Lamellar eutectic growth with anisotropic interphase boundaries: Experimental study using the rotating directional solidification method

We report on an experimental study of the effects of interphase boundary anisotropy on eutectic microstructures using a new methodology called rotating directional solidification (RDS), which consists of rotating a thin sample with respect to a fixed unidirectional thermal gradient. The systems used are thin, large eutectic grains of the CBr₄–C₂Cl₆ and In–In₂Bi lamellar eutectic alloys. The shape of the observed RDS lamellar trajectories turns out to be a reproducible eutectic-grain-dependent feature, in agreement with the theoretical prediction that these trajectories are approximately homothetic to the Wulff form of the interphase boundary in the sample plane. We show that different modes of lamellar growth, ranging from quasi-isotropic to (crystallographically) locked, exist in different eutectic grains of the two alloys studied. A detailed characterisation of these modes is given, with particular attention to the as-yet poorly understood aspects of locked lamellar growth.     

A theory of thin lamellar eutectic growth with anisotropic interphase boundaries

We present a semiempirical theory of the effects of an orientation dependence of the surface free energy of interphase boundaries (interphase boundary anisotropy) on lamellar eutectic growth in thin samples. We show that, to a good approximation, thin lamellar eutectic patterns with a strong interphase boundary anisotropy travel along the growth front at such a velocity – or, equivalently, at such an inclination angle of the lamellae left behind in the solid – that the surface tension force of the interphase boundary is nearly parallel to the applied thermal gradient. This explains, among other things, the crystallographic locking of lamellar eutectic patterns that occurs in those eutectic grains, which have cusp singularities in the Wulff plot of the interphase boundary. Based on this theory, we show that the rotating directional solidification method, by which a thin sample is rotated with respect to a fixed unidirectional thermal gradient, must yield eutectic lamellae whose trajectories are nearly homothetic to the two-dimensional Wulff form of the interphase boundary. This opens up new possibilities for the experimental study of interphase boundary anisotropy in eutectic alloys.     

Development of a simple capillary electrophoretic determination of glucosamine in nutritional supplements using in-capillary derivatisation with o-phthalaldehyde

A simple capillary electrophoretic method was developed for the determination of glucosamine using in-capillary derivatisation. Glucosamine in commercial products was extracted with purified water. The CE separation was achieved on an uncoated fused-silica capillary using a 20 mM borate buffer (pH 9.2) containing 5 mM o-phthalaldehyde (OPA) and 5 mM 3-mercaptopropionic acid (MPA) at 25 kV, followed by UV detection at 340 nm. The detector response was linear (r² > 0.999) in the concentration range 10–1000 μg/mL. The limit of detection (LOD) was 1.3 mg/g. Spiked glucosamine recoveries at 50 and 100 mg/g level were 95.1% and 104.3%, respectively. The method was applied to 16 commercial products. The concentrations of glucosamine were 109–705 mg/g, and the ratios of detected glucosamine content to the labelled value were 88.8–124%. No significant bias was observed (r² = 0.989, p < 0.01), between results obtained by the proposed CE method and an official colorimetric method (Japanese Health Food & Nutrition Food Association).     

Well‐Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

Low‐temperature anionic ring‐opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal‐free catalyst system, 3‐phenyl‐1‐propanol (PPA) (an initiator) and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris‐(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄) (a promoter) in order to obtain well‐defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring‐opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well‐defined linear AGE‐homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE‐homopolymer in a unimodal narrow molecular‐weight distribution. In this case, however, a side reaction (i.e., chain‐transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well‐defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post‐modification products are examined. Overall, this study demonstrates that a low‐temperature metal‐free anionic ROP using the PPA/t‐Bu‐P₄ catalyst system is suitable for the production of well‐defined linear AGE‐homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post‐modifications, nanostructures, and their applications.     

Polypropylene plasticization and photodegradation with a TiO2/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of polypropylene (PP) film was performed by a TiO₂/polyethylene oxide (PEO)/plant oil paint photocatalyst system. The photodegradation underwent two stages of development as follows: Initially PP reacted with linoleic acid radical originated from the photoreaction of plant oil component. Second, the linoleic acid graft‐polymer was decomposed, and then PP chain scission was caused. The process was studied using methyl linoleate (ML) in detail. The melting point of the 24 h‐photodegraded PP slightly decreased, and those of the 48 h‐ and 96 h‐ones drastically did as compared with the pristine PP. The crystallinity (χ_c) decreased at the 48 h photodegradation time and drastically increased at the 96 h one. The 24 h‐photodegraded PP showed the 77% Young's modulus, 88% tensile strength, and 103% strain at break values to those of the pristine PP. The ML graft‐polymerization and decomposition brought about the PP plasticizing and chemi‐crystallization, causing the PP degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39909.     

Three-dimensional simulating of concentrator photovoltaic modules using ray trace and equivalent circuit simulators

A 3-dimensional (3D) simulation for a concentrator photovoltaic (CPV) module using a triple-junction solar cell was developed. By connecting ray-trace simulation for an optics model and 3D equivalent circuit simulation for a triple-junction solar cell, the operating characteristics of a CPV module were calculated. By using the 3D simulation, we considered the influence of tracking error on the CPV module. It was found that maximum output power was not correlated with optical efficiency of the optics system and was strongly dependent on fill factor. We can use this total 3D simulation for the evaluation and optimization of CPV modules.     

