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.     

Nanostructured poly(3-hexylthiophene-2,5-diyl) films with tunable dimensions through self-assembly with polystyrene

Poly(3-hexylthiophene-2,5-diyl) is among the most widely used conjugated polymers for opto-electronic applications. To enhance its properties, researchers have attempted to nanostructure this polymer using various processes including breath figure arrays, nanolithography and elaborated organic synthesis. We here demonstrate a simple process to nanostructure the conjugated polymer using self-assembly with polystyrene and selective removal of one of the phases. The influence of the molecular weight of each polymer on the thin film morphology was systematically studied by atomic force microscopy. Using this approach, we observe two types of nanostructure, namely, nanoporous and nanoisland structures, of which the dimensions can be tuned by modifying the molecular weight of each polymer in the blend. This simple process introduces a cost-effective alternative to produce thin films of conjugated polymer with average nano-features from 100 nm up to 500 nm which could be used in a wide range of applications.     

Controlled radical polymerization with polyolefin macroinitiator: a convenient and versatile approach to polyolefin-based block and graft copolymers

This paper introduces the new synthetic methodology of polyolefin-based block and graft copolymers with polar segments [e.g., polystyrene and poly(meth)acrylates]. Various brominated polyolefins were prepared by bromination of polyolefins with N-bromosuccinimide. The resulting brominated polyolefins were able to initiate the controlled radical polymerization of polar monomers, such as methyl methacrylate, ethyl acrylate, t-butyl acrylate, styrene and 2-(dimethylamino)ethyl acrylate, using a CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system, leading to a variety of polyolefin-based copolymers with a different content of the corresponding polar segment. Because of the accessible synthesis of polyolefin macroinitiators, this synthetic methodology is expected to result in the preparation of a wide range of polyolefin-based block and graft copolymers.     

Experimental study on method of estimating strength of weld metal in steel structure

We conducted the welding experiment using three kinds of test piece, actual size, diaphragm and butt joint. Then, we examined the influence on strength, cooling time and carbon equivalent of weld metal by welding conditions on the different test pieces. We calculated an estimate of cooling time and chemical components. Consequently, we concluded that the strength of weld metal can be estimated by heat input, interpass temperature, carbon equivarent of welding wire and shape of test piece.     

Excitation density dependence of luminescence spectrum of electron-hole plasma in diamond

Time-resolved band edge luminescence spectrum in IIa diamond has been measured with the 5th harmonics of a pulsed YAG laser (5.82 eV) and an ICCD image intensifier of 5 ns gate width at 290 K. The time-resolved luminescence spectrum is decomposed into three components of free exciton (FE), excitonic complex (EC) and electron-hole plasma (EHP). The decay times of the FE and EC luminescence are 45 and 27 ns, respectively and that of the EHP luminescence has been seen to be shorter than the gate width, 5 ns. The low energy onset of the EHP luminescence spectrum has been observed to decrease with increasing excitation density and attains the onset of the electron-hole drop luminescence spectrum at the excitation density of 0.6 J/cm², at which the electron-hole pair density is 1.2 × 10²⁰ cm^? 3. Furthermore, the excitation density dependences of the FE, EC and EHP luminescence intensities are explained with the percolation theory.     

Effect of active oxygen species on the productivity of torularhodin by Rhodotorula glutinis No. 21

The effect of active oxygen species on the productivity of torularhodin, an effective antioxidant, by soil yeast, Rhodotorula glutinis no. 21, was examined. Methylene blue, methyviologen and AAPH [2,2'-azobis(2-amidinopropane) dihydrochloride] were used as generators of singlet oxygen, superoxide anion radicals and peroxy radicals, respectively. All of them indicated effectiveness at a dose of 1.0 x 10(-10) to 3.0 x 10(-6) M. Addition of these generators to the culture medium had almost no influence on the biosynthesis of beta-carotene, whereas it had marked enhancement on those of torulene and torularhodin. Production of uric acid by xanthineoxidase remained unchanged at a torularhodin concentration of up to 100 microM. This result suggests that torularhodin does not directly affect the productivity of superoxide anions. It has been proved that torularhodin has a more potent effect on the scavenging of peroxyl radicals and inhibits substrate degradation by singlet oxygen more effectively than beta-carotene does. Continuous addition of methylene blue enhanced the torularhodin accumulation more markedly than single addition.     

Numerical prediction of fraction of eutectic phase in Sn−Ag−Cu soldring using the phase-field method

A combination of macroscale solidification simulation and phase-field calculation is employed to predict the volume fraction of the eutectic phase in Sn-4.0 mass% Ag-XCu solder alloys (X=0.5–1.1 mass%). The solidification simulation incorporates the cooling rate in the phase-field simulation. We assume the residual liquid solidifies as eutectic phase when the driving force for the nucleation of Cu₆Sn₅ amounts to a critical value, which is determined based on the experimental data. Though the calculation results depend on the experimental data, the obtained fractions are about 40% for 0.5 mass% Cu and more than 90% for 1.1 mass% Cu alloy, which shows good agreement with the experimental data.