Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

The roles of the Trommsdorff–Norrish effect in phase separation of binary polymer mixtures induced by photopolymerization

Influence of the Trommsdorff–Norrish (T–N) effect on the phase separation of methyl methacrylate (MMA)/poly(ethyl acrylate) (PEA) mixtures undergoing photo-polymerization was examined by a combination of several experimental techniques. By FT-IR spectroscopy, it was found that the polymerization conversion explosively increases at the onset of this T–N effect. The characteristic irradiation time τ at which this effect occurs, strongly depends on the light intensity and gradually shifts to early time as the irradiation intensity increases. The shrinkage of the mixture observed in situ by laser-scanning confocal microscopy exhibits a transition at a particular irradiation time which is slightly longer than the characteristic time τ. By gel permeation chromatography (GPC), it was found that the molecular weight of the resulting PMMA was almost unchanged before τ and suddenly increases about an order of magnitude after the onset of the auto-acceleration effect. Finally, the characteristic length scales of the morphology also quickly increase with irradiation time and are eventually frozen by this T–N effect. These experimental results indicate that the Trommsdorff–Norrish effect plays an important role in the kinetic processes of polymerization-induced phase separation, suggesting an efficient tool to control the morphology of the polymerizing mixture.     

Different support effect of M/ZrO2 and M/CeO2 (M = Pd and Pt) catalysts on CO adsorption: A periodic density functional study

CO adsorption over Pd₄ and Pt₄ cluster supported by c-ZrO₂(1 1 1) and CeO₂(1 1 1) catalyst systems was investigated using periodic density functional method in order to clarify the support effect on CO activation. We found that the support increases the CO activation for bridge and three-fold sites but decreases for the atop site. Moreover, it was found that the support changes the site preference for the CO adsorption. Bridge site on both the Pt₄/c-ZrO₂ and Pt₄/CeO₂ show larger CO adsorption energies than those on the other sites while the atop site is energetically preferable on isolated Pt₄ cluster. c-ZrO₂ supported Pd shows the largest CO activation with large charge transfer from the catalyst to the CO molecule. This reveals that ZrO₂ supported Pd can be a good catalyst for CO activation because of its higher probability to the three-fold site CO adsorption. We also found that positively charged M₄ clusters on the support keep their strong electron-donating properties and have enough charge density to contribute to the activation of an adsorbed CO molecule by a charge transfer.     

Mammalian Cytochrome P450-Dependent Metabolism of Polychlorinated Dibenzo-p-dioxins and Coplanar Polychlorinated Biphenyls

Polychlorinated dibenzo-p-dioxins (PCDDs) and coplanar polychlorinated biphenyls (PCBs) contribute to dioxin toxicity in humans and wildlife after bioaccumulation through the food chain from the environment. The authors examined human and rat cytochrome P450 (CYP)-dependent metabolism of PCDDs and PCBs. A number of human CYP isoforms belonging to the CYP1 and CYP2 families showed remarkable activities toward low-chlorinated PCDDs. In particular, human CYP1A1, CYP1A2, and CYP1B1 showed high activities toward monoCDDs, diCDDs, and triCDDs but no detectable activity toward 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-tetraCDD). Large amino acids located at putative substrate-recognition sites and the F-G loop in rat CYP1A1 contributed to the successful metabolism of 2,3,7,8-tetraCDD. Rat, but not human, CYP1A1 metabolized 3,3'',4,4'',5-pentachlorobiphenyl (CB126) to two hydroxylated metabolites. These metabolites are probably less toxic than is CB126, due to their higher solubility. Homology models of human and rat CYP1A1s and CB126 docking studies indicated that two amino acid differences in the CB126-binding cavity were important for CB126 metabolism. In this review, the importance of CYPs in the metabolism of dioxins and PCBs in mammals and the species-based differences between humans and rats are described. In addition, the authors reveal the molecular mechanism behind the binding modes of dioxins and PCBs in the heme pocket of CYPs.     

A study on the preparation of supported metal oxide catalysts using JRC-reference catalysts. I. Preparation of a molybdena–alumina catalyst. Part 4. Preparation parameters and impact index

The effects of the volume and pH of the impregnation solution and of the calcination conditions were examined on the physicochemical and catalytic properties of a 13 wt% MoO₃/Al₂O₃ extrudate catalyst. The Al₂O₃ support and drying procedures (static conditions without flowing air) were fixed in the preparations. In the present series of catalysts, the amount of crystalline MoO₃ was marginally small. It was found that the dispersion of Mo oxide species increased as the volume of the impregnation solution increased, gradually approaching a maximum value. The increase in pH (2–8) of the impregnation solution was found to reduce the dispersion of Mo oxide species. The Mo dispersion increased slightly for the impregnation catalysts as the calcination temperature increased (673–873 K), whereas it decreased for the equilibrium adsorption catalysts. The effects of the calcination atmosphere (with or without flowing air, or with flowing humid air) were very small on the dispersion of Mo oxide species under the present preparation conditions. On the other hand, the methanol oxidation activity of MoO₃/Al₂O₃ was sensitive to the preparation parameters examined here. It was demonstrated by means of EPMA and XPS that a considerable migration of Mo took place during the calcination.