Kinetic Study of the Prooxidant Effect of α-Tocopherol. Hydrogen Abstraction from Lipids by α-Tocopheroxyl Radical

A kinetic study of the prooxidant effect of α-tocopherol was performed. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl stearate 1, ethyl oleate 2, ethyl linoleate 3, ethyl linolenate 4, and ethyl arachidonate 5) by α-tocopheroxyl radical in toluene were determined, using a double-mixing stopped-flow spectrophotometer. The second-order rate constants (k _p) obtained are <1 × 10⁻² M⁻¹ s⁻¹ for 1, 1.90 × 10⁻² M⁻¹ s⁻¹ for 2, 8.33 × 10⁻² M⁻¹ s⁻¹ for 3, 1.92 × 10⁻¹ M⁻¹ s⁻¹ for 4, and 2.43 × 10⁻¹ M⁻¹ s⁻¹ for 5 at 25.0 °C. Fatty acid esters 3, 4, and 5 contain two, four, and six –CH₂– hydrogen atoms activated by two π-electron systems (–C=C–CH₂–C=C–). On the other hand, fatty acid ester 2 has four –CH₂– hydrogen atoms activated by a single π-electron system (–CH₂–C=C–CH₂–). Thus, the rate constants, k _abstr/H, given on an available hydrogen basis are k _p/4 = 4.75 × 10⁻³ M⁻¹ s⁻¹ for 2, k _p/2 = 4.16 × 10⁻² M⁻¹ s⁻¹ for 3, k _p/4 = 4.79 × 10⁻² M⁻¹ s⁻¹ for 4, and k _p/6 = 4.05 × 10⁻² M⁻¹ s⁻¹ for 5. The k _abstr/H values obtained for 3, 4, and 5 are similar to each other, and are by about one order of magnitude higher than that for 2. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils, fats, and low-density lipoproteins may be induced by the above hydrogen abstraction reaction.     

The result of a wall failure in-pile experiment under the EAGLE project

The WF (wall failure) test of the EAGLE program, in which 2 kg of uranium dioxide fuel-pins were melted by nuclear heating, was successfully conducted in the IGR (Impulse Graphite Reactor) of NNC/Kazakhstan. In this test, a 3 mm-thick stainless steel (SS) wall structure was placed between fuel pins and a 10 mm-thick sodium-filled channel (sodium gap). During the transient, fuel pins were heated, which led to the formation of a fuel-steel mixture pool. Under the transient nuclear heating condition, the SS wall was strongly heated by the molten pool, leading to wall failure. The time needed for fuel penetration into the sodium-filled gap was very short (less than 1 s after the pool formation). The result suggests that molten core materials formed in hypothetical LMFBR core disruptive accidents have a certain potential to destroy SS-wall boundaries early in the accident phase, thereby providing fuel escape paths from the core region. The early establishment of such fuel escape paths is regarded as a favorable characteristic in eliminating the possibility of severe re-criticality events. A preliminary interpretation on the WF test results is presented in this paper.     

Change in fine structure of nylon 6 gut yarn in twisting,annealing, and untwisting processes. I. Observation by WAXD,SAXD, and EM

To obtain information on the change in fine structure of nylon 6 taking place during practical false-twisting processes, the manner of change in the three elemental processes, i.e., twisting, annealing, and untwisting, was studied. For simplicity, nylon 6 gut yarn was used instead of multifilament yarn. Wide- and small-angle x-ray diffraction (WAXD and SAXD) together with electron microscopy (EM) were used here. The degree of molecular orientation in the crystalline region of the twisted yarn gradually decreases with increase of the twist number (TN) in the region of TN ? 100. The long spacing, determined by SAXD, of the twisted yarn increases with increases in TN. The increase in long spacing cannot be interpreted only by macroscopic strain or elongation of the yarn in the twisting process. This difference seems to arise from the contribution of the decrease of lateral size of lamellae to the average long spacing; therefore the increase in long spacing should be attributed to the elongation of the amorphous region, deduced from the crystallinity measured by WAXD and the long spacing diffraction. The angle between the streak line on the surface of twisted yarn observed by EM and the fiber axis agrees well with the twist angle of the yarn. The crystal lamellae are stacked normal to the streak line at the initial stage, i.e., at a low value of TN, but they begin to deviate from the normal direction with increase in TN, accompanied by their partial destruction. Based on SAXD and density measurements, the internal strain of yarn annealed after twisting is fully relaxed. When the yarn is untwisted after twisting and annealing, the crystal orientation recovers gradually to that of the untreated yarn. The chain axis within the lamellae in the center region of the yarn becomes nearly parallel to the fiber axis, but the chain axis in the outer region does not.     

Composite of Au nanoparticles and molecularly imprinted polymer as a sensing material

A molecularly imprinted polymer with immobilized Au nanoparticles (Au-MIP) is reported as a novel type of sensing material. The sensing mechanism is based upon the variable proximity of the Au nanoparticles immobilized in the imprinted polymer, which exhibits selective binding of a given analyte accompanied by swelling that causes a blue-shift in the plasmon absorption band of the immobilized Au nanoparticles. Using adrenaline as the model analyte, it was shown that molecular imprinting effectively enhanced the sensitivity and selectivity, and accordingly, Au-MIP selectively detects the analyte at 5 microM. The combination of molecular imprinting and the Au nanoparticle-based sensing system was shown to be a general strategy for constructing sensing materials in a tailor-made fashion due to wide applicability of the imprinting technique and the independence of the sensing mechanism from the analyte recognition system.