination between the polymer radical and the nitroxide radical. The overall activation energy of the polymerization was 27.8 kcal/mol.     

Direct synthesis of syndiotactic-rich poly(N-isopropylacrylamide) via radical polymerization of hydrogen-bond-complexed monomer

Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene was investigated in the presence of hexamethylphosphoramide (HMPA). We succeeded in directly preparing syndiotactic-rich poly(NIPAAm), the syndiotacticity of which (r=70%) is the highest among those of radically-prepared poly(NIPAAm)s so far reported, by lowering polymerization temperature to −60 °C in the presence of a two-fold amount of HMPA. The NMR analysis revealed that the induced syndiotactic-specificity was ascribed to 1:1 complex formation between NIPAAm and HMPA. Furthermore, thermodynamic analysis described that the induced syndiotactic-specificity was enthalpically achieved.