In the present study on the preparation of a 13 wt% MoO₃/Al₂O₃ catalyst, an impact index is proposed to measure the magnitude of the effects of the respective parameter(s) on the physicochemical and catalytic properties. With the Mo dispersion, the effects of the preparation parameter decreased in the order, surface area of the support >> drying process > volume of the impregnation solution > pH, calcination temperature and atmosphere. The size of the impact index for the dispersion of Mo sulfide species is 70–75% of that for the Mo oxide species. The HDS activity of the catalyst was less affected by the preparation parameters than the Mo sulfide dispersion. The preparation parameters affected the segregation of Mo on the outer surface of extrudates in a decreasing order: drying process > volume of the impregnation solution > pH, calcination conditions. It was found that the oxidation of methanol was affected most intensely by the drying procedures. The volume of the impregnation solution, calcination conditions and pH of the impregnation solution also strongly affected the oxidation activity. The impact index suggests that the sensitivity to the preparation variables of the physicochemical and catalytic properties of MoO₃/Al₂O₃ decreases in the order, methanol oxidation activity > surface Mo segregation > Mo oxide dispersion > Mo sulfide dispersion > HDS activity.     

Detection of lumen-intima interface of posterior wall for measurement of elasticity of the human carotid artery

In our series of studies on noninvasive assessment of the regional elasticity of the arterial wall, the displacement gradient (change in thickness) of the arterial wall caused by the heartbeat was measured by the phased tracking method. Because the displacement gradient corresponds to the strain due to the change in blood pressure, the elasticity can be evaluated from the displacement gradient of the arterial wall and the blood pressure, which are noninvasively measured at the upper arm. In the measurement of the elasticity of the arterial wall by our method, the region in which the elastic modulus is estimated must be assigned beforehand; currently, the lumen-intima boundary of the arterial wall is manually determined by the operator. For the real-time measurement of the elasticity of the arterial wall, a fast, automated method is necessary for detection of the boundary. In this paper, a cost function is proposed for differentiation of the arterial wall from the lumen. The proposed cost function was applied to ultrasound data, which were noninvasively obtained for five human carotid arteries. In comparison with the case of detection using only the amplitude of the echo, the root mean square error between the automatically detected lumen-intima boundary and the manually assigned boundary was significantly improved by using the proposed cost function. Furthermore, the lumen- intima boundary was automatically detected in a short period. Such a method is required for real-time measurement of the elasticity of the arterial wall, though detection of the outer boundary of the adventitia, which is not described in this paper, is also necessary to realize real-time elasticity measurement by our method.     

Chemical modification of group IV graphene analogs

Mono-elemental two-dimensional (2D) crystals (graphene, silicene, germanene, stanene, and so on), termed 2D-Xenes, have been brought to the forefront of scientific research. The stability and electronic properties of 2D-Xenes are main challenges in developing practical devices. Therefore, in this review, we focus on 2D free-standing group-IV graphene analogs (graphene quantum dots, silicane, and germanane) and the functionalization of these sheets with organic moieties, which could be handled under ambient conditions. We highlight the present results and future opportunities, functions and applications, and novel device concepts.     

Growth and characterization of stoichiometric BCN films on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition

Hexagonal boron carbonitride (h-BCN) hybrid films have been synthesized on highly oriented pyrolytic graphite by radiofrequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane as a single-source molecular precursor. The films were characterized by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS) and Raman spectroscopic measurements. XPS measurement showed that the B atoms were bonded to C and N atoms to form the sp²-B-C-N atomic hybrid chemical environment. The atomic composition estimated from the XPS of the typical sample was found to be almost B₁C₁N₁. NEXAFS spectra of the B K-edge and the N K-edge had the peaks due to the π* and σ* resonances of sp² hybrid orbitals implying the existence of the sp² hybrid configurations of h-BCN around the B atoms. The G band at 1592 and D band at 1352 cm^− 1 in the Raman spectra also suggested the presence of the graphite-like sp²-B-C-N atomic hybrid bonds. The films consisted of micrometer scale crystalline structure of around 10 µm thick has been confirmed by the field emission scanning electron microscopy